JP2022129980A - Chemically amplified positive photosensitive composition, photosensitive dry film, method for producing patterned resist film, method for producing substrate with template, and method for producing plated model - Google Patents

Abstract

To provide a chemically amplified positive photosensitive composition that has a high solid content and excellent storage stability and can form a photosensitive layer less prone to developer rejection and swelling and having excellent crack resistance; a photosensitive dry film having a photosensitive layer composed of the chemically amplified positive photosensitive composition; a method for producing a patterned resist film by using the chemically amplified positive photosensitive composition; a method for producing a cast substrate; and a method for producing a plated molding.SOLUTION: A chemically amplified positive photosensitive composition contains an acid generator (A) that generates an acid by irradiation with active rays or radiation and a resin (B) that shows increased solubility to alkali by the action of an acid. The resin (B) contains an acrylic resin (B3). The acrylic resin (B3) contains a specific constitutional unit. The solid content is 25 mass% or more and 70 mass% or less.SELECTED DRAWING: None

Description

The present invention uses a chemically amplified positive photosensitive composition, a photosensitive dry film having a photosensitive layer made of the chemically amplified positive photosensitive composition, and the chemically amplified positive photosensitive composition. It relates to a method for manufacturing a patterned resist film, a method for manufacturing a substrate with a mold, and a method for manufacturing a plated model.

Currently, photofabrication is the mainstream of precision microfabrication technology. Photofabrication is a process in which a photoresist composition is applied to the surface of a workpiece to form a photoresist layer, the photoresist layer is patterned by photolithography, and the patterned photoresist layer (photoresist pattern) is used as a mask to perform chemical etching and electrolysis. It is a general term for techniques for manufacturing various precision parts such as semiconductor packages by performing electroforming, which is mainly based on etching or electroplating.

In recent years, with the downsizing of electronic equipment, high-density mounting technology for semiconductor packages has progressed. Based on this, the improvement of the mounting density is attempted. In such high-density mounting technology, connection terminals include protruding electrodes (mounting terminals) such as bumps protruding from the package, and metal posts that connect rewiring extending from peripheral terminals on a wafer to mounting terminals. etc. are arranged on the substrate with high precision.

A photoresist composition is used in the photofabrication as described above. As such a photoresist composition, a chemically amplified photosensitive composition containing an acid generator is known (Patent Documents 1 and 2). etc.). In a chemically amplified photosensitive composition, an acid is generated from an acid generator by radiation exposure (exposure), diffusion of the acid is promoted by heat treatment, and an acid catalytic reaction occurs with the base resin or the like in the composition. Its alkali solubility is changed.

Such a chemically amplified photosensitive composition can be used for the formation of patterned insulating films, etching masks, and the formation of plated objects such as bumps, metal posts, and Cu rewirings by a plating process. used for Specifically, using a chemically amplified photosensitive composition, a photoresist layer having a desired thickness is formed on a support such as a metal substrate, exposed through a predetermined mask pattern, developed, and A photoresist pattern is formed which is used as a mold from which portions for forming a plated model are selectively removed (exfoliated). Then, after embedding a conductor such as copper in the removed portion (non-resist portion) by plating, the photoresist pattern around it is removed, whereby bumps, metal posts, and Cu rewiring can be formed. .

JP-A-9-176112 JP-A-11-52562

In some cases, such as when the photoresist layer (photosensitive layer) to be formed is thick, a chemically amplified photosensitive composition with an increased solid content concentration is used.
However, conventional chemically amplified photosensitive compositions have a problem of poor storage stability when the solid content concentration is high. If the storage stability of the chemically amplified photosensitive composition is poor, for example, the viscosity of the chemically amplified photosensitive composition increases over time.

Moreover, when a conventional chemically amplified photosensitive composition is used, there is a problem that the photoresist layer may repel the developer during development. If the developer is repelled, the developer cannot sufficiently contact the photosensitive layer, resulting in poor pattern formation, such as areas where the resist pattern is not formed, or the formed resist pattern does not have the desired shape. phenomenon occurs.

Moreover, when a conventional positive-type chemically amplified photosensitive composition is used, there is a problem that the photoresist layer may swell due to contact of the exposed photoresist layer with a developer during development. If the photoresist layer swells during development, the unexposed areas may dissolve. Further, when the photoresist layer swells during development, wrinkles due to the swelling may appear in the unexposed areas of the formed resist pattern, or swelling and distortion due to the swelling may occur.

Moreover, when a conventional positive-type chemically amplified photosensitive composition is used, there is a problem that cracks may be formed in the formed resist pattern. If cracks are formed in the resist pattern, for example, when the resist pattern is used as a mold for forming a plated modeled article, it is difficult to form a plated modeled article having a desired shape. Accordingly, the chemically amplified photosensitive composition is also desired to suppress the occurrence of cracks, that is, to be excellent in crack resistance.

The present invention has been made in view of the above problems. An amplification type positive photosensitive composition, a photosensitive dry film comprising a photosensitive layer made of the chemically amplified positive photosensitive composition, and a patterned film using the chemically amplified positive photosensitive composition An object of the present invention is to provide a method for manufacturing a resist film, a method for manufacturing a substrate with a mold, and a method for manufacturing a plated model.

As a result of intensive studies to achieve the above object, the present inventors have found an acid generator (A) that generates an acid when irradiated with actinic rays or radiation, and a resin that increases the solubility in alkali by the action of an acid. (B), the resin (B) contains an acrylic resin (B3), the acrylic resin (B3) contains a structural unit represented by the following formula (B3-1), and the solid content concentration is 25% by mass or more and 70 The present inventors have found that the above problems can be solved by a chemically amplified positive photosensitive composition with a mass % or less, and have completed the present invention. Specifically, the present invention provides the following.

（式（Ｂ３－１）中、Ｒ^ｂ０１は、水素原子又はメチル基であり、Ｒ^ｂ０２は、単結合、又は連結基であり、Ｒ^ｂ０３は、水素原子又は脂肪族炭化水素基であり、Ｒ^ｂ０４及びＲ^ｂ０５は、それぞれ独立に、単結合又は脂肪族炭化水素基であり、Ｒ^ｂ０４及びＲ^ｂ０５が同時に単結合であることはなく、Ｒ^ｂ０６及びＲ^ｂ０７は、それぞれ独立に、水素原子又は脂肪族炭化水素基であり、Ｒ^ｂ０２及びＲ^ｂ０３の一方が、アクリル樹脂（Ｂ３）の主鎖を構成する炭素原子と結合して環を形成してもよく、Ｒ^ｂ０２とＲ^ｂ０３とが結合して環を形成してもよく、Ｒ^ｂ０２とＲ^ｂ０５とが結合して環を形成してもよく、Ｒ^ｂ０６とＲ^ｂ０７とが結合して環を形成してもよい。）
で表される構成単位を含み、
固形分濃度が、２５質量％以上７０質量％以下である、化学増幅型ポジ型感光性組成物である。 A first aspect of the present invention comprises an acid generator (A) that generates an acid upon exposure to actinic rays or radiation, and a resin (B) that increases in alkali solubility under the action of acid,
The resin (B) contains an acrylic resin (B3),
The acrylic resin (B3) has the following formula (B3-1):

(In formula (B3-1), R ^b01 is a hydrogen atom or a methyl group, R ^b02 is a single bond or a linking group, R ^b03 is a hydrogen atom or an aliphatic hydrocarbon group, R ^b04 and R ^b05 are each independently a single bond or an aliphatic hydrocarbon group, R ^b04 and R ^b05 are not both single bonds, and R ^b06 and R ^b07 are each independently a hydrogen atom or It is an aliphatic hydrocarbon group, one of R ^b02 and R ^b03 may be bonded to a carbon atom constituting the main chain of the acrylic resin (B3) to form a ring, and R ^b02 and R ^b03 are bonded may form a ring, R ^b02 and R ^b05 may combine to form a ring, and R ^b06 and R ^b07 may combine to form a ring.)
contains a structural unit represented by
The chemically amplified positive photosensitive composition has a solid content concentration of 25% by mass or more and 70% by mass or less.

A second aspect of the present invention is a chemically amplified positive photosensitive composition comprising a substrate film and a photosensitive layer formed on the surface of the substrate film, wherein the photosensitive layer is according to the first aspect. It is a photosensitive dry film consisting of.

A third aspect of the present invention is
A lamination step of laminating a photosensitive layer made of the chemically amplified positive photosensitive composition according to the first aspect on a substrate;
an exposure step of position-selectively irradiating the photosensitive layer with actinic rays or radiation;
and a developing step of developing the exposed photosensitive layer.

A fourth aspect of the present invention is
A lamination step of laminating a photosensitive layer made of the chemically amplified positive photosensitive composition according to the first aspect on a substrate having a metal surface;
an exposure step of position-selectively irradiating the photosensitive layer with actinic rays or radiation;
and a developing step of developing the exposed photosensitive layer to form a mold for forming a plated modeled article.

A fifth aspect of the present invention includes a step of plating a substrate with a mold manufactured by the method for manufacturing a substrate with a mold according to the fourth aspect to form a plated molded object in the mold. is a manufacturing method.

According to the present invention, there is provided a chemically amplified positive photosensitive composition which has a high solid content concentration, good storage stability, suppresses developer repelling and swelling, and can form a photosensitive layer having excellent crack resistance. , a photosensitive dry film having a photosensitive layer made of the chemically amplified positive photosensitive composition, a method for producing a patterned resist film using the chemically amplified positive photosensitive composition, and a mold A method for manufacturing a substrate and a method for manufacturing a plated model can be provided.

<<Chemically amplified positive photosensitive composition>>
A chemically amplified positive photosensitive composition (hereinafter also referred to as a photosensitive composition) contains an acid generator (A) (hereinafter also referred to as an acid generator (A)) that generates an acid upon exposure to actinic rays or radiation. ) and a resin (B) (hereinafter also referred to as resin (B)) whose solubility in alkali increases under the action of acid. The resin (B) contains an acrylic resin (B3), and the acrylic resin (B3) contains a structural unit represented by the following formula (B3-1). The photosensitive resin composition optionally contains components such as an acid diffusion inhibitor (C), an alkali-soluble resin (D), a sulfur-containing compound (E), a dye (F), and an organic solvent (S). You can stay.
Moreover, the chemically amplified positive photosensitive composition has a solid content concentration of 25% by mass or more and 70% by mass or less. When the solid content concentration is within this range, it is easy to form a thick photosensitive layer. The solid content concentration of the photosensitive composition may be 30% by mass or more and 60% by mass or less, or 40% by mass or more and 50% by mass or less. In addition, solid content is components other than an organic solvent (S) and water.

The essential or optional components contained in the photosensitive composition and the method for producing the photosensitive composition are described below.

<Acid generator (A)>
The acid generator (A) is a compound that generates an acid upon irradiation with actinic rays or radiation, and is not particularly limited as long as it is a compound that directly or indirectly generates an acid upon exposure to light. As the acid generator (A), the acid generators of the first to fifth embodiments described below are preferred. Among the acid generators (A) that are preferably used in the positive photosensitive composition, preferable ones are described below as the first to fifth embodiments.

A first aspect of the acid generator (A) includes compounds represented by the following formula (a1).

In formula (a1) above, X ^1a represents a sulfur atom or an iodine atom with a valence of g, where g is 1 or 2. h represents the number of repeating units of the structure in parentheses. R ^1a is an organic group bonded to X ^1a , and is an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, represents an alkenyl group having 2 to 30 carbon atoms or an alkynyl group having 2 to 30 carbon atoms, and R ^1a is alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthio at least one selected from the group consisting of carbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, and nitro groups, and halogen seeds may be substituted. The number of R ^1a is g+h(g−1)+1, and each R ^1a may be the same or different. Two or more R ^1a may be directly connected to each other, or —O—, —S—, —SO—, —SO ₂ —, —NH—, —NR ^2a —, —CO—, —COO—, —CONH— , an alkylene group having 1 to 3 carbon atoms, or a phenylene group to form a ring structure containing X ^1a . R ^2a is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

^X2a is a structure represented by the following formula (a2).

In the above formula (a2), X ^4a is an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a divalent group of a heterocyclic compound having 8 to 20 carbon atoms. X ^4a is selected from the group consisting of alkyl having 1 to 8 carbon atoms, alkoxy having 1 to 8 carbon atoms, aryl having 6 to 10 carbon atoms, hydroxy, cyano, nitro groups, and halogen It may be substituted with at least one selected. X ^5a is -O-, -S-, -SO-, -SO ₂ -, -NH-, -NR ^2a -, -CO-, -COO-, -CONH-, alkylene having 1 to 3 carbon atoms; group, or a phenylene group. h represents the number of repeating units of the structure in parentheses. The h+1 X ^4a and the h X ^5a may be the same or different. ^R2a is the same as defined above.

X ^3a- is a counter ion of onium, and includes a fluorinated alkylfluorophosphate anion represented by the following formula (a17) or a borate anion represented by the following formula (a18).

In formula (a17) above, R ^3a represents an alkyl group in which 80% or more of the hydrogen atoms are substituted with fluorine atoms. j indicates the number and is an integer of 1 or more and 5 or less. j R ^3a may be the same or different.

In the above formula (a18), R ^4a to R ^7a each independently represent a fluorine atom or a phenyl group, and part or all of the hydrogen atoms in the phenyl group are selected from the group consisting of a fluorine atom and a trifluoromethyl group. may be substituted with at least one of

The onium ion in the compound represented by the formula (a1) includes triphenylsulfonium, tri-p-tolylsulfonium, 4-(phenylthio)phenyldiphenylsulfonium, bis[4-(diphenylsulfonio)phenyl]sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonio}phenyl]sulfide, bis{4-[bis(4-fluorophenyl)sulfonio]phenyl}sulfide, 4-(4-benzoyl-2- Chlorophenylthio)phenylbis(4-fluorophenyl)sulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10 -thia-9,10-dihydroanthracen-2-yldiphenylsulfonium, 2-[(diphenyl)sulfonio]thioxanthone, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium, 4- (4-benzoylphenylthio)phenyldiphenylsulfonium, diphenylphenacylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, phenyl[4- (4-biphenylthio)phenyl]4-biphenylsulfonium, phenyl[4-(4-biphenylthio)phenyl]3-biphenylsulfonium, [4-(4-acetophenylthio)phenyl]diphenylsulfonium, octadecylmethylphenacylsulfonium , diphenyliodonium, di-p-tolyliodonium, bis(4-dodecylphenyl)iodonium, bis(4-methoxyphenyl)iodonium, (4-octyloxyphenyl)phenyliodonium, bis(4-decyloxy)phenyliodonium, 4- (2-hydroxytetradecyloxy)phenylphenyliodonium, 4-isopropylphenyl(p-tolyl)iodonium, 4-isobutylphenyl(p-tolyl)iodonium, and the like.

Of the onium ions in the compound represented by formula (a1) above, preferred onium ions include sulfonium ions represented by formula (a19) below.

In the above formula (a19), each R ^8a is independently from a hydrogen atom, alkyl, hydroxy, alkoxy, alkylcarbonyl, alkylcarbonyloxy, alkyloxycarbonyl, halogen atom, optionally substituted aryl, arylcarbonyl, represents a group selected from the group consisting of X ^2a has the same meaning as X ^2a in formula (a1) above.

Specific examples of the sulfonium ion represented by the above formula (a19) include 4-(phenylthio)phenyldiphenylsulfonium, 4-(4-benzoyl-2-chlorophenylthio)phenylbis(4-fluorophenyl)sulfonium, 4- (4-benzoylphenylthio)phenyldiphenylsulfonium, phenyl[4-(4-biphenylthio)phenyl]4-biphenylsulfonium, phenyl[4-(4-biphenylthio)phenyl]3-biphenylsulfonium, [4-(4 -acetophenylthio)phenyl]diphenylsulfonium, diphenyl[4-(p-terphenylthio)phenyl]diphenylsulfonium.

In the fluorinated alkylfluorophosphate anion represented by the above formula (a17), R ^3a represents an alkyl group substituted with a fluorine atom, preferably has 1 or more and 8 or less carbon atoms, more preferably 1 or more carbon atoms. 4 or less. Specific examples of alkyl groups include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl and tert-butyl; and cyclopropyl, cyclobutyl and cyclopentyl. , cycloalkyl groups such as cyclohexyl, etc., and the ratio of hydrogen atoms in the alkyl groups substituted with fluorine atoms is usually 80% or more, preferably 90% or more, more preferably 100%. If the substitution rate of fluorine atoms is less than 80%, the acid strength of the onium fluorinated alkylfluorophosphate represented by formula (a1) is lowered.

Particularly preferred R ^3a is a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms and having a fluorine atom substitution rate of 100%, and specific examples thereof include CF ₃ and CF ₃ CF. ₂ , _{( CF3} ) _2CF , _CF3CF2CF2 , _{CF3CF2CF2CF2 , ( CF3} ) _{2CFCF2 , CF3CF2 ( CF3} )CF _{, ( CF3} ) _3C mentioned. The number j of R ^3a is an integer of 1 or more and 5 or less, preferably 2 or more and 4 or less, and particularly preferably 2 or 3.

Specific examples of preferred fluorinated alkylfluorophosphate anions include [(CF ₃ CF ₂ ) ₂ PF ₄ ] ⁻ , [(CF ₃ CF ₂ ) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ⁻ , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ⁻ , [(CF ₃ CF ₂ CF ₂ ) ₂ PF ₄ ] ⁻ , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ⁻ , [ _{( ( CF3} ) _2CFCF2 ) _2PF4 ] ^- _, [ _{( ( CF3} ) _2CFCF2 ) _{3PF3 ]} ^- , [ _{( CF3CF2CF2CF2} ) _{2PF4 ]} ^- , or [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , among which [(CF ₃ CF ₂ ) ₃ PF ₃ ] ^- , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ⁻ , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ⁻ , or [(( CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ^- is particularly preferred.

Preferred specific examples of the borate anion represented by the formula (a18) include tetrakis(pentafluorophenyl)borate ([B(C ₆ F ₅ ) ₄ ] ⁻ ), tetrakis[(trifluoromethyl)phenyl]borate ( [B(C ₆ H ₄ CF ₃ ) ₄ ] ⁻ ), difluorobis(pentafluorophenyl)borate ([(C ₆ F ₅ ) ₂ BF ₂ ] ⁻ ), trifluoro(pentafluorophenyl)borate ([(C ₆ F ₅ )BF ₃ ] ⁻ ), tetrakis(difluorophenyl)borate ([B(C ₆ H ₃ F ₂ ) ₄ ] ⁻ ), and the like. Among these, tetrakis(pentafluorophenyl)borate ([B(C ₆ F ₅ ) ₄ ] ⁻ ) is particularly preferred.

As a second embodiment of the acid generator (A), 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2 -(2-furyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methyl-2-furyl)ethenyl]-s-triazine, 2,4-bis( trichloromethyl)-6-[2-(5-ethyl-2-furyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-propyl-2-furyl)ethenyl ]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-dimethoxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2 -(3,5-diethoxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-dipropoxyphenyl)ethenyl]-s-triazine, 2, 4-bis(trichloromethyl)-6-[2-(3-methoxy-5-ethoxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3-methoxy- 5-propoxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-methylenedioxyphenyl)ethenyl]-s-triazine, 2,4-bis( trichloromethyl)-6-(3,4-methylenedioxyphenyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4 -bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3, 5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(2-furyl)ethenyl]-4,6-bis( trichloromethyl)-1,3,5-triazine, 2-[2-(5-methyl-2-furyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[ 2-(3,5- dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)- 1,3,5-triazine, 2-(3,4-methylenedioxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, tris(1,3-dibromopropyl)-1 ,3,5-triazine, tris(2,3-dibromopropyl)-1,3,5-triazine, and other halogen-containing triazine compounds, and tris(2,3-dibromopropyl)isocyanurate, etc. of the following formula (a3) Halogen-containing triazine compounds represented by are mentioned.

In formula (a3) above, R ^9a , R ^10a and R ^11a each independently represent a halogenated alkyl group.

Further, as a third aspect of the acid generator (A), α-(p-toluenesulfonyloxyimino)-phenylacetonitrile, α-(benzenesulfonyloxyimino)-2,4-dichlorophenylacetonitrile, α-(benzene sulfonyloxyimino)-2,6-dichlorophenylacetonitrile, α-(2-chlorobenzenesulfonyloxyimino)-4-methoxyphenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, and oximesulfonate groups and a compound represented by the following formula (a4).

In formula (a4) above, R ^12a represents a monovalent, divalent, or trivalent organic group, and R ^13a represents a substituted or unsubstituted saturated hydrocarbon group, an unsaturated hydrocarbon group, or an aromatic group. and n represents the number of repeating units of the structure in parentheses.

In the above formula (a4), examples of aromatic groups include aryl groups such as phenyl group and naphthyl group, and heteroaryl groups such as furyl group and thienyl group. These may have one or more suitable substituents such as halogen atoms, alkyl groups, alkoxy groups, nitro groups, etc. on the ring. Further, R ^13a is particularly preferably an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group and a butyl group. Particularly preferred are compounds in which R ^12a is an aromatic group and R ^13a is an alkyl group having 1 to 4 carbon atoms.

As the acid generator represented by the above formula (a4), when n=1, R ^12a is any one of a phenyl group, a methylphenyl group, or a methoxyphenyl group, and R ^13a is a methyl group. Specifically, α-(methylsulfonyloxyimino)-1-phenylacetonitrile, α-(methylsulfonyloxyimino)-1-(p-methylphenyl)acetonitrile, α-(methylsulfonyloxyimino)-1-(p- methoxyphenyl)acetonitrile, [2-(propylsulfonyloxyimino)-2,3-dihydroxythiophen-3-ylidene](o-tolyl)acetonitrile and the like. When n=2, the acid generator represented by the above formula (a4) specifically includes an acid generator represented by the following formula.

A fourth aspect of the acid generator (A) is an onium salt having a naphthalene ring in the cation moiety. The phrase "having a naphthalene ring" means having a structure derived from naphthalene, and means that at least two ring structures and their aromaticity are maintained. The naphthalene ring has a substituent such as a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. good too. The structure derived from the naphthalene ring may be a monovalent group (one free atom valence) or a divalent group (two free atom valences) or more, but it is preferable that it is a monovalent group. Desirable (however, at this time, free valences shall be counted excluding the portions bonded to the above substituents). The number of naphthalene rings is preferably 1 or more and 3 or less.

As the cation moiety of such an onium salt having a naphthalene ring in the cation moiety, a structure represented by the following formula (a5) is preferable.

In the above formula (a5), at least one of R ^14a , R ^15a and R ^16a represents a group represented by the following formula (a6), and the rest are linear or branched having 1 to 6 carbon atoms , a phenyl group which may have a substituent, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. Alternatively, one of R ^14a , R ^15a , and R ^16a is a group represented by the following formula (a6), and the remaining two are each independently linear or branched having 1 to 6 carbon atoms and these terminals may be combined to form a ring.

In the above formula (a6), R ^17a and R ^18a each independently represent a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a linear or branched alkoxy group having 1 to 6 carbon atoms. Represents a branched alkyl group, and R ^19a represents a single bond or an optionally substituted linear or branched alkylene group having 1 to 6 carbon atoms. l and m each independently represent an integer of 0 or more and 2 or less, and l+m is 3 or less. However, when multiple R ^17a are present, they may be the same or different. Moreover, when multiple R ^18a are present, they may be the same or different from each other.

Among R ^14a , R ^15a , and R ^16a , the number of groups represented by the above formula (a6) is preferably one from the viewpoint of the stability of the compound, and the rest are straight groups having 1 to 6 carbon atoms. It is a chain or branched alkylene group, and these terminals may be combined to form a ring. In this case, the two alkylene groups form a 3- to 9-membered ring including a sulfur atom. The number of atoms (including sulfur atoms) constituting the ring is preferably 5 or more and 6 or less.

Further, examples of the substituent that the alkylene group may have include an oxygen atom (in this case, forming a carbonyl group together with the carbon atoms constituting the alkylene group), a hydroxyl group, and the like.

Examples of substituents that the phenyl group may have include a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, and a linear or branched group having 1 to 6 carbon atoms. and the like.

Preferred examples of these cation moieties include those represented by the following formulas (a7) and (a8), and the structures represented by the following formula (a8) are particularly preferred.

Such a cation moiety may be an iodonium salt or a sulfonium salt, but a sulfonium salt is preferable from the viewpoint of acid generation efficiency.

Therefore, an anion capable of forming a sulfonium salt is desirable as an anion moiety of an onium salt having a naphthalene ring in the cation moiety.

The anion part of such an acid generator is a fluoroalkylsulfonate ion or an arylsulfonate ion in which some or all of the hydrogen atoms are fluorinated.

The alkyl group in the fluoroalkylsulfonate ion may be linear, branched, or cyclic, having 1 to 20 carbon atoms, and the number of carbon atoms should be 1 to 10, considering the bulkiness of the generated acid and its diffusion distance. is preferred. In particular, branched or ring-shaped ones are preferable because they have a short diffusion distance. Moreover, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, and the like can be mentioned as preferable ones because they can be synthesized at low cost.

The aryl group in the arylsulfonate ion is an aryl group having 6 to 20 carbon atoms, and includes an alkyl group, a phenyl group which may or may not be substituted with a halogen atom, and a naphthyl group. In particular, an aryl group having 6 or more and 10 or less carbon atoms is preferable because it can be synthesized at low cost. Preferable specific examples include phenyl group, toluenesulfonyl group, ethylphenyl group, naphthyl group, methylnaphthyl group and the like.

In the above fluoroalkylsulfonate ion or arylsulfonate ion, when some or all of the hydrogen atoms are fluorinated, the fluorination rate is preferably 10% or more and 100% or less, more preferably 50% or more and 100%. It is below, and it is particularly preferable to replace all the hydrogen atoms with fluorine atoms because the strength of the acid increases. Specific examples of such compounds include trifluoromethanesulfonate, perfluorobutanesulfonate, perfluorooctane sulfonate, and perfluorobenzenesulfonate.

Among these, preferred anion moieties include those represented by the following formula (a9).

In formula (a9) above, R ^20a is a group represented by formulas (a10), (a11), and (a12) below.

In the above formula (a10), x represents an integer of 1 or more and 4 or less. In the above formula (a11), R ^21a is a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched chain having 1 to 6 carbon atoms. represents an alkoxy group, and y represents an integer of 1 or more and 3 or less. Among these, trifluoromethanesulfonate and perfluorobutanesulfonate are preferred from the viewpoint of safety.

Further, as the anion moiety, those containing nitrogen represented by the following formulas (a13) and (a14) can also be used.

In the above formulas (a13) and (a14), X ^a represents a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and the number of carbon atoms in the alkylene group is 2 or more and 6 or less, preferably 3 or more and 5 or less, most preferably 3 carbon atoms. Y ^a and Z ^a each independently represent a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the number of carbon atoms in the alkyl group is 1 or more and 10 or less. , preferably 1 or more and 7 or less, more preferably 1 or more and 3 or less.

The smaller the number of carbon atoms in the alkylene group of X ^a or the number of carbon atoms in the alkyl groups of ^Ya and ^Za , the better the solubility in organic solvents, which is preferable.

Moreover, in the alkylene group of X ^a or the alkyl group of Y ^a or Z ^a , the greater the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength, which is preferable. The ratio of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination rate is preferably 70% or more and 100% or less, more preferably 90% or more and 100% or less, and most preferably all hydrogen atoms are fluorine It is an atom-substituted perfluoroalkylene group or perfluoroalkyl group.

Preferable onium salts having a naphthalene ring in the cation moiety include compounds represented by the following formulas (a15) and (a16).

Further, as a fifth aspect of the acid generator (A), bis(p-toluenesulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(2,4- bissulfonyldiazomethanes such as dimethylphenylsulfonyl)diazomethane; 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, nitrobenzyl tosylate, dinitrobenzyl tosylate, nitrobenzylsulfonate, nitro Nitrobenzyl derivatives such as benzyl carbonate and dinitrobenzyl carbonate; Sulfonic acid esters such as oxymaleimide and N-methylsulfonyloxyphthalimide; N-(trifluoromethylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)-1,8-naphthalimide, N-(trifluoromethyl sulfonyloxy)-4-butyl-1,8-naphthalimide and other trifluoromethanesulfonic acid esters; diphenyliodonium hexafluorophosphate, (4-methoxyphenyl)phenyliodonium trifluoromethanesulfonate, bis(p-tert-butyl Onium salts such as phenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, (p-tert-butylphenyl) diphenylsulfonium trifluoromethanesulfonate; benzoin tosylates such as lactate and α-methylbenzoin tosylate; other diphenyliodonium salts, triphenylsulfonium salts, phenyldiazonium salts, benzyl carbonate and the like.

（式（ａ２１）中、Ｒ^２２ａは、１価の有機基であり、Ｒ^２３ａ、Ｒ^２４ａ、Ｒ^２５ａ、及びＲ^２６ａは、それぞれ独立に、水素原子又は１価の有機基であり、Ｒ^２３ａとＲ^２４ａと、Ｒ^２４ａとＲ^２５ａと、又はＲ^２５ａとＲ^２６ａとは、それぞれ互いに結合して環を形成してもよい。） As the acid generator (A), a naphthalic acid derivative represented by the following formula (a21) is also preferred.

(In formula (a21), R ^22a is a monovalent organic group, R ^23a , R ^24a , R ^25a and R ^26a are each independently a hydrogen atom or a monovalent organic group, and R ^23a and R ^24a , R ^24a and R ^25a , or R ^25a and R ^26a may each combine to form a ring.)

The organic group for R ^22a is not particularly limited as long as it does not impair the object of the present invention. The organic group may be a hydrocarbon group and may contain heteroatoms such as O, N, S, P, and halogen atoms. The structure of the organic group may be linear, branched, cyclic, or a combination of these structures.

Organic groups suitable for R ^22a include aliphatic hydrocarbon groups having 1 to 18 carbon atoms which may be substituted with halogen atoms and/or alkylthio groups, and 6 carbon atoms which may be substituted. aryl group of 20 or less, optionally substituted aralkyl group of 7 or more and 20 or less carbon atoms, optionally substituted alkylaryl group of 7 or more and 20 or less carbon atoms, camphor-10- an yl group, and the following formula (a21a):
—R ^27a —(O) _a —R ^28a —(O) _b —Y ¹ —R ^29a (a21a)
(In formula (a21a), Y ¹ is a single bond or an alkanediyl group having 1 to 4 carbon atoms; R ^27a and R ^28a each have 2 or more carbon atoms which may be substituted with a halogen atom; an alkanediyl group of 6 or less, or an arylene group having 6 or more and 20 or less carbon atoms which may be substituted with a halogen atom, R ^29a is an alkyl having 1 or more and 18 or less carbon atoms which may be substituted with a halogen atom; alicyclic hydrocarbon group having 3 to 12 carbon atoms, aryl group having 6 to 20 carbon atoms which may be substituted with halogen atoms, 7 to 20 carbon atoms which may be substituted by halogen atoms the following aralkyl groups: a and b are each 0 or 1, and at least one of a and b is 1;
The group represented by is mentioned.

When the organic group for R ^22a has a halogen atom as a substituent, examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom and a fluorine atom.

When the organic group for R ^22a is an alkyl group having 1 to 18 carbon atoms substituted with an alkylthio group, the alkylthio group preferably has 1 to 18 carbon atoms.
Examples of alkylthio groups having 1 to 18 carbon atoms include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, sec-butylthio, tert-butylthio, isobutylthio and n-pentylthio. group, isopentylthio group, tert-pentylthio group, n-hexylthio group, n-heptylthio group, isoheptylthio group, tert-heptylthio group, n-octylthio group, isooctylthio group, tert-octylthio group, 2-ethylhexylthio group , n-nonylthio group, n-decylthio group, n-undecylthio group, n-dodecylthio group, n-tridecylthio group, n-tetradecylthio group, n-pentadecylthio group, n-hexadecylthio group, n-heptadecylthio group, and n-octadecylthio groups.

When the organic group as R ^22a is an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted with a halogen atom and/or an alkylthio group, the aliphatic hydrocarbon group is an unsaturated di It may contain a double bond.
The structure of the aliphatic hydrocarbon group is not particularly limited, and may be linear, branched, cyclic, or a combination of these structures.

When the organic group for R ^22a is an alkenyl group, preferred examples thereof include an allyl group and a 2-methyl-2-propenyl group.

When the organic group for R ^22a is an alkyl group, preferred examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl and isobutyl groups. , n-pentyl group, isopentyl group, tert-pentyl group, n-hexyl group, n-hexan-2-yl group, n-hexan-3-yl group, n-heptyl group, n-heptan-2-yl group , n-heptan-3-yl group, isoheptyl group, tert-heptyl group, n-octyl group, isooctyl group, tert-octyl group, 2-ethylhexyl group, n-nonyl group, isononyl group, n-decyl group, n -undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, and n-octadecyl group.

When the organic group for R ^22a is an alicyclic hydrocarbon group, examples of the alicyclic hydrocarbon constituting the main skeleton of the alicyclic hydrocarbon group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, bicyclo[2.1.1]hexane, bicyclo[2.2.1]heptane, bicyclo[3.2.1]octane, bicyclo[2.2.2]octane, and adamantane is mentioned. The alicyclic hydrocarbon group is preferably a group obtained by removing one hydrogen atom from these alicyclic hydrocarbons.

When the organic group as R ^22a is an aliphatic hydrocarbon group substituted with a halogen atom, preferred examples include trifluoromethyl group, pentafluoroethyl group, 2-chloroethyl group, 2-bromoethyl group, heptafluoro -n-propyl group, 3-bromopropyl group, nonafluoro-n-butyl group, tridecafluoro-n-hexyl group, heptadecafluoro-n-octyl group, 2,2,2-trifluoroethyl group, 1, 1-difluoroethyl group, 1,1-difluoro-n-propyl group, 1,1,2,2-tetrafluoro-n-propyl group, 3,3,3-trifluoro-n-propyl group, 2,2 , 3,3,3-pentafluoro-n-propyl group, 2-norbornyl-1,1-difluoroethyl group, 2-norbornyltetrafluoroethyl group, and 3-adamantyl-1,1,2,2- A tetrafluoropropyl group is mentioned.

When the organic group as R ^22a is an aliphatic hydrocarbon group substituted with an alkylthio group, preferred examples thereof include a 2-methylthioethyl group, a 4-methylthio-n-butyl group and a 2-n-butylthio group. An ethyl group is mentioned.

When the organic group for R ^22a is an aliphatic hydrocarbon group substituted with a halogen atom and an alkylthio group, a preferred example is a 3-methylthio-1,1,2,2-tetrafluoro-n-propyl group. is mentioned.

When the organic group for R ^22a is an aryl group, preferred examples thereof include a phenyl group, a naphthyl group and a biphenylyl group.

When the organic group for R ^22a is an aryl group substituted with a halogen atom, preferred examples thereof include a pentafluorophenyl group, a chlorophenyl group, a dichlorophenyl group and a trichlorophenyl group.

When the organic group for R ^22a is an aryl group substituted with an alkylthio group, preferred examples include a 4-methylthiophenyl group, a 4-n-butylthiophenyl group, a 4-n-octylthiophenyl group, a 4 -n-dodecylthiophenyl group.

When the organic group for R ^22a is an aryl group substituted with a halogen atom and an alkylthio group, preferred examples include a 1,2,5,6-tetrafluoro-4-methylthiophenyl group, 1,2,5 ,6-tetrafluoro-4-n-butylthiophenyl group and 1,2,5,6-tetrafluoro-4-n-dodecylthiophenyl group.

When the organic group for R ^22a is an aralkyl group, preferred examples thereof include a benzyl group, a phenethyl group, a 2-phenylpropan-2-yl group, a diphenylmethyl group and a triphenylmethyl group.

When the organic group for R ^22a is an aralkyl group substituted with a halogen atom, preferred examples include a pentafluorophenylmethyl group, a phenyldifluoromethyl group, a 2-phenyltetrafluoroethyl group, a 2-(pentafluorophenyl ) ethyl group.

A preferred example of an aralkyl group substituted with an alkylthio group as the organic group for R ^22a is a p-methylthiobenzyl group.

When the organic group for R ^22a is an aralkyl group substituted with a halogen atom and an alkylthio group, a preferred example is a 2-(2,3,5,6-tetrafluoro-4-methylthiophenyl)ethyl group. mentioned.

When the organic group for R ^22a is an alkylaryl group, preferred examples include a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 3-isopropylphenyl group, a 4-isopropylphenyl group, 4-n-butylphenyl group, 4-isobutylphenyl group, 4-tert-butylphenyl group, 4-n-hexylphenyl group, 4-cyclohexylphenyl group, 4-n-octylphenyl group, 4-(2-ethyl -n-hexyl)phenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3, 5-dimethylphenyl group, 2,4-di-tert-butylphenyl group, 2,5-di-tert-butylphenyl group, 2,6-di-tert-butylphenyl group, 2,4-di-tert- pentylphenyl group, 2,5-di-tert-pentylphenyl group, 2,5-di-tert-octylphenyl group, 2-cyclohexylphenyl group, 3-cyclohexylphenyl group, 4-cyclohexylphenyl group, 2,4, 5-trimethylphenyl group, 2,4,6-trimethylphenyl group and 2,4,6-triisopropylphenyl group.

The group represented by formula (a21a) is an ether group-containing group.
In formula (a21a), the alkanediyl group having 1 to 4 carbon atoms represented by Y ¹ includes methylene group, ethane-1,2-diyl group, ethane-1,1-diyl group, propane-1 ,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, butane-1,3-diyl group, butane-2,3-diyl group, butane-1,2-diyl group is mentioned.
In formula (a21a), the alkanediyl group having 2 to 6 carbon atoms represented by R ^27a or R ^28a includes ethane-1,2-diyl group, propane-1,3-diyl group, propane-1 ,2-diyl group, butane-1,4-diyl group, butane-1,3-diyl group, butane-2,3-diyl group, butane-1,2-diyl group, pentane-1,5-diyl group , pentane-1,3-diyl group, pentane-1,4-diyl group, pentane-2,3-diyl group, hexane-1,6-diyl group, hexane-1,2-diyl group, hexane-1, 3-diyl group, hexane-1,4-diyl group, hexane-2,5-diyl group, hexane-2,4-diyl group and hexane-3,4-diyl group.

In formula (a21a), when R ^27a or R ^28a is a halogen-substituted alkanediyl group having 2 to 6 carbon atoms, the halogen atoms include chlorine, bromine, iodine and fluorine. Atoms. Examples of alkanediyl groups substituted with halogen atoms include tetrafluoroethane-1,2-diyl group, 1,1-difluoroethane-1,2-diyl group, 1-fluoroethane-1,2-diyl group, 1,2-difluoroethane-1,2-diyl group, hexafluoropropane-1,3-diyl group, 1,1,2,2,-tetrafluoropropane-1,3-diyl group, 1,1,2, A 2,-tetrafluoropentane-1,5-diyl group can be mentioned.

Examples of the case where R ^27a or R ^28a in formula (a21a) is an arylene group include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 2,5-dimethyl-1, 4-phenylene group, biphenyl-4,4'-diyl group, diphenylmethane-4,4'-diyl group, 2,2,-diphenylpropane-4,4'-diyl group, naphthalene-1,2-diyl group, naphthalene-1,3-diyl group, naphthalene-1,4-diyl group, naphthalene-1,5-diyl group, naphthalene-1,6-diyl group, naphthalene-1,7-diyl group, naphthalene-1,8 -diyl group, naphthalene-2,3-diyl group, naphthalene-2,6-diyl group and naphthalene-2,7-diyl group.

In formula (a21a), when R ^27a or R ^28a is an arylene group substituted with a halogen atom, examples of the halogen atom include chlorine, bromine, iodine and fluorine atoms. Examples of arylene groups substituted with halogen atoms include 2,3,5,6-tetrafluoro-1,4-phenylene groups.

In the formula (a21a), the optionally branched alkyl group having 1 to 18 carbon atoms represented by R ^29a includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl group. , sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, isopentyl group, tert-pentyl group, n-hexyl group, n-hexan-2-yl group, n-hexan-3-yl group, n-heptyl group, n-heptan-2-yl group, n-heptan-3-yl group, isoheptyl group, tert-heptyl group, n-octyl group, isooctyl group, tert-octyl group, 2-ethylhexyl group, n -nonyl group, isononyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl groups.

In formula (a21a), when R ^29a is an alkyl group having 1 to 18 carbon atoms substituted with a halogen atom, the halogen atom includes a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom. . Examples of alkyl groups substituted with halogen atoms include trifluoromethyl group, pentafluoroethyl group, heptafluoro-n-propyl group, nonafluoro-n-butyl group, tridecafluoro-n-hexyl group, heptadecafluoro -n-octyl group, 2,2,2-trifluoroethyl group, 1,1-difluoroethyl group, 1,1-difluoro-n-propyl group, 1,1,2,2-tetrafluoro-n-propyl 3,3,3-trifluoro-n-propyl group, 2,2,3,3,3-pentafluoro-n-propyl group, 1,1,2,2-tetrafluorotetradecyl group .

In formula (a21a), when R ^29a is an alicyclic hydrocarbon group having 3 or more and 12 or less carbon atoms, examples of the alicyclic hydrocarbon constituting the main skeleton of the alicyclic hydrocarbon group include , cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, bicyclo[2.1.1]hexane, bicyclo[2.2.1]heptane, bicyclo[3.2.1]octane, bicyclo [2.2.2] octane and adamantane. The alicyclic hydrocarbon group is preferably a group obtained by removing one hydrogen atom from these alicyclic hydrocarbons.

In formula (a21a), when R ^29a is an aryl group, a halogenated aryl group, an aralkyl group, or a halogenated aralkyl group, preferred examples of these groups are the same as those for R ^22a .

A preferred group among the groups represented by formula (a21a) is a group represented by R ^27a in which a carbon atom bonded to a sulfur atom is substituted with a fluorine atom. Such preferred groups preferably have from 2 to 18 carbon atoms.

R ^22a is preferably a perfluoroalkyl group having 1 to 8 carbon atoms. A camphor-10-yl group is also preferable as R ^22a because it facilitates the formation of a high-definition resist pattern.

In formula (a21), R ^23a to R ^26a are hydrogen atoms or monovalent organic groups. Also, R ^23a and R ^24a , R ^24a and R ^25a , or R ^25a and R ^26a may combine with each other to form a ring. For example, an acenaphthene skeleton may be formed by combining R ^24a and R ^25a to form a 5-membered ring together with a naphthalene ring.

As the monovalent organic group, an alicyclic hydrocarbon group, a heterocyclic group (heterocyclyl group), or an optionally branched alkyl group having 4 to 18 carbon atoms which may be substituted with a halogen atom , an alkoxy group; a heterocyclyloxy group; an alicyclic hydrocarbon group, a heterocyclic group (heterocyclyl group), or an optionally branched alkylthio group having 4 to 18 carbon atoms which may be substituted with a halogen atom ; heterocyclylthio group; is preferred.
Also preferred is a group in which a methylene group at any position not adjacent to an oxygen atom of the alkoxy group is substituted with -CO-.
A group in which the alkoxy group is interrupted by a -O-CO- bond or a -O-CO-NH- bond is also preferred. The left ends of the --O--CO-- bond and --O--CO--NH-- bond are closer to the naphthalic acid mother nucleus in the alkoxy group.
Furthermore, an alicyclic hydrocarbon group, a heterocyclic group, or an optionally branched alkylthio group having 4 to 18 carbon atoms which may be substituted with a halogen atom is also preferable as R ^23a to R ^26a .
A group in which a methylene group at any position not adjacent to the sulfur atom of the alkylthio group is substituted with -CO- is also preferred.
A group in which the alkylthio group is interrupted by an --O--CO-- bond or --O--CO--NH-- bond is also preferred. The left ends of the --O--CO-- and --O--CO--NH-- bonds are closer to the naphthalic acid mother nucleus in the alkylthio group.

As R ^23a to R ^26a , R ^23a is an organic group and R ^24a to R ^26a are hydrogen atoms, or R ^24a is an organic group and R ^23a , R ^25a and R ^26a are hydrogen atoms. is preferred. Also, all of R ^23a to R ^26a may be hydrogen atoms.

Examples of R ^23a to R ^26a being unsubstituted alkyl groups include n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, isopentyl group and tert-pentyl group. , n-hexyl group, n-heptyl group, isoheptyl group, tert-heptyl group, n-octyl group, isooctyl group, tert-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group and n-octadecyl group.

Examples of the case where R ^23a to R ^26a are unsubstituted alkoxy groups include n-butyloxy group, sec-butyloxy group, tert-butyloxy group, isobutyloxy group, n-pentyloxy group, isopentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, isoheptyloxy group, tert-heptyloxy group, n-octyloxy group, isooctyloxy group, tert-octyloxy group, 2-ethylhexyl group , n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group and n-octadecyloxy group.

When R ^23a to R ^26a are unsubstituted alkylthio groups, examples thereof include n-butylthio group, sec-butylthio group, tert-butylthio group, isobutylthio group, n-pentylthio group, isopentylthio group, tert -pentylthio group, n-hexylthio group, n-heptylthio group, isoheptylthio group, tert-heptylthio group, n-octylthio group, isooctylthio group, tert-octylthio group, 2-ethylhexylthio group, n-nonylthio group, n- decylthio group, n-undecylthio group, n-dodecylthio group, n-tridecylthio group, n-tetradecylthio group, n-pentadecylthio group, n-hexadecylthio group, n-heptadecylthio group, n-octadecylthio group .

When R ^23a to R ^26a are an alkyl group, alkoxy group or alkylthio group substituted with an alicyclic hydrocarbon group, examples of the alicyclic hydrocarbon constituting the main skeleton of the alicyclic hydrocarbon group include , cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, bicyclo[2.1.1]hexane, bicyclo[2.2.1]heptane, bicyclo[3.2.1]octane, bicyclo [2.2.2] octane and adamantane. The alicyclic hydrocarbon group is preferably a group obtained by removing one hydrogen atom from these alicyclic hydrocarbons.

When R ^23a to R ^26a are an alkyl group, alkoxy group or alkylthio group substituted with a heterocyclic group, or when R ^23a to R ^26a are a heterocyclyloxy group, the main skeleton of the heterocyclic group or heterocyclyloxy group is Examples of constituent heterocycles include pyrrole, thiophene, furan, pyran, thiopyran, imidazole, pyrazole, thiazole, isothiazole, oxazole, isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, pyrrolidine, pyrazolidine, imidazolidine, isoxazolidine. , isothiazolidine, piperidine, piperazine, morpholine, thiomorpholine, chroman, thiochroman, isochroman, isothiochroman, indoline, isoindoline, pyridine, indolizine, indole, indazole, purine, quinolizine, isoquinoline, quinoline, naphthyridine, phthalazine, quinoxaline , quinazoline, cinnoline, pteridine, acridine, perimidine, phenanthroline, carbazole, carboline, phenazine, antilysine, thiadiazole, oxadiazole, triazine, triazole, tetrazole, benzimidazole, benzoxazole, benzothiazole, benzothiadiazole, benzofuroxane, Naphthimidazole, benzotriazole, tetraazaindene. Among these heterocycles, a saturated heterocycle obtained by hydrogenating a ring having a conjugate bond is also preferred.
The heterocyclic group contained in the heterocyclic group substituting the alkyl group, the alkoxy group or the alkylthio group, or the heterocyclic group contained in the heterocyclyloxy group is preferably a group obtained by removing one hydrogen atom from the above heterocyclic ring.

Examples of R ^23a to R ^26a being an alkoxy group containing an alicyclic hydrocarbon group include a cyclopentyloxy group, a methylcyclopentyloxy group, a cyclohexyloxy group, a fluorocyclohexyloxy group, a chlorocyclohexyloxy group and a cyclohexylmethyl oxy group, methylcyclohexyloxy group, norbornyloxy group, ethylcyclohexyloxy group, cyclohexylethyloxy group, dimethylcyclohexyloxy group, methylcyclohexylmethyloxy group, norbornylmethyloxy group, trimethylcyclohexyloxy group, 1-cyclohexyl butyloxy group, adamantyloxy group, menthyloxy group, n-butylcyclohexyloxy group, tert-butylcyclohexyloxy group, bornyloxy group, isobornyloxy group, decahydronaphthyloxy group, dicyclopentadienoxy group, 1 -cyclohexylpentyloxy group, methyladamantyloxy group, adamantylmethyloxy group, 4-pentylcyclohexyloxy group, cyclohexylcyclohexyloxy group, adamantylethyloxy group and dimethyladamantyloxy group.

Examples of R ^23a to R ^26a representing heterocyclyloxy groups include tetrahydrofuranyloxy, furfuryloxy, tetrahydrofurfuryloxy, tetrahydropyranyloxy, butyrolactonyloxy, indolyloxy groups.

Examples of R ^23a to R ^26a being alkylthio groups containing alicyclic hydrocarbon groups include cyclopentylthio, cyclohexylthio, cyclohexylmethylthio, norbornylthio and isonorbornylthio groups.

Examples of heterocyclylthio groups for R ^23a to R ^26a include furfurylthio and tetrahydrofuranylthio.

Examples of R ^23a to R ^26a in which a methylene group at any position not adjacent to an oxygen atom of an alkoxy group is substituted with —CO— include 2-ketobutyl-1-oxy group and 2-ketopentyl -1-oxy group, 2-ketohexyl-1-oxy group, 2-ketoheptyl-1-oxy group, 2-ketooctyl-1-oxy group, 3-ketobutyl-1-oxy group, 4-ketopentyl-1-oxy group , 5-ketohexyl-1-oxy group, 6-ketoheptyl-1-oxy group, 7-ketooctyl-1-oxy group, 3-methyl-2-ketopentane-4-oxy group, 2-ketopentane-4-oxy group, 2-methyl-2-ketopentan-4-oxy group, 3-ketoheptane-5-oxy group, and 2-adamantanone-5-oxy group.

Examples of R ^23a to R ^26a in which a methylene group at any position not adjacent to the sulfur atom of an alkylthio group is substituted with —CO— include 2-ketobutyl-1-thio group and 2-ketopentyl -1-thio group, 2-ketohexyl-1-thio group, 2-ketoheptyl-1-thio group, 2-ketooctyl-1-thio group, 3-ketobutyl-1-thio group, 4-ketopentyl-1-thio group , 5-ketohexyl-1-thio group, 6-ketoheptyl-1-thio group, 7-ketooctyl-1-thio group, 3-methyl-2-ketopentane-4-thio group, 2-ketopentane-4-thio group, 2-methyl-2-ketopentane-4-thio group and 3-ketoheptane-5-thio group.

Specific examples of the compound represented by formula (a21) include the following compounds.

The acid generator (A) may be used alone or in combination of two or more. The content of the acid generator (A) is preferably 0.1% by mass or more and 10% by mass or less, and 0.2% by mass or more and 6% by mass or less, relative to the total solid content of the photosensitive composition. It is more preferable to set it as 0.5 mass % or more and 3 mass % or less is especially preferable. By setting the amount of the acid generator (A) to be within the above range, it is easy to prepare a photosensitive composition that has good sensitivity, is a uniform solution, and has excellent storage stability.

<Resin (B)>
The photosensitive composition contains, as an essential component, an acrylic resin (B3) as a resin (B) whose solubility in alkali increases under the action of acid. The acrylic resin (B3) contains a structural unit represented by formula (B3-1).
The photosensitive composition may contain, together with the acrylic resin (B3), any resin other than the acrylic resin (B3) whose solubility in alkali increases under the action of an acid. However, the ratio of the mass of the acrylic resin (B3) to the mass of the resin (B) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. It is preferably 100% by mass or more, and particularly preferably 100% by mass or more.
Any resin other than the acrylic resin (B3) whose alkali solubility is increased by the action of an acid includes a novolac resin (B1) whose alkali solubility is increased by the action of an acid, and a novolac resin (B1) whose alkali solubility is increased by the action of an acid. Examples include polyhydroxystyrene resin (B2), which is increasing, and acrylic resin, other than acrylic resin (B3), whose solubility in alkali is increased by the action of acid.
Each resin will be specifically described below.

[Novolac resin (B1)]
As the novolak resin (B1), a resin containing a structural unit represented by the following formula (b1) can be used.

In formula (b1) above, R ^1b represents an acid dissociable, dissolution inhibiting group, and R ^2b and R ^3b each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Examples of the acid dissociable, dissolution inhibiting group represented by R ^1b include groups represented by the following formulas (b2) and (b3), linear, branched, or cyclic alkyl groups having 1 to 6 carbon atoms. is preferably a group, a vinyloxyethyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, or a trialkylsilyl group.

In the above formulas (b2) and (b3), R ^4b and R ^5b each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to ⁶ carbon atoms; represents a linear, branched or cyclic alkyl group having 1 to 10 atoms, R ^7b represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms; represents 0 or 1.

Examples of the linear or branched alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. . Moreover, a cyclopentyl group, a cyclohexyl group, etc. are mentioned as said cyclic alkyl group.

Here, specific examples of the acid dissociable, dissolution inhibiting group represented by the above formula (b2) include a methoxyethyl group, an ethoxyethyl group, an n-propoxyethyl group, an isopropoxyethyl group, an n-butoxyethyl group, isobutoxyethyl group, tert-butoxyethyl group, cyclohexyloxyethyl group, methoxypropyl group, ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1-ethoxy-1-methylethyl group and the like. Specific examples of the acid-dissociable, dissolution-inhibiting group represented by the above formula (b3) include a tert-butoxycarbonyl group and a tert-butoxycarbonylmethyl group. Examples of the trialkylsilyl group include groups having 1 to 6 carbon atoms in each alkyl group such as a trimethylsilyl group and a tri-tert-butyldimethylsilyl group.

[Polyhydroxystyrene resin (B2)]
As the polyhydroxystyrene resin (B2), a resin containing a structural unit represented by the following formula (b4) can be used.

In formula (b4) above, R ^8b represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ^9b represents an acid dissociable, dissolution inhibiting group.

The alkyl group having 1 to 6 carbon atoms is, for example, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. Linear or branched alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. A cyclopentyl group, a cyclohexyl group, etc. are mentioned as a cyclic alkyl group.

As the acid-dissociable, dissolution-inhibiting group represented by ^R9b , the same acid-dissociable, dissolution-inhibiting groups as exemplified in the above formulas (b2) and (b3) can be used.

Furthermore, the polyhydroxystyrene resin (B2) can contain other polymerizable compounds as structural units for the purpose of appropriately controlling physical and chemical properties. Examples of such polymerizable compounds include known radically polymerizable compounds and anionically polymerizable compounds. Examples of such polymerizable compounds include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; 2-methacryloyloxyethylsuccinic acid, 2- Methacrylic acid derivatives having a carboxy group and an ester bond such as methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylic acid alkyl esters such as (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and other (meth) acrylic acid hydroxyalkyl esters; phenyl (meth) acrylate, (meth)acrylic acid aryl esters such as benzyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, vinyl group-containing aromatic compounds such as α-methylhydroxystyrene and α-ethylhydroxystyrene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; nitrile group-containing polymerizable compounds; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; amide bond-containing polymerizable compounds such as acrylamide and methacrylamide;

（式（Ｂ３－１）中、Ｒ^ｂ０１は、水素原子又はメチル基であり、Ｒ^ｂ０２は、単結合、又は連結基であり、Ｒ^ｂ０３は、水素原子又は脂肪族炭化水素基であり、Ｒ^ｂ０４及びＲ^ｂ０５は、それぞれ独立に、単結合又は脂肪族炭化水素基であり、Ｒ^ｂ０４及びＲ^ｂ０５が同時に単結合であることはなく、Ｒ^ｂ０６及びＲ^ｂ０７は、それぞれ独立に、水素原子又は脂肪族炭化水素基であり、Ｒ^ｂ０２及びＲ^ｂ０３の一方が、アクリル樹脂（Ｂ３）の主鎖を構成する炭素原子と結合して環を形成してもよく、Ｒ^ｂ０２とＲ^ｂ０３とが結合して環を形成してもよく、Ｒ^ｂ０２とＲ^ｂ０５とが結合して環を形成してもよく、Ｒ^ｂ０６とＲ^ｂ０７とが結合して環を形成してもよい。） [Acrylic resin (B3)]
The acrylic resin (B3) as the resin (B) whose solubility in alkali increases under the action of acid contains a structural unit represented by the following formula (B3-1).

(In formula (B3-1), R ^b01 is a hydrogen atom or a methyl group, R ^b02 is a single bond or a linking group, R ^b03 is a hydrogen atom or an aliphatic hydrocarbon group, R ^b04 and R ^b05 are each independently a single bond or an aliphatic hydrocarbon group, R ^b04 and R ^b05 are not both single bonds, and R ^b06 and R ^b07 are each independently a hydrogen atom or It is an aliphatic hydrocarbon group, one of R ^b02 and R ^b03 may be bonded to a carbon atom constituting the main chain of the acrylic resin (B3) to form a ring, and R ^b02 and R ^b03 are bonded may form a ring, R ^b02 and R ^b05 may combine to form a ring, and R ^b06 and R ^b07 may combine to form a ring.)

In the present specification, the "acrylic resin" means that the ratio of structural units derived from a monomer having a (meth)acryloyloxy group to the total structural units constituting the resin is 50 mol% or more, preferably The resin is 70 mol % or more, more preferably 90 mol % or more.
Moreover, in this specification, "(meth)acryl" means both "acryl" and "methacryl". "(Meth)acrylate" means both "acrylate" and "methacrylate". "(Meth)acryloyloxy" means both "acryloyloxy" and "methacryloyloxy".

In formula (B3-1), the linking group for R ^b02 includes -COO-, -OCO-, -CONH-, -O-, a hydrocarbon group, and combinations thereof. Examples of the hydrocarbon group include aliphatic hydrocarbon groups having 1 to 10 carbon atoms. R ^b02 is preferably a group in which -COO- and a hydrocarbon group are bonded, or -COO-. In the group in which -COO- and a hydrocarbon group are bonded, the carbon atom of -COO- may be bonded to the carbon atom constituting the main chain of the acrylic resin (B3), and the carbon atom of the hydrocarbon group may be bonded to a carbon atom constituting the main chain of the acrylic resin (B3).

In formula (B3-1), examples of the aliphatic hydrocarbon group for R ^b03 include aliphatic hydrocarbon groups having 1 to 10 carbon atoms.
Examples of aliphatic hydrocarbon groups include linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl. group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decyl group.

In formula (B3-1), examples of the aliphatic hydrocarbon group for R ^b04 and R ^b05 include aliphatic hydrocarbon groups having 1 to 4 carbon atoms.
Examples of aliphatic hydrocarbon groups include linear or branched alkylene groups such as methylene, ethane-1,2-diyl, propane-1,3-diyl and propane-1,2-diyl groups. mentioned.

In formula (B3-1), examples of the aliphatic hydrocarbon group for R ^b06 and R ^b07 include aliphatic hydrocarbon groups having 1 to 10 carbon atoms.
Examples of aliphatic hydrocarbon groups include linear, branched or cyclic alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert -butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and cyclohexyl group.

A ring formed by binding one of R ^b02 and R ^b03 to a carbon atom constituting the main chain of the acrylic resin (B3), a ring formed by binding R ^b02 and R ^b03 , and R ^b02 and R ^b05 The ring formed by combining and the ring formed by combining R ^b06 and R ^b07 include aliphatic hydrocarbon rings.
The aliphatic hydrocarbon ring may be a monocyclic structure or a polycyclic structure. The aliphatic hydrocarbon ring includes cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, and norbornane ring.

（式（Ｂ３－２）中、Ｒ^ｂ０１、Ｒ^ｂ０３、Ｒ^ｂ０４、Ｒ^ｂ０５、Ｒ^ｂ０６、及びＲ^ｂ０７は前記式（Ｂ３－１）中のこれらと同様であり、Ｒ^ｂ０１０は、単結合又は炭化水素基であり、Ｒ^ｂ０５とＲ^ｂ０１０とが結合して環を形成してもよい。） As the structural unit represented by formula (B3-1), a structural unit represented by the following formula (B3-2) is preferable.

(In formula (B3-2), R ^b01 , R ^b03 , R ^b04 , R ^b05 , R ^b06 , and R ^b07 are the same as those in formula (B3-1) above, and R ^b010 is a single bond or It is a hydrocarbon group, and R ^b05 and R ^b010 may combine to form a ring.)

In formula (B3-2), the hydrocarbon group for R ^b010 includes an aliphatic hydrocarbon group having 1 to 10 carbon atoms.
Examples of aliphatic hydrocarbon groups include linear or branched alkylene groups such as methylene, ethane-1,2-diyl, propane-1,3-diyl and propane-1,2-diyl groups. mentioned.

In formula (B3-2), R ^b03 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ^b04 and R ^b05 are each independently a single bond or a methylene group, R ^b06 and R Preferably, ^b07 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ^b010 is a methylene group.

（式（Ｂ３－３）及び（式３－４）中、Ｒ^ｂ０１、Ｒ^ｂ０３、Ｒ^ｂ０６、Ｒ^ｂ０７、及びＲ^ｂ０１０は前述の式（Ｂ３－２）中のこれらと同様である。） As the structural unit represented by the formula (B3-2), a structural unit represented by the following formula (B3-3) or (B3-4) is preferable.

(In formulas (B3-3) and (3-4), R ^b01 , R ^b03 , R ^b06 , R ^b07 , and R ^b010 are the same as those in formula (B3-2) above.)

（式中、Ｒ^ｂ０１～Ｒ^ｂ０７は前述の式（Ｂ３－１）中のこれらと同様である。） The structural unit represented by the formula (B3-1) is, for example, the acrylic resin (B3) by polymerizing or copolymerizing the following compound, which is a monomer corresponding to the formula (B3-1): can be introduced.

(Wherein, R ^b01 to R ^b07 are the same as those in the above formula (B3-1).)

（式中、Ｒ^ｂ０１は前述の式（Ｂ３－１）中のＲ^ｂ０１と同様である。） Specific examples of structural units represented by formula (B3-1) include the following structural units.

(In the formula, R ^b01 is the same as R ^b01 in the above formula (B3-1).)

When the solid content concentration is high, the storage stability is poor, and for example, the viscosity of the photosensitive composition tends to change over time.
However, by using an acrylic resin (B3) containing a structural unit represented by the formula (B3-1) as the resin (B) and making the solid content concentration in the range of 25% by mass or more and 70% by mass or less, the solid It is possible to realize a photosensitive composition having excellent storage stability in spite of its high concentration.
For example, the viscosity of the photosensitive composition when measured using an E-type viscometer at 25 ° C. is V1, and the photosensitive composition is allowed to stand at 40 ° C. for 2 weeks, and the photosensitive composition after standing is 25 V2/V1 can be less than 1.1, where V2 is the viscosity measured at °C using an E-type viscometer.
Since the photosensitive composition has a high solid content concentration, it is easy to form a thick photosensitive layer (for example, 70 μm or more). Therefore, the photosensitive composition can be preferably used, for example, for forming a plated modeled article.

In addition, the photosensitive layer formed using the above photosensitive composition is inhibited from repelling the developer after exposure. Therefore, for example, the developer can be brought into contact with the entire photosensitive layer, and a resist pattern having a desired shape corresponding to the mask or the like can be formed over the entire area where the photosensitive layer is provided.

In addition, swelling of the photosensitive layer formed using the photosensitive composition described above is suppressed during development after exposure. For this reason, for example, wrinkles, dissolution of unexposed portions, lifting and distortion caused by swelling are suppressed in the obtained resist pattern.

In addition, the photosensitive layer formed using the photosensitive composition described above is inhibited from cracking, that is, has excellent crack resistance. Therefore, for example, when the obtained resist pattern is used as a mold for forming a plated modeled article, it is easy to form a plated modeled article having a desired shape.

The amount of the structural unit represented by the formula (B3-1) in the acrylic resin (B3) is not particularly limited, but the mass of the structural unit represented by the formula (B3-1) with respect to the mass of the acrylic resin (B3) is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 40% by mass or less, and even more preferably 10% by mass or more and 30% by mass or less.

The acrylic resin (B3) may contain a structural unit (b-3) derived from an acrylic acid ester containing, for example, a —SO ₂ —containing cyclic group or a lactone-containing cyclic group. In such a case, when forming a resist pattern, it is easy to form a resist pattern having a preferable cross-sectional shape. However, if it has a —SO ₂ -containing cyclic group or a lactone _- containing cyclic group, the storage stability of the photosensitive composition deteriorates. It is preferable not to contain or to have little content.

(—SO ₂ -containing cyclic group)
Here, the “—SO ₂ —containing cyclic group” refers to a cyclic group containing a ring containing —SO ₂ — in its ring skeleton. Specifically, the sulfur atom in —SO ₂ — ( S) is a cyclic group that forms part of the ring skeleton of a cyclic group. A ring containing —SO ₂ — in its ring skeleton is counted as the first ring, and if it contains only the ring, it is a monocyclic group, and if it has another ring structure, it is a polycyclic group regardless of its structure. called. The —SO ₂ —containing cyclic group may be monocyclic or polycyclic.

A —SO ₂ —containing cyclic group is particularly a cyclic group containing —O—SO ₂ — in its ring skeleton, ie, —O—S— in —O—SO ₂ — forms part of the ring skeleton. Preferred are cyclic groups containing a forming sultone ring.

The number of carbon atoms in the —SO ₂ —-containing cyclic group is preferably 3 or more and 30 or less, more preferably 4 or more and 20 or less, still more preferably 4 or more and 15 or less, and particularly preferably 4 or more and 12 or less. The number of carbon atoms is the number of carbon atoms constituting the ring skeleton, and does not include the number of carbon atoms in the substituents.

The -SO ₂ -containing cyclic group may be an -SO ₂ -containing aliphatic cyclic group or a -SO ₂ -containing aromatic cyclic group. An --SO ₂ --containing aliphatic cyclic group is preferred.

As the —SO ₂ —-containing aliphatic cyclic group, hydrogen atoms are removed from an aliphatic hydrocarbon ring in which some of the carbon atoms constituting the ring skeleton are replaced with —SO ₂ — or —O—SO ₂ —. Groups with at least one removed are included. More specifically, a group obtained by removing at least one hydrogen atom from an aliphatic hydrocarbon ring in which —CH ₂ — constituting the ring skeleton is substituted with —SO ₂ —, or —CH ₂ — constituting the ring. Examples thereof include groups obtained by removing at least one hydrogen atom from an aliphatic hydrocarbon ring in which CH ₂ — is substituted with —O—SO ₂ —.

The number of carbon atoms in the alicyclic hydrocarbon ring is preferably 3 or more and 20 or less, more preferably 3 or more and 12 or less. The alicyclic hydrocarbon ring may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocycloalkane having 3 or more and 6 or less carbon atoms. Examples of the monocycloalkane include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon ring is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane having 7 to 12 carbon atoms, and specific examples of the polycycloalkane include adamantane and norbornane. , isobornane, tricyclodecane, tetracyclododecane, and the like.

The —SO ₂ —-containing cyclic group may have a substituent. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, halogenated alkyl groups, hydroxyl groups, oxygen atoms (=O), -COOR'', -OC(=O)R'', hydroxyalkyl groups, cyano groups, and the like. is mentioned.

As the alkyl group as the substituent, an alkyl group having 1 to 6 carbon atoms is preferable. The alkyl group is preferably linear or branched. Specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group and the like. be done. Among these, a methyl group or an ethyl group is preferred, and a methyl group is particularly preferred.

As the alkoxy group as the substituent, an alkoxy group having 1 to 6 carbon atoms is preferable. The alkoxy group is preferably linear or branched. Specifically, groups in which the alkyl group exemplified above as the alkyl group as the substituent is bonded to an oxygen atom (--O--) can be mentioned.

A halogen atom as the substituent includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.

Examples of the halogenated alkyl group as the substituent include groups in which some or all of the hydrogen atoms of the aforementioned alkyl group have been substituted with the aforementioned halogen atoms.

Examples of the halogenated alkyl group as the substituent include a group in which some or all of the hydrogen atoms of the alkyl group exemplified above as the alkyl group as the substituent are substituted with the above-described halogen atoms. As the halogenated alkyl group, a fluorinated alkyl group is preferable, and a perfluoroalkyl group is particularly preferable.

R" in -COOR" and -OC(=O)R" described above is either a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms.

When R″ is a linear or branched alkyl group, the number of carbon atoms in the chain alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and particularly preferably 1 or 2.

When R″ is a cyclic alkyl group, the number of carbon atoms in the cyclic alkyl group is preferably 3 or more and 15 or less, more preferably 4 or more and 12 or less, and particularly preferably 5 or more and 10 or less. , or removing one or more hydrogen atoms from monocycloalkanes, which may or may not be substituted with fluorinated alkyl groups, and polycycloalkanes such as bicycloalkanes, tricycloalkanes, and tetracycloalkanes. More specifically, one or more hydrogen atoms are added from monocycloalkanes such as cyclopentane and cyclohexane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. groups excepted.

As the hydroxyalkyl group as the substituent, a hydroxyalkyl group having 1 to 6 carbon atoms is preferable. Specifically, a group in which at least one hydrogen atom of the alkyl group exemplified above as the alkyl group as the substituent is substituted with a hydroxyl group is exemplified.

（式中、Ａ’は酸素原子若しくは硫黄原子を含んでいてもよい炭素原子数１以上５以下のアルキレン基、酸素原子又は硫黄原子であり、ｚは０以上２以下の整数であり、Ｒ^１０ｂはアルキル基、アルコキシ基、ハロゲン化アルキル基、水酸基、－ＣＯＯＲ”、－ＯＣ（＝Ｏ）Ｒ”、ヒドロキシアルキル基、又はシアノ基であり、Ｒ”は水素原子、又はアルキル基である。） More specific examples of the —SO ₂ —containing cyclic group include groups represented by the following formulas (3-1) to (3-4).

(Wherein, A′ is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, z is an integer of 0 to 2, and R ^10b is an alkyl group, an alkoxy group, a halogenated alkyl group, a hydroxyl group, -COOR", -OC(=O)R", a hydroxyalkyl group, or a cyano group, and R" is a hydrogen atom or an alkyl group.)

In the above formulas (3-1) to (3-4), A' is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom (-O-) or a sulfur atom (-S-) , an oxygen atom, or a sulfur atom. The alkylene group having 1 to 5 carbon atoms in A' is preferably a linear or branched alkylene group, and examples thereof include a methylene group, an ethylene group, an n-propylene group and an isopropylene group.

When the alkylene group contains an oxygen atom or a sulfur atom, specific examples thereof include groups in which -O- or -S- is interposed between the terminals or carbon atoms of the above-mentioned alkylene group, for example, -O- CH ₂ -, -CH ₂ -O-CH ₂ -, -S-CH ₂ -, -CH ₂ -S-CH ₂ - and the like. A′ is preferably an alkylene group having 1 to 5 carbon atoms or —O—, more preferably an alkylene group having 1 to 5 carbon atoms, and most preferably a methylene group.

z can be 0, 1, and 2, with 0 being most preferred. When z is 2, multiple R ^10b may be the same or different.

The alkyl group, alkoxy group, halogenated alkyl group, -COOR'', -OC(=O)R'', and hydroxyalkyl group for R ^10b may each have a -SO ₂ -containing cyclic group. The alkyl group, alkoxy group, halogenated alkyl group, -COOR'', -OC(=O)R'', and hydroxyalkyl group mentioned as substituents are the same as those described above.

Specific examples of the cyclic groups represented by formulas (3-1) to (3-4) are given below. "Ac" in the formula represents an acetyl group.

Among the above, the —SO ₂ —-containing cyclic group is preferably a group represented by the aforementioned formula (3-1), and the aforementioned chemical formulas (3-1-1) and (3-1-18). , (3-3-1), and (3-4-1) are more preferably at least one selected from the group consisting of groups represented by the above chemical formula (3-1-1) are most preferred.

(lactone-containing cyclic group)
A “lactone-containing cyclic group” refers to a cyclic group containing a ring containing —O—C(=O)— in its ring skeleton (lactone ring). A lactone ring is counted as the first ring, and a group containing only a lactone ring is called a monocyclic group, and a group containing other ring structures is called a polycyclic group regardless of the structure. A lactone-containing cyclic group may be a monocyclic group or a polycyclic group.

Any lactone cyclic group in the structural unit (b-3) can be used without any particular limitation. Specifically, the lactone-containing monocyclic group includes a group obtained by removing one hydrogen atom from a 4- to 6-membered ring lactone, for example, a group obtained by removing one hydrogen atom from β-propionolactone, and a group obtained by removing one hydrogen atom from γ-butyrolactone. Examples thereof include a group obtained by removing one hydrogen atom, and a group obtained by removing one hydrogen atom from δ-valerolactone. Examples of lactone-containing polycyclic groups include groups obtained by removing one hydrogen atom from bicycloalkanes, tricycloalkanes, and tetracycloalkanes having a lactone ring.

As the structural unit (b-3), the structure of the other portion is not particularly limited as long as it has a —SO ₂ —containing cyclic group or a lactone-containing cyclic group. a structural unit (b-3-S), which is a structural unit derived from an acrylate ester in which a hydrogen atom may be substituted by a substituent and contains a —SO ₂ —containing cyclic group, and a carbon atom at the α-position; selected from the group consisting of a structural unit (b-3-L) containing a lactone-containing cyclic group, which is a structural unit derived from an acrylic ester in which the hydrogen atom bonded to is optionally substituted with a substituent At least one structural unit is preferred.

[Structural unit (b-3-S)]
More specific examples of the structural unit (b-3-S) include structural units represented by the following formula (b-S1).

（式中、Ｒは水素原子、炭素原子数１以上５以下のアルキル基、又は炭素原子数１以上５以下のハロゲン化アルキル基であり、Ｒ^１１ｂは－ＳＯ_２－含有環式基であり、Ｒ^１２ｂは単結合、又は２価の連結基である。）

(wherein R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, R ^11b is a —SO ₂ —containing cyclic group, R ^12b is a single bond or a divalent linking group.)

In formula (b-S1), R is the same as defined above.
R ^11b is the same as the —SO ₂ —containing cyclic group mentioned above.
R ^12b may be either a single bond or a divalent linking group.

The divalent linking group for R ^12b is not particularly limited, but preferred examples thereof include a divalent hydrocarbon group optionally having a substituent, a divalent linking group containing a hetero atom, and the like.

- Divalent hydrocarbon group optionally having a substituent The hydrocarbon group as the divalent linking group may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group without aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated. A saturated hydrocarbon group is usually preferred. More specifically, the aliphatic hydrocarbon group includes a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in its structure, and the like.

The number of carbon atoms in the linear or branched aliphatic hydrocarbon group is preferably 1 or more and 10 or less, more preferably 1 or more and 8 or less, and even more preferably 1 or more and 5 or less.

A linear alkylene group is preferable as the linear aliphatic hydrocarbon group. Specifically, methylene group [-CH ₂ -], ethylene group [-(CH ₂ ) ₂ -], trimethylene group [-(CH ₂ ) ₃ -], tetramethylene group [-(CH ₂ ) ₄ -] , a pentamethylene group [-(CH ₂ ) ₅ -] and the like.

A branched alkylene group is preferable as the branched aliphatic hydrocarbon group. Specifically, -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₃ ) Alkylmethylene groups such as (CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) ₂ -; -CH(CH ₃ )CH ₂ -, -CH(CH ₃ )CH(CH ₃ )- , -C(CH ₃ ) ₂ CH ₂ -, -CH(CH ₂ CH ₃ )CH ₂ -, -C(CH ₂ CH ₃ ) ₂ -CH ₂ -, alkylethylene groups such as -CH(CH ₃ )CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ - and other alkyltrimethylene groups; -CH(CH ₃ )CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ CH ₂ - and alkylalkylene groups such as alkyltetramethylene groups such as As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

The straight-chain or branched-chain aliphatic hydrocarbon group may or may not have a substituent (a group or atom other than a hydrogen atom) for substituting a hydrogen atom. Examples of the substituent include a fluorine atom, a fluorine-substituted fluorinated alkyl group having 1 to 5 carbon atoms, and an oxo group (=O).

As the aliphatic hydrocarbon group containing a ring in the above structure, a cyclic aliphatic hydrocarbon group (with two hydrogen atoms removed from the aliphatic hydrocarbon ring) which may contain a substituent containing a hetero atom in the ring structure group), a group in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, a group in which the cyclic aliphatic hydrocarbon group is linear or branched Examples thereof include groups interposed in the middle of aliphatic hydrocarbon groups. Examples of the straight-chain or branched-chain aliphatic hydrocarbon group include those mentioned above.

The number of carbon atoms in the cyclic aliphatic hydrocarbon group is preferably 3 or more and 20 or less, more preferably 3 or more and 12 or less.

A cyclic aliphatic hydrocarbon group may be polycyclic or monocyclic. As the monocyclic aliphatic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferable. The number of carbon atoms in the monocycloalkane is preferably 3 or more and 6 or less. Specific examples include cyclopentane and cyclohexane. As the polycyclic aliphatic hydrocarbon group, a group obtained by removing two hydrogen atoms from polycycloalkane is preferable. The number of carbon atoms in the polycycloalkane is preferably 7 or more and 12 or less. Specific examples include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

A cyclic aliphatic hydrocarbon group may or may not have a substituent (a group or atom other than a hydrogen atom) for substituting a hydrogen atom. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and an oxo group (=O).

The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group.

The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group. is more preferred, and a methoxy group and an ethoxy group are particularly preferred.

Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferred.

Examples of the halogenated alkyl group as the above-mentioned substituent include groups in which some or all of the hydrogen atoms of the above-mentioned alkyl group are substituted with the above-mentioned halogen atoms.

In the cyclic aliphatic hydrocarbon group, part of the carbon atoms constituting the ring structure may be substituted with -O- or -S-. Preferred heteroatom-containing substituents are -O-, -C(=O)-O-, -S-, -S(=O) ₂ - and -S(=O) ₂ -O-.

An aromatic hydrocarbon group as a divalent hydrocarbon group is a divalent hydrocarbon group having at least one aromatic ring and may have a substituent. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 or more and 30 or less, more preferably 5 or more and 20 or less, still more preferably 6 or more and 15 or less, and particularly preferably 6 or more and 12 or less. However, the number of carbon atoms does not include the number of carbon atoms of the substituent.

Specific examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocyclic rings in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms; etc. The heteroatom in the aromatic heterocycle includes oxygen atom, sulfur atom, nitrogen atom and the like. Specific examples of aromatic heterocycles include pyridine rings and thiophene rings.

Specifically, the aromatic hydrocarbon group as the divalent hydrocarbon group is a group obtained by removing two hydrogen atoms from the above aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); A group obtained by removing two hydrogen atoms from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); A group obtained by removing one hydrogen atom from the above aromatic hydrocarbon ring or aromatic heterocycle ( aryl group or heteroaryl group) in which one of the hydrogen atoms is substituted with an alkylene group (e.g., benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2- a group obtained by removing one hydrogen atom from an aryl group in an arylalkyl group such as a naphthylethyl group); and the like.

The number of carbon atoms in the alkylene group bonded to the aryl group or heteroaryl group is preferably 1 or more and 4 or less, more preferably 1 or more and 2 or less, and particularly preferably 1.

In the above aromatic hydrocarbon group, a hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent. For example, a hydrogen atom bonded to an aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and an oxo group (=O).

The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and a tert-butyl group.

The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group. is preferred, and a methoxy group and an ethoxy group are more preferred.

The halogen atom as the substituent includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferred.

Examples of the halogenated alkyl group as the substituent include groups in which some or all of the hydrogen atoms of the above-mentioned alkyl group are substituted with the above-mentioned halogen atoms.

- Bivalent linking group containing a hetero atom The hetero atom in the bivalent linking group containing a hetero atom is an atom other than a carbon atom and a hydrogen atom, such as an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom. etc.

Specific examples of the divalent linking group containing a heteroatom include -O-, -C(=O)-, -C(=O)-O-, -OC(=O)-O-, -S-, -S(=O) ₂ -, -S(=O) ₂ -O-, -NH-, -NH-C(=O)-, -NH-C(=NH)-, =N and a combination of at least one of these non-hydrocarbon linking groups and a divalent hydrocarbon group. Examples of the divalent hydrocarbon group include the same divalent hydrocarbon groups that may have a substituent as described above, and a linear or branched aliphatic hydrocarbon group is preferable. .

Among the above, -NH-, -NH- in -C(=O)-NH-, H in -NH-C(=NH)- are substituted with substituents such as alkyl groups and acyl groups, respectively. may have been The number of carbon atoms in the substituent is preferably 1 or more and 10 or less, more preferably 1 or more and 8 or less, and particularly preferably 1 or more and 5 or less.

The divalent linking group for R ^12b is particularly preferably a linear or branched alkylene group, a cyclic aliphatic hydrocarbon group, or a heteroatom-containing divalent linking group.

When the divalent linking group for R ^12b is a linear or branched alkylene group, the number of carbon atoms in the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and 1 or more and 4 or less. is particularly preferred, and 1 or more and 3 or less is most preferred. Specifically, in the description of the "optionally substituted divalent hydrocarbon group" as the divalent linking group described above, the linear or branched aliphatic hydrocarbon group and the same as the straight-chain alkylene group and branched-chain alkylene group.

When the divalent linking group for R ^12b is a cyclic aliphatic hydrocarbon group, the cyclic aliphatic hydrocarbon group may have a substituent as the divalent linking group described above. The same as the cyclic aliphatic hydrocarbon group mentioned as the "aliphatic hydrocarbon group containing a ring in the structure" in the description of "divalent hydrocarbon group" can be mentioned.

The cyclic aliphatic hydrocarbon group is particularly preferably a group obtained by removing two or more hydrogen atoms from cyclopentane, cyclohexane, norbornane, isobornane, adamantane, tricyclodecane, or tetracyclododecane.

When the divalent linking group for R ^12b is a heteroatom-containing divalent linking group, preferred examples of the linking group include -O-, -C(=O)-O-, -C(=O )-, -OC(=O)-O-, -C(=O)-NH-, -NH- (H may be substituted with a substituent such as an alkyl group or an acyl group), -S-, -S(=O) ₂ -, -S(=O) ₂ -O-, general formula -Y ¹ -O-Y ² -, -[Y ¹ -C(=O)-O] _{m '} -Y ² -, or a group represented by -Y ¹ -OC(=O)-Y ₂ - [wherein Y ¹ and Y ² each independently have a substituent It is a good divalent hydrocarbon group, O is an oxygen atom, and m' is an integer of 0 or more and 3 or less. ] and the like.

When the divalent linking group in R ^12b is -NH-, the hydrogen atom in -NH- may be substituted with a substituent such as an alkyl group or acyl. The number of carbon atoms in the substituent (alkyl group, acyl group, etc.) is preferably 1 or more and 10 or less, more preferably 1 or more and 8 or less, and particularly preferably 1 or more and 5 or less.

_Y ^{_ _ _ _ _ _ 1} and Y ² are each independently a divalent hydrocarbon group optionally having a substituent. Examples of the divalent hydrocarbon group include those similar to the "optionally substituted divalent hydrocarbon group" mentioned in the description of the divalent linking group.

Y ¹ is preferably a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 5 carbon atoms, a methylene group, and ethylene groups are particularly preferred.

^Y2 is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group, or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.

In the group represented by the formula -[Y ¹ -C(=O)-O] _m' -Y ² -, m' is an integer of 0 or more and 3 or less, preferably an integer of 0 or more and 2 or less, and 0 or 1 is more preferred, and 1 is particularly preferred. That is, the group represented by the formula -[Y ¹ -C(=O)-O] _m' -Y ² - is represented by the formula -Y ¹ -C(=O)-O-Y ² - groups are particularly preferred. Among them, a group represented by the formula -(CH ₂ ) _a' -C(=O)-O-(CH ₂ ) _b' - is preferred. In the formula, a' is an integer of 1 or more and 10 or less, preferably an integer of 1 or more and 8 or less, more preferably an integer of 1 or more and 5 or less, more preferably 1 or 2, and most preferably 1. b' is an integer of 1 or more and 10 or less, preferably an integer of 1 or more and 8 or less, more preferably an integer of 1 or more and 5 or less, still more preferably 1 or 2, and most preferably 1.

As for the divalent linking group for R ^12b , the heteroatom-containing divalent linking group is preferably an organic group consisting of a combination of at least one non-hydrocarbon group and a divalent hydrocarbon group. Among them, a straight-chain group having an oxygen atom as a heteroatom, such as a group containing an ether bond or an ester bond, is preferred, and the aforementioned formulas -Y ¹ -O-Y ² -, -[Y ¹ -C(= O)—O] _m′ —Y ² — or a group represented by —Y ¹ —OC(=O)—Y ² — is more preferable, and the group represented by the above formula —[Y ¹ —C(=O) A group represented by —O] _m′ —Y ² — or —Y ¹ —O—C(═O)—Y ² — is particularly preferred.

The divalent linking group for R ^12b preferably contains an alkylene group or an ester bond (--C(=O)--O--).

The alkylene group is preferably a linear or branched alkylene group. Preferable examples of the linear aliphatic hydrocarbon group include a methylene group [--CH.sub.2--], an ethylene group [-- ₍ CH.sub.2) _.sub.2-- ], a trimethylene group [-- ₍ CH.sub.2) _.sub.3-- ] _, A tetramethylene group [-(CH ₂ ) ₄ -], a pentamethylene group [-(CH ₂ ) ₅ -] and the like can be mentioned. Preferable examples of the branched chain alkylene group include -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CH ₃ )(CH ₂ Alkylmethylene groups such as CH ₃ )—, —C(CH ₃ )(CH ₂ CH ₂ CH ₃ )—, —C(CH ₂ CH ₃ ) ₂ —; —CH(CH ₃ )CH ₂ —, —CH( Alkyl ethylenes such as CH ₃ )CH(CH ₃ )—, —C(CH ₃ ) ₂ CH ₂ —, —CH(CH ₂ CH ₃ )CH ₂ —, —C(CH ₂ CH ₃ ) ₂ —CH ₂ — Alkyltrimethylene groups such as -CH(CH ₃ )CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ -; -CH(CH ₃ )CH ₂ CH ₂ CH ₂ -, -CH ₂ CH and alkylalkylene groups such as alkyltetramethylene groups such as (CH ₃ )CH ₂ CH ₂ —.

The divalent linking group containing an ester bond is particularly represented by the formula: -R ^13b -C(=O)-O- [wherein R ^13b is a divalent linking group. ] is preferable. That is, the structural unit (b-3-S) is preferably a structural unit represented by the following formula (b-S1-1).

（式中、Ｒ、及びＲ^１１ｂはそれぞれ前記と同様であり、Ｒ^１３ｂは２価の連結基である。）

(Wherein, R and R ^11b are the same as defined above, and R ^13b is a divalent linking group.)

R ^13b is not particularly limited, and includes, for example, the same divalent linking groups for R ^12b described above.
The divalent linking group for R ^13b is preferably a linear or branched alkylene group, an aliphatic hydrocarbon group containing a ring in its structure, or a divalent linking group containing a hetero atom. Alternatively, a branched alkylene group or a divalent linking group containing an oxygen atom as a heteroatom is preferred.

As the linear alkylene group, a methylene group or an ethylene group is preferred, and a methylene group is particularly preferred. The branched alkylene group is preferably an alkylmethylene group or an alkylethylene group, and particularly -CH(CH ₃ )-, -C(CH ₃ ) ₂ - or -C(CH ₃ ) ₂ CH ₂ -. preferable.

^{The divalent} linking group containing an oxygen atom is preferably ^a divalent linking group containing an ether bond or an ester bond. )—O] _m′ —Y ² — or —Y ¹ —O—C(=O)—Y ² — are more preferred. Y ¹ and Y ² are each independently a divalent hydrocarbon group which may have a substituent, and m' is an integer of 0 or more and 3 or less. Among them, -Y ¹ -OC(=O)-Y ² - is preferred, and a group represented by -(CH ₂ ) _c -OC(=O)-(CH ₂ ) _d - is particularly preferred. . c is an integer of 1 or more and 5 or less, preferably 1 or 2; d is an integer of 1 or more and 5 or less, preferably 1 or 2;

The structural unit (b-3-S) is particularly preferably a structural unit represented by the following formula (b-S1-11) or (b-S1-12), and the formula (b-S1-12) Structural units shown are more preferred.

（式中、Ｒ、Ａ’、Ｒ^１０ｂ、ｚ、及びＲ^１３ｂはそれぞれ前記と同じである。）

(Wherein, R, A', R ^10b , z, and R ^13b are the same as above.)

In formula (b-S1-11), A' is preferably a methylene group, an oxygen atom (--O--), or a sulfur atom (--S--).

R ^13b is preferably a linear or branched alkylene group or a divalent linking group containing an oxygen atom. The straight-chain or branched-chain alkylene group and the divalent linking group containing an oxygen atom for R ^13b are the above-mentioned straight-chain or branched-chain alkylene groups and the divalent linking group containing an oxygen atom, respectively. and similar ones.

As the structural unit represented by the formula (b-S1-12), a structural unit represented by the following formula (b-S1-12a) or (b-S1-12b) is particularly preferable.

（式中、Ｒ、及びＡ’はそれぞれ前記と同じであり、ｃ～ｅはそれぞれ独立に１以上３以下の整数である。）

(Wherein, R and A' are the same as above, and c to e are each independently an integer of 1 or more and 3 or less.)

[Structural unit (b-3-L)]
Examples of the structural unit (b-3-L) include those obtained by substituting R ^11b in the above formula (b-S1) with a lactone-containing cyclic group, and more specifically, the following formula ( Structural units represented by b-L1) to (b-L5) are exemplified.

（式中、Ｒは水素原子、炭素原子数１以上５以下のアルキル基、又は炭素原子数１以上５以下のハロゲン化アルキル基であり；Ｒ’はそれぞれ独立に水素原子、アルキル基、アルコキシ基、ハロゲン化アルキル基、水酸基、－ＣＯＯＲ”、－ＯＣ（＝Ｏ）Ｒ”、ヒドロキシアルキル基、又はシアノ基であり、Ｒ”は水素原子、又はアルキル基であり；Ｒ^１２ｂは単結合、又は２価の連結基であり、ｓ”は０以上２以下の整数であり；Ａ”は酸素原子若しくは硫黄原子を含んでいてもよい炭素原子数１以上５以下のアルキレン基、酸素原子、又は硫黄原子であり；ｒは０又は１である。）

(Wherein, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms; R 'is each independently a hydrogen atom, an alkyl group, an alkoxy group , a halogenated alkyl group, a hydroxyl group, —COOR″, —OC(═O)R″, a hydroxyalkyl group, or a cyano group, and R″ is a hydrogen atom or an alkyl group; R ^12b is a single bond, or is a divalent linking group, s″ is an integer of 0 or more and 2 or less; A″ is an alkylene group having 1 or more and 5 or less carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom, or sulfur atom; r is 0 or 1.)

R in formulas (b-L1) to (b-L5) is the same as described above.
The alkyl group, alkoxy group, halogenated alkyl group, -COOR'', -OC(=O)R'', and hydroxyalkyl group in R' may each have a -SO ₂ -containing cyclic group. Examples of the alkyl group, alkoxy group, halogenated alkyl group, —COOR″, —OC(═O)R″, and hydroxyalkyl group mentioned above as substituents include the same groups as those described above.

R' is preferably a hydrogen atom in view of industrial availability.
The alkyl group for R″ may be linear, branched or cyclic.
When R″ is a linear or branched alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.
When R″ is a cyclic alkyl group, it preferably has 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes, which may or may not be substituted with a fluorine atom or a fluorinated alkyl group, one or more Examples include groups from which a hydrogen atom is removed, etc. Specifically, monocycloalkanes such as cyclopentane and cyclohexane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane, and one or more Groups other than hydrogen atoms are included.
A″ includes the same as A′ in the above formula (3-1). A″ is an alkylene group having 1 to 5 carbon atoms, an oxygen atom (—O—) or a sulfur atom. (-S-) is preferable, and an alkylene group having 1 to 5 carbon atoms or -O- is more preferable. The alkylene group having 1 to 5 carbon atoms is more preferably a methylene group or a dimethylmethylene group, most preferably a methylene group.

R ^12b is the same as R ^12b in formula (b-S1) above.
In formula (b-L1), s″ is preferably 1 or 2.
Specific examples of structural units represented by formulas (b-L1) to (b-L3) are shown below. In each formula below, R ^α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

The structural unit (b-3-L) is preferably at least one selected from the group consisting of the structural units represented by the above formulas (b-L1) to (b-L5), and the formula (b-L1 ) to (b-L3) are more preferably at least one selected from the group consisting of structural units represented by the above formula (b-L1) or (b-L3). At least one selected from the group is particularly preferred.
Among them, the above formulas (b-L1-1), (b-L1-2), (b-L2-1), (b-L2-7), (b-L2-12), (b-L2 -14), (b-L3-1), and (b-L3-5) are preferably at least one selected from the group consisting of structural units.

式（ｂ－Ｌ６）及び（ｂ－Ｌ７）中、Ｒ及びＲ^１２ｂは前述と同様である。 As the structural unit (b-3-L), structural units represented by the following formulas (b-L6) to (b-L7) are also preferred.

In formulas (b-L6) and (b-L7), R and ^R12b are the same as above.

In addition, the acrylic resin (B3) is a structural unit represented by the following formulas (b5) to (b7) having an acid dissociable group as a structural unit that increases the alkali solubility of the acrylic resin (B3) by the action of acid. including.

In the above formulas (b5) to (b7), R ^14b and R ^18b to R ^23b are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a fluorine atom, or represents a linear or branched fluorinated alkyl group having 1 to 6 carbon atoms, and R ^15b to R ^17b each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms; represents a ^linear or branched ^fluorinated alkyl group having 1 to 6 carbon atoms, or an aliphatic cyclic group having 5 to 20 carbon atoms; A hydrocarbon ring having 5 to 20 carbon atoms may be formed together with the bonded carbon atoms, Y ^b represents an optionally substituted aliphatic cyclic group or an alkyl group, and p represents an integer of 0 or more and 4 or less, and q represents 0 or 1.

Examples of the linear or branched alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. mentioned. A fluorinated alkyl group is one in which some or all of the hydrogen atoms of the above alkyl group are substituted with fluorine atoms.
Specific examples of aliphatic cyclic groups include groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. Specifically, groups obtained by removing one hydrogen atom from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. is mentioned. In particular, groups obtained by removing one hydrogen atom from cyclohexane and adamantane (which may further have a substituent) are preferred.

When the above R ^16b and R ^17b do not bind to each other to form a hydrocarbon ring, as the above R ^15b , R ^16b and R ^17b , a carbon atom A linear or branched alkyl group having 1 to 4 carbon atoms is preferable, and a linear or branched alkyl group having 2 to 4 carbon atoms is more preferable. R ^19b , R ^20b , R ^22b and R ^23b are preferably hydrogen atoms or methyl groups.

R ^16b and R ^17b may form an aliphatic cyclic group having 5 or more and 20 or less carbon atoms together with the carbon atoms to which they are bonded. Specific examples of such aliphatic cyclic groups include groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes and tetracycloalkanes. Specifically, one or more hydrogen atoms are removed from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane and cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane. groups. In particular, groups obtained by removing one or more hydrogen atoms from cyclohexane and adamantane (which may further have a substituent) are preferred.

Furthermore, when the aliphatic cyclic group formed by R ^16b and R ^17b has a substituent on its ring skeleton, examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, an oxygen atom (=O ), and linear or branched alkyl groups having 1 to 4 carbon atoms. As the polar group, an oxygen atom (=O) is particularly preferred.

The above ^Yb is an aliphatic cyclic group or an alkyl group, and includes groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. . Specifically, one or more hydrogen atoms are removed from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane and cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane. and the like. In particular, a group obtained by removing one or more hydrogen atoms from adamantane (which may further have a substituent) is preferred.

Furthermore, when the aliphatic cyclic group of ^Yb has a substituent on its ring skeleton, examples of the substituent include a polar group such as a hydroxyl group, a carboxyl group, a cyano group, and an oxygen atom (=O). and linear or branched alkyl groups having 1 to 4 carbon atoms. As the polar group, an oxygen atom (=O) is particularly preferred.

When ^Yb is an alkyl group, it is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 6 to 15 carbon atoms. Such alkyl groups are particularly preferably alkoxyalkyl groups, and examples of such alkoxyalkyl groups include 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-isopropoxy ethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1-tert-butoxyethyl group, 1-methoxypropyl group, 1-ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1 -ethoxy-1-methylethyl group and the like.

Preferable specific examples of the structural unit represented by the above formula (b5) include those represented by the following formulas (b5-1) to (b5-33).

In formulas (b5-1) to (b5-33) above, R ^24b represents a hydrogen atom or a methyl group.

Preferable specific examples of the structural unit represented by the above formula (b6) include those represented by the following formulas (b6-1) to (b6-26).

In formulas (b6-1) to (b6-26) above, R ^24b represents a hydrogen atom or a methyl group.

Preferable specific examples of the structural unit represented by the above formula (b7) include those represented by the following formulas (b7-1) to (b7-15).

In formulas (b7-1) to (b7-15) above, R ^24b represents a hydrogen atom or a methyl group.

Among the structural units represented by the formulas (b5) to (b7) described above, the structural unit represented by the formula (b6) is preferable because it is easy to synthesize and relatively easy to achieve high sensitivity. Further, among the structural units represented by the formula (b6), structural units in which ^Yb is an alkyl group are preferable, and structural units in which one or both of ^R19b and ^R20b are an alkyl group are preferable.

Furthermore, the acrylic resin (B3) is a resin composed of a copolymer containing structural units derived from a polymerizable compound having an ether bond together with the structural units represented by the above formulas (b5) to (b7). is preferred.

Examples of the polymerizable compound having an ether bond include radically polymerizable compounds such as (meth)acrylic acid derivatives having an ether bond and an ester bond, and specific examples include 2-methoxyethyl (meth)acrylate. , 2-ethoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate Acrylate, methoxypolypropylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate and the like. Moreover, the polymerizable compound having an ether bond is preferably 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, or methoxytriethylene glycol (meth)acrylate. These polymerizable compounds may be used alone or in combination of two or more.

Furthermore, the acrylic resin (B3) can contain other polymerizable compounds as structural units for the purpose of appropriately controlling physical and chemical properties. Examples of such polymerizable compounds include known radically polymerizable compounds and anionically polymerizable compounds.

Examples of such polymerizable compounds include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; 2-methacryloyloxyethylsuccinic acid and 2-methacryloyloxy Methacrylic acid derivatives having a carboxy group and an ester bond such as ethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) ) acrylate, cyclohexyl (meth) acrylate and other (meth) acrylic acid alkyl esters; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and other (meth) acrylic acid hydroxyalkyl esters; phenyl ( (meth)acrylic acid aryl esters such as meth)acrylate and benzyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene , hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene and other vinyl group-containing aromatic compounds; vinyl group-containing aliphatic compounds such as vinyl acetate; butadiene, isoprene and other conjugated diolefins; acrylonitrile, methacrylic nitrile group-containing polymerizable compounds such as ronitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; amide bond-containing polymerizable compounds such as acrylamide and methacrylamide;

As described above, the acrylic resin (B3) may contain a structural unit derived from a polymerizable compound having a carboxy group such as the above monocarboxylic acids or dicarboxylic acids. However, since it is easy to form a resist pattern including a non-resist portion having a rectangular cross-sectional shape, the ratio of structural units derived from a polymerizable compound having a carboxy group in the acrylic resin (B3) is 20. Less than mass % is preferable, 0.1 mass % or more and 15 mass % or less is more preferable, and 1 mass % or more and 10 mass % or less is especially preferable.

Examples of the polymerizable compound include (meth)acrylic acid esters having an acid non-dissociable aliphatic polycyclic group, vinyl group-containing aromatic compounds, and the like. As the acid non-dissociable aliphatic polycyclic group, a tricyclodecanyl group, adamantyl group, tetracyclododecanyl group, isobornyl group, norbornyl group and the like are particularly preferable in terms of industrial availability. These aliphatic polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.

Specific examples of (meth)acrylic acid esters having an acid non-dissociable aliphatic polycyclic group include structures of the following formulas (b8-1) to (b8-5). can.

In formulas (b8-1) to (b8-5) above, R ^25b represents a hydrogen atom or a methyl group.

When the acrylic resin (B3) contains a structural unit (b-3) containing a —SO ₂ —containing cyclic group or a lactone-containing cyclic group, the structural unit (b-3) in the acrylic resin (B3) The content is preferably 50% by mass or less, more preferably 30% by mass or less.

In addition, the acrylic resin (B3) preferably contains 5% by mass or more, more preferably 10% by mass or more, and 10% by mass or more of the structural units represented by the above formulas (b5) to (b7). It is particularly preferable to contain 50% by mass or less.

The acrylic resin (B3) preferably contains a structural unit derived from the polymerizable compound having an ether bond. The content of structural units derived from a polymerizable compound having an ether bond in the acrylic resin (B3) is preferably 0% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 40% by mass or less, and 5% by mass. % or more and 30 mass % or less is more preferable.

The acrylic resin (B3) preferably contains structural units derived from the (meth)acrylic acid esters having the acid non-dissociable aliphatic polycyclic group. In the acrylic resin (B3), the content of structural units derived from (meth)acrylic acid esters having an acid non-dissociable aliphatic polycyclic group is preferably 0% by mass or more and 60% by mass or less. It is more preferably from 5% by mass to 50% by mass, and even more preferably from 5% by mass to 30% by mass.

As long as the photosensitive composition contains a predetermined amount of the acrylic resin (B3), an acrylic resin other than the acrylic resin (B3) described above can also be used as the resin (B). Such an acrylic resin other than the acrylic resin (B3) is not particularly limited as long as it contains the structural units represented by the above formulas (b5) to (b7).

The polystyrene equivalent mass average molecular weight of the resin (B) described above is preferably 10,000 or more and 600,000 or less, more preferably 20,000 or more and 400,000 or less, and still more preferably 30,000 or more and 300,000 or less. With such a weight average molecular weight, it is possible to maintain sufficient strength of the photosensitive layer composed of the photosensitive composition without deteriorating the releasability from the substrate, and furthermore, the swelling of the profile during plating and the occurrence of cracks. easy to prevent from occurring.

Moreover, the degree of dispersion of the resin (B) is preferably 1.05 or more. Here, the degree of dispersion is a value obtained by dividing the weight average molecular weight by the number average molecular weight. Such a degree of dispersion makes it possible to avoid the problem of the desired stress resistance to plating and the tendency of the metal layer obtained by plating to swell.

The content of the resin (B) is preferably 5% by mass or more and 70% by mass or less with respect to the total mass of the photosensitive composition.
In addition, the content of the resin (B) is preferably 5% by mass or more and 99% by mass or less, more preferably 50% by mass or more and 99% by mass or less, relative to the total solid mass of the photosensitive composition. preferable.

<Acid diffusion inhibitor (C)>
The photosensitive composition preferably further contains an acid diffusion inhibitor (C) in order to improve the shape of the resist pattern and the storage stability of the photosensitive resin film. As the acid diffusion inhibitor (C), a nitrogen-containing compound (C1) is preferable, and if necessary, an organic carboxylic acid, or an oxoacid of phosphorus or a derivative thereof (C2) can be contained.

[Nitrogen-containing compound (C1)]
Nitrogen-containing compounds (C1) include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tri-n-pentylamine, tribenzylamine, diethanolamine, triethanolamine, and n-hexylamine. , n-heptylamine, n-octylamine, n-nonylamine, ethylenediamine, N,N,N',N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4 '-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propion Amide, benzamide, pyrrolidone, N-methylpyrrolidone, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, imidazole, benz imidazole, 4-methylimidazole, 8-oxyquinoline, acridine, purine, pyrrolidine, piperidine, 2,4,6-tri(2-pyridyl)-S-triazine, morpholine, 4-methylmorpholine, piperazine, 1,4- Dimethylpiperazine, 1,4-diazabicyclo[2.2.2]octane, pyridine and the like can be mentioned. These may be used alone or in combination of two or more.

In addition, ADEKA STAB LA-52, ADEKA STAB LA-57, ADEKA STAB LA-63P, ADEKA STAB LA-68, ADEKA STAB LA-72, ADEKA STAB LA-77Y, ADEKA STAB LA-77G, ADEKA STAB LA-81, ADEKA STAB LA-82, and ADEKA STAB LA -87 (both manufactured by ADEKA), commercially available hindered amine compounds such as 4-hydroxy-1,2,2,6,6-pentamethylpiperidine derivatives, 2,6-diphenylpyridine, and 2,6- A pyridine substituted with a substituent such as a hydrocarbon group at the 2,6-positions such as di-tert-butylpyridine can also be used as the nitrogen-containing compound (C1).

The nitrogen-containing compound (C1) is usually used in a range of 0 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total mass of the resin (B) and the alkali-soluble resin (D) below, and is used in an amount of 0 parts by mass or more. It is particularly preferable to use it in the range of 3 parts by mass or less.

[Organic carboxylic acid, or phosphorus oxo acid or derivative thereof (C2)]
Among organic carboxylic acids, phosphorus oxoacids, or derivatives thereof (C2), malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, and the like are preferable as organic carboxylic acids. , especially salicylic acid.

Phosphorus oxoacids or derivatives thereof include phosphoric acid, phosphoric acid such as di-n-butyl phosphate, diphenyl phosphate, and derivatives such as esters thereof; Phosphonic acids such as di-n-butyl ester, phenylphosphonic acid, diphenyl phosphonate, dibenzyl phosphonate and derivatives such as esters thereof; phosphinic acids such as phosphinic acid, phenylphosphinic acid and esters thereof; derivative; and the like. Among these, phosphonic acid is particularly preferred. These may be used alone or in combination of two or more.

The organic carboxylic acid or phosphorus oxoacid or derivative thereof (C2) is usually 0 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total mass of the resin (B) and the alkali-soluble resin (D) below. It is particularly preferably used in the range of 0 to 3 parts by mass.

In addition, in order to form a salt and stabilize the organic carboxylic acid or phosphorus oxoacid or its derivative (C2), it is preferable to use an amount equivalent to that of the nitrogen-containing compound (C1).

<Alkali-soluble resin (D)>
The photosensitive composition may not contain the alkali-soluble resin (D), but may contain the alkali-soluble resin (D). Here, the alkali-soluble resin is a resin solution having a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate). When immersed for 1 minute, refers to those that dissolve 0.01 μm or more, and refers to those that do not fall under the above-mentioned resin (B) (typically resins whose alkali solubility does not substantially change due to the action of acid) point.). The alkali-soluble resin (D) is preferably at least one resin selected from the group consisting of novolak resins (D1), polyhydroxystyrene resins (D2), and acrylic resins (D3).

[Novolac resin (D1)]
A novolak resin is obtained, for example, by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as "phenols") and aldehydes in the presence of an acid catalyst.

Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2 ,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5- Trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, phloroglucinol, hydroxydiphenyl, bisphenol A, gallic acid, gallic acid ester, α-naphthol, β-naphthol and the like.
Examples of the aldehydes include formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde.
The catalyst for the addition condensation reaction is not particularly limited, but acid catalysts such as hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid and acetic acid are used.

The flexibility of the novolac resin can be further improved by using o-cresol, substituting the hydrogen atoms of the hydroxyl groups in the resin with other substituents, or using bulky aldehydes. is.

The mass-average molecular weight of the novolac resin (D1) is not particularly limited as long as the object of the present invention is not impaired, but is preferably 1,000 or more and 50,000 or less.

[Polyhydroxystyrene resin (D2)]
Examples of hydroxystyrene-based compounds constituting the polyhydroxystyrene resin (D2) include p-hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene and the like.
Furthermore, the polyhydroxystyrene resin (D2) is preferably a copolymer with a styrene resin. Styrene-based compounds constituting such styrene resins include styrene, chlorostyrene, chloromethylstyrene, vinyltoluene, α-methylstyrene and the like.

The mass average molecular weight of the polyhydroxystyrene resin (D2) is not particularly limited as long as it does not impair the object of the present invention, but it is preferably 1000 or more and 50000 or less.

[Acrylic resin (D3)]
The acrylic resin (D3) preferably contains structural units derived from a polymerizable compound having an ether bond and structural units derived from a polymerizable compound having a carboxy group.

Examples of the polymerizable compound having an ether bond include 2-methoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxypolyethylene glycol ( (Meth)acrylic acid derivatives having an ether bond and an ester bond such as meth)acrylate, methoxypolypropylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and the like can be exemplified. The polymerizable compound having an ether bond is preferably 2-methoxyethyl acrylate or methoxytriethylene glycol acrylate. These polymerizable compounds may be used alone or in combination of two or more.

Examples of the polymerizable compound having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; 2-methacryloyloxyethylsuccinic acid and 2-methacryloyloxy compounds having a carboxy group and an ester bond such as ethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid; The polymerizable compound having a carboxy group is preferably acrylic acid or methacrylic acid. These polymerizable compounds may be used alone or in combination of two or more.

The mass average molecular weight of the acrylic resin (D3) is not particularly limited as long as it does not interfere with the object of the present invention, but it is preferably 50,000 or more and 800,000 or less.

The content of the alkali-soluble resin (D) is preferably 0 parts by mass or more and 80 parts by mass or less, and 0 parts by mass or more and 60 parts by mass, when the total of the resin (B) and the alkali-soluble resin (D) is 100 parts by mass. Part by mass or less is more preferable. By setting the content of the alkali-soluble resin (D) within the above range, there is a tendency that film reduction during development can be prevented.

<Sulfur-containing compound (E)>
When the photosensitive composition is used for pattern formation on a metal substrate, the photosensitive composition preferably contains a sulfur-containing compound (E). A sulfur-containing compound (E) is a compound containing a sulfur atom capable of coordinating to a metal. In addition, with respect to compounds that can produce two or more tautomers, when at least one tautomer contains a sulfur atom that coordinates to the metal that constitutes the surface of the metal substrate, the compound is a sulfur-containing compound. Applicable.
When forming a resist pattern used as a mold for plating on a surface made of a metal such as Cu, problems in the cross-sectional shape such as footing are likely to occur. However, when the photosensitive composition contains the sulfur-containing compound (E), even when a resist pattern is formed on the metal surface of the substrate, it is easy to suppress the occurrence of cross-sectional defects such as footing. Note that "footing" is a phenomenon in which the width of the bottom of the non-resist portion becomes narrower than the width of the top due to the resist portion projecting toward the non-resist portion near the contact surface between the substrate surface and the resist pattern. is.
When the photosensitive composition is used for pattern formation on a substrate other than a metal substrate, it is not particularly necessary for the photosensitive composition to contain a sulfur-containing compound. When the photosensitive composition is used for pattern formation on a substrate other than a metal substrate, the reduction in the number of components of the photosensitive composition facilitates the production of the photosensitive composition and the production of the photosensitive composition. It is preferable that the photosensitive composition does not contain the sulfur-containing compound (E) from the viewpoint of cost reduction.
In addition, there is no particular problem when the photosensitive composition used for pattern formation on a substrate other than a metal substrate contains the sulfur-containing compound (E).

Sulfur atoms that can coordinate to metals include, for example, a mercapto group (-SH), a thiocarboxy group (-CO-SH), a dithiocarboxy group (-CS-SH), and a thiocarbonyl group (-CS-). etc. are included in sulfur-containing compounds.
It is preferable that the sulfur-containing compound has a mercapto group because it is easily coordinated to the metal and has an excellent effect of suppressing footing.

（式中、Ｒ^ｅ１及びＲ^ｅ２は、それぞれ独立に水素原子又はアルキル基を示し、Ｒ^ｅ３は単結合又はアルキレン基を示し、Ｒ^ｅ４は炭素以外の原子を含んでいてもよいｕ価の脂肪族基を示し、ｕは２以上４以下の整数を示す。） Preferred examples of sulfur-containing compounds having a mercapto group include compounds represented by the following formula (e1).

(Wherein, R ^e1 and R ^e2 each independently represent a hydrogen atom or an alkyl group, R ^e3 represents a single bond or an alkylene group, and R ^e4 represents a u-valent aliphatic which may contain an atom other than carbon. group group, and u is an integer of 2 or more and 4 or less.)

When R ^e1 and R ^e2 are alkyl groups, the alkyl groups may be linear or branched, preferably linear. When R ^e1 and R ^e2 are alkyl groups, the number of carbon atoms in the alkyl group is not particularly limited as long as the object of the present invention is not impaired. The number of carbon atoms in the alkyl group is preferably 1 or more and 4 or less, particularly preferably 1 or 2, and most preferably 1. As for the combination of R ^e1 and R ^e2 , one is preferably a hydrogen atom and the other is an alkyl group, and one is particularly preferably a hydrogen atom and the other is a methyl group.

When R ^e3 is an alkylene group, the alkylene group may be linear or branched, preferably linear. When R ^e3 is an alkylene group, the number of carbon atoms in the alkylene group is not particularly limited as long as the object of the present invention is not impaired. The number of carbon atoms in the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, particularly preferably 1 or 2, and most preferably 1.

R ^e4 is a divalent to tetravalent aliphatic group which may contain an atom other than carbon. Atoms other than carbon that R ^e4 may contain include a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. The structure of the aliphatic group represented by R ^e4 may be linear, branched, cyclic, or a combination of these structures.

（式（ｅ２）中、Ｒ^ｅ４及びｕは、式（ｅ１）と同意である。） Among the compounds represented by the formula (e1), compounds represented by the following formula (e2) are more preferable.

(In formula (e2), R ^e4 and u are the same as in formula (e1).)

Among the compounds represented by formula (e2) above, the following compounds are preferred.

（式（ｅ３－Ｌ１）～（ｅ３－Ｌ７）中、Ｒ’、ｓ”、Ａ”、及びｒは、アクリル樹脂（Ｂ３）について前述した、式（ｂ－Ｌ１）～（ｂ－Ｌ７）と同様である。） Compounds represented by the following formulas (e3-L1) to (e3-L7) are also preferred examples of sulfur-containing compounds having a mercapto group.

(In the formulas (e3-L1) to (e3-L7), R′, s″, A″, and r are the formulas (b-L1) to (b-L7) described above for the acrylic resin (B3). It is the same.)

Preferable specific examples of the mercapto compounds represented by the above formulas (e3-L1) to (e3-L7) include the following compounds.

（式（ｅ３－１）～（ｅ３－４）中の略号の定義については、アクリル樹脂（Ｂ３）に関して前述した、式（３－１）～（３－４）について前述した通りである。） Compounds represented by the following formulas (e3-1) to (e3-4) are also preferred examples of sulfur-containing compounds having a mercapto group.

(The definitions of the abbreviations in the formulas (e3-1) to (e3-4) are as described for the formulas (3-1) to (3-4) described above for the acrylic resin (B3).)

Preferred specific examples of the mercapto compounds represented by formulas (e3-1) to (e3-4) above include the following compounds.

（式（ｅ４）において、Ｒ^ｅ５は、水酸基、炭素原子数１以上４以下のアルキル基、炭素原子数１以上４以下のアルコキシ基、炭素数１以上４以下のアルキルチオ基、炭素数１以上４以下のヒドロキシアルキル基、炭素数１以上４以下のメルカプトアルキル基、炭素数１以上４以下のハロゲン化アルキル基及びハロゲン原子からなる群より選択される基であり、ｎ１は０以上３以下の整数であり、ｎ０は０以上３以下の整数であり、ｎ１が２又は３である場合、Ｒ^ｅ５は同一であっても異なっていてもよい。） Moreover, suitable examples of compounds having a mercapto group include compounds represented by the following formula (e4).

(In formula (e4), R ^e5 is a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, A group selected from the group consisting of the following hydroxyalkyl groups, mercaptoalkyl groups having 1 to 4 carbon atoms, halogenated alkyl groups having 1 to 4 carbon atoms and halogen atoms, and n1 is an integer of 0 to 3 and n0 is an integer of 0 or more and 3 or less, and when n1 is 2 or 3, ^Re5 may be the same or different.)

Specific examples of when R ^e5 is an alkyl group optionally having a hydroxyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an isobutyl group. groups, sec-butyl groups, and tert-butyl groups. Among these alkyl groups, methyl group, hydroxymethyl group and ethyl group are preferred.

Specific examples of R ^e5 being an alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy and tert-butyloxy groups. Among these alkoxy groups, a methoxy group and an ethoxy group are preferred, and a methoxy group is more preferred.

Specific examples of R ^e5 being an alkylthio group having 1 to 4 carbon atoms include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio and sec-butylthio. , and tert-butylthio groups. Among these alkylthio groups, a methylthio group and an ethylthio group are preferred, and a methylthio group is more preferred.

Specific examples of R ^e5 being a hydroxyalkyl group having 1 to 4 carbon atoms include a hydroxymethyl group, a 2-hydroxyethyl group, a 1-hydroxyethyl group, a 3-hydroxy-n-propyl group, and 4 -hydroxy-n-butyl group and the like. Among these hydroxyalkyl groups, hydroxymethyl group, 2-hydroxyethyl group and 1-hydroxyethyl group are preferred, and hydroxymethyl group is more preferred.

Specific examples of R ^e5 being a mercaptoalkyl group having 1 to 4 carbon atoms include a mercaptomethyl group, a 2-mercaptoethyl group, a 1-mercaptoethyl group, a 3-mercapto-n-propyl group, and 4 -Mercapto-n-butyl group and the like. Among these mercaptoalkyl groups, mercaptomethyl group, 2-mercaptoethyl group and 1-mercaptoethyl group are preferred, and mercaptomethyl group is more preferred.

When R ^e5 is a halogenated alkyl group having 1 to 4 carbon atoms, examples of the halogen atom contained in the halogenated alkyl group include fluorine, chlorine, bromine and iodine. Specific examples of the case where R ^e5 is a halogenated alkyl group having 1 to 4 carbon atoms include a chloromethyl group, a bromomethyl group, an iodomethyl group, a fluoromethyl group, a dichloromethyl group, a dibromomethyl group, a difluoromethyl group, trichloromethyl group, tribromomethyl group, trifluoromethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-fluoroethyl group, 1,2-dichloroethyl group, 2,2-difluoroethyl group, 1-chloro- 2-fluoroethyl group, 3-chloro-n-propyl group, 3-bromo-n-propyl group, 3-fluoro-n-propyl group, 4-chloro-n-butyl group and the like. Among these halogenated alkyl groups, chloromethyl group, bromomethyl group, iodomethyl group, fluoromethyl group, dichloromethyl group, dibromomethyl group, difluoromethyl group, trichloromethyl group, tribromomethyl group and trifluoromethyl group is preferred, and chloromethyl, dichloromethyl, trichloromethyl and trifluoromethyl groups are more preferred.

Specific examples of R ^e5 being a halogen atom include fluorine, chlorine, bromine, and iodine.

In formula (e4), n1 is an integer of 0 or more and 3 or less, and 1 is more preferable. When n1 is 2 or 3, multiple ^Re5 may be the same or different.

In the compound represented by formula (e4), the substitution position of ^Re5 on the benzene ring is not particularly limited. The substitution position of R ^e5 on the benzene ring is preferably meta or para with respect to the bonding position of —(CH ₂ ) _n0 —SH.

The compound represented by formula (e4) is preferably a compound having at least one group selected from the group consisting of an alkyl group, a hydroxyalkyl group, and a mercaptoalkyl group as R ^e5 , and R ^e5 is an alkyl More preferred are compounds having one group selected from the group consisting of groups, hydroxyalkyl groups, and mercaptoalkyl groups. When the compound represented by formula (e4) has one group selected from the group consisting of an alkyl group, a hydroxyalkyl group, and a mercaptoalkyl group as R ^e5 , an alkyl group, a hydroxyalkyl group, or a mercaptoalkyl group The substitution position of the group on the benzene ring is preferably meta or para to the bonding position of —(CH ₂ ) _n0 —SH, more preferably para.

In formula (e4), n0 is an integer of 0 or more and 3 or less. n0 is preferably 0 or 1, more preferably 0, because of ease of compound preparation and availability.

Specific examples of the compound represented by formula (e4) include p-mercaptophenol, p-thiocresol, m-thiocresol, 4-(methylthio)benzenethiol, 4-methoxybenzenethiol, 3-methoxybenzenethiol, 4-ethoxybenzenethiol, 4-isopropyloxybenzenethiol, 4-tert-butoxybenzenethiol, 3,4-dimethoxybenzenethiol, 3,4,5-trimethoxybenzenethiol, 4-ethylbenzenethiol, 4-isopropylbenzenethiol , 4-n-butylbenzenethiol, 4-tert-butylbenzenethiol, 3-ethylbenzenethiol, 3-isopropylbenzenethiol, 3-n-butylbenzenethiol, 3-tert-butylbenzenethiol, 3,5-dimethylbenzene Thiol, 3,4-dimethylbenzenethiol, 3-tert-butyl-4-methylbenzenethiol, 3-tert-4-methylbenzenethiol, 3-tert-butyl-5-methylbenzenethiol, 4-tert-butyl- 3-methylbenzenethiol, 4-mercaptobenzyl alcohol, 3-mercaptobenzyl alcohol, 4-(mercaptomethyl)phenol, 3-(mercaptomethyl)phenol, 1,4-di(mercaptomethyl)phenol, 1,3-di (mercaptomethyl)phenol, 4-fluorobenzenethiol, 3-fluorobenzenethiol, 4-chlorobenzenethiol, 3-chlorobenzenethiol, 4-bromobenzenethiol, 4-iodobenzenethiol, 3-bromobenzenethiol, 3,4- dichlorobenzenethiol, 3,5-dichlorobenzenethiol, 3,4-difluorobenzenethiol, 3,5-difluorobenzenethiol, 4-mercaptocatechol, 2,6-di-tert-butyl-4-mercaptophenol, 3, 5-di-tert-butyl-4-methoxybenzenethiol, 4-bromo-3-methylbenzenethiol, 4-(trifluoromethyl)benzenethiol, 3-(trifluoromethyl)benzenethiol, 3,5-bis( trifluoromethyl)benzenethiol, 4-methylthiobenzenethiol, 4-ethylthiobenzenethiol, 4-n-butylthiobenzenethiol, 4-tert-butylthiobenzenethiol, and the like.

Examples of sulfur-containing compounds having a mercapto group include compounds containing a nitrogen-containing aromatic heterocycle substituted with a mercapto group, and tautomers of compounds containing a nitrogen-containing aromatic heterocycle substituted with a mercapto group. be done.
Preferred specific examples of nitrogen-containing aromatic heterocycles include imidazole, pyrazole, 1,2,3-triazole, 1,2,4-triazole, oxazole, thiazole, pyridine, pyrimidine, pyridazine, pyrazine, 1,2, 3-triazine, 1,2,4-triazine, 1,3,5-triazine, indole, indazole, benzimidazole, benzoxazole, benzothiazole, 1H-benzotriazole, quinoline, isoquinoline, cinnoline, phthalazine, quinazoline, quinoxaline, and 1,8-naphthyridine.

Specific examples of nitrogen-containing heterocyclic compounds suitable as sulfur-containing compounds and suitable tautomers of nitrogen-containing heterocyclic compounds include the following compounds.

When the photosensitive composition contains a sulfur-containing compound (E), the amount used is 0.01 parts by mass or more and 5 parts by mass with respect to 100 parts by mass of the total mass of the resin (B) and the alkali-soluble resin (D). Part or less is preferable, 0.02 to 3 parts by mass is more preferable, and 0.05 to 2 parts by mass is particularly preferable.

<Dye (F)>
The photosensitive composition may contain a dye (F).
Examples of the dye (F) include azo compounds and curcumin, but other dyes may also be used. Specific examples of the dye (F) include 2-benzeneazo-4-methylphenol, 2,2',4,4'-tetrahydroxybenzophenone, 4-dimethylamino-2',4'-dihydroxybenzophenone, 5-amino -3-methyl-1-phenyl-4-(4-hydroxyphenylazo)pyrazole, 4-dimethylamino-4'-hydroxyazobenzene, 4-diethylamino-4'-ethoxyazobenzene, 4-diethylaminoazobenzene, curcumin, 1, 7-bis(3-methoxy-4-hydroxyphenyl)-1,6-heptadiene-3,5-dione, 5-hydroxy-4-(4-methoxyphenylazo)-3-methyl-1-phenylpyrazole and the like mentioned.

When the photosensitive composition contains the dye (F), the amount used is 0.0005 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total mass of the resin (B) and the alkali-soluble resin (D). is preferable, 0.001 to 3 parts by mass is more preferable, and 0.003 to 1 part by mass is particularly preferable.

<Organic solvent (S)>
The photosensitive composition preferably contains an organic solvent (S). The type of organic solvent (S) is not particularly limited as long as the object of the present invention is not impaired, and it can be appropriately selected from organic solvents conventionally used in photosensitive compositions.

Specific examples of the organic solvent (S) include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate. , propylene glycol monomethyl ether acetate, dipropylene glycol, monomethyl ether of dipropylene glycol monoacetate, monoethyl ether, monopropyl ether, monobutyl ether, monophenyl ether and other polyhydric alcohols and derivatives thereof; cyclic ethers such as dioxane Group; ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate aromatic hydrocarbons such as toluene and xylene; and the like. These may be used alone or in combination of two or more.

The organic solvent (S) has a solid content concentration of 25% by mass or more and 70% by mass or less, preferably 30% by mass or more and 60% by mass or less, more preferably 40% by mass or more and 50% by mass or less. used in

<Other ingredients>
The photosensitive composition may further contain a polyvinyl resin to improve plasticity. Specific examples of polyvinyl resins include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinyl benzoic acid, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl phenol, and copolymers thereof. are mentioned. The polyvinyl resin is preferably polyvinyl methyl ether because of its low glass transition point.

The photosensitive composition may contain a Lewis acidic compound. When the photosensitive composition contains a Lewis acidic compound, it is easy to obtain a highly sensitive photosensitive composition, and it is easier to form a resist pattern having a rectangular cross-sectional shape using the photosensitive composition.
Further, when a pattern is formed using a photosensitive composition, it is difficult to form a pattern of a desired shape and size if the time required for each step during pattern formation or the time required between each step is long. Adverse effects such as deterioration of developability may occur. However, by incorporating a Lewis acidic compound into the photosensitive composition, such adverse effects on the pattern shape and developability can be mitigated, and the process margin can be widened.

Here, the Lewis acidic compound means "a compound having an empty orbit capable of accepting at least one electron pair and acting as an electron pair acceptor".
The Lewis acidic compound is not particularly limited as long as it corresponds to the above definition and is recognized as a Lewis acidic compound by those skilled in the art. As the Lewis acidic compound, compounds other than Bronsted acids (protonic acids) are preferably used.
Specific examples of Lewis acidic compounds include boron fluoride and ether complexes of boron fluoride (e.g., BF ₃ .Et _{2 O, BF 3 .Me 2 O ,} BF ₃ .THF, etc. Et is an ethyl group, Me is a methyl group, and THF is tetrahydrofuran.), organic boron compounds (e.g., tri-n-octyl borate, tri-n-butyl borate, triphenyl borate, triphenyl boron, etc.), titanium chloride, chloride Aluminum, aluminum bromide, gallium chloride, gallium bromide, indium chloride, thallium trifluoroacetate, tin chloride, zinc chloride, zinc bromide, zinc iodide, zinc trifluoromethanesulfonate, zinc acetate, zinc nitrate, tetrafluoroborate zinc oxide, manganese chloride, manganese bromide, nickel chloride, nickel bromide, nickel cyanide, nickel acetylacetonate, cadmium chloride, cadmium bromide, stannous chloride, stannous bromide, stannous sulfate, and and stannous tartrate.
Further, other specific examples of Lewis acidic compounds include rare earth metal elements such as chloride, bromide, sulfate, nitrate, carboxylate, or trifluoromethanesulfonate, and cobalt chloride, ferrous chloride, and yttrium chloride. be done.
Examples of rare earth metal elements include lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.

The Lewis acidic compound preferably contains a Lewis acidic compound containing an element of Group 13 of the periodic table because it is easily available and the effect of its addition is good.
Here, elements of Group 13 of the periodic table include boron, aluminum, gallium, indium, and thallium.
Among the above Group 13 elements of the periodic table, boron is preferable because it is easy to obtain a Lewis acidic compound and the addition effect is particularly excellent. That is, the Lewis acidic compound preferably contains a Lewis acidic compound containing boron.

Examples of Lewis acidic compounds containing boron include boron halides such as boron fluoride, boron fluoride ether complexes, boron chloride and boron bromide, and various organic boron compounds. As the Lewis acidic compound containing boron, an organic boron compound is preferable because the content ratio of halogen atoms in the Lewis acidic compound is small and the photosensitive composition can be easily applied to applications requiring a low halogen content.

Preferred examples of organic boron compounds include the following formula (f1):
B(R ^f1 ) _t1 (OR ^f2 ) _(3−t1) (f1)
(In the formula (f1), R ^f1 and R ^f2 are each independently a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have one or more substituents, and t1 is an integer of 0 or more and 3 or less, and when a plurality of R ^f1 are present, two of the plurality of R ^f1 may be bonded to each other to form a ring, and when a plurality of OR ^f2 are present, a plurality of OR Two of ^f2 may be joined together to form a ring.)
A boron compound represented by is mentioned. The photosensitive composition preferably contains one or more boron compounds represented by the above formula (f1) as the Lewis acidic compound.

When R ^f1 and R ^f2 in formula (f1) are hydrocarbon groups, the hydrocarbon group has 1 or more and 20 or less carbon atoms. The hydrocarbon group having 1 to 20 carbon atoms may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a hydrocarbon group consisting of a combination of an aliphatic group and an aromatic group. There may be.
As the hydrocarbon group having 1 to 20 carbon atoms, a saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group is preferable. The number of carbon atoms in the hydrocarbon groups for R ^f1 and R ^f2 is preferably 1 or more and 10 or less. When the hydrocarbon group is an aliphatic hydrocarbon group, the number of carbon atoms thereof is more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 4 or less.
The hydrocarbon groups for R ^f1 and R ^f2 may be saturated hydrocarbon groups or unsaturated hydrocarbon groups, and are preferably saturated hydrocarbon groups.
When the hydrocarbon group for R ^f1 and R ^f2 is an aliphatic hydrocarbon group, the aliphatic hydrocarbon group may be linear, branched, or cyclic, Combinations of these structures may also be used.

Preferred specific examples of aromatic hydrocarbon groups include phenyl, naphthalene-1-yl, naphthalene-2-yl, 4-phenylphenyl, 3-phenylphenyl and 2-phenylphenyl groups. be done. Among these, a phenyl group is preferred.

An alkyl group is preferred as the saturated aliphatic hydrocarbon group. Preferred specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl and n-hexyl. n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl groups.

The hydrocarbon groups as R ^f1 and R ^f2 may have one or more substituents. Examples of substituents include halogen atoms, hydroxyl groups, alkyl groups, aralkyl groups, alkoxy groups, cycloalkyloxy groups, aryloxy groups, aralkyloxy groups, alkylthio groups, cycloalkylthio groups, arylthio groups, aralkylthio groups, and acyl groups. , acyloxy group, acylthio group, alkoxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, amino group, N-monosubstituted amino group, N,N-disubstituted amino group, carbamoyl group (-CO-NH ₂ ) , N-monosubstituted carbamoyl group, N,N-disubstituted carbamoyl group, nitro group, cyano group and the like.
The number of carbon atoms in the substituent is not particularly limited as long as the object of the present invention is not impaired, but is preferably 1 to 10, more preferably 1 to 6.

Suitable specific examples of the organoboron compound represented by the above formula (f1) include the following compounds. In the following formulas, Pen represents a pentyl group, Hex represents a hexyl group, Hep represents a heptyl group, Oct represents an octyl group, Non represents a nonyl group, and Dec represents a decyl group.

The Lewis acidic compound is preferably used in a range of 0.01 parts by mass or more and 5 parts by mass or less, more preferably 0 parts by mass, based on 100 parts by mass of the total mass of the resin (B) and the alkali-soluble resin (D). It is used in the range of 0.01 to 3 parts by mass, more preferably in the range of 0.05 to 2 parts by mass.

In addition, when the photosensitive composition is used to form a pattern that serves as a mold for forming a plated model, the photosensitive composition is used to improve the adhesion between the mold formed using the photosensitive composition and the metal substrate. may also contain adhesion promoters.

In addition, the photosensitive composition may further contain a surfactant in order to improve coating properties, defoaming properties, leveling properties, and the like. As the surfactant, for example, fluorine-based surfactants and silicone-based surfactants are preferably used.
Specific examples of fluorosurfactants include BM-1000, BM-1100 (all manufactured by BM Chemie), Megafac F142D, Megafac F172, Megafac F173, and Megafac F183 (all from Dainippon Ink and Chemicals). company), Florado FC-135, Florado FC-170C, Florard FC-430, Florard FC-431 (all manufactured by Sumitomo 3M), Surflon S-112, Surfon S-113, Surfon S-131, Surfon S- 141, Surflon S-145 (both manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (both manufactured by Toray Silicone Co., Ltd.) and other commercially available fluorine-based surfactants include, but are not limited to.
Examples of silicone-based surfactants include unmodified silicone-based surfactants, polyether-modified silicone-based surfactants, polyester-modified silicone-based surfactants, alkyl-modified silicone-based surfactants, aralkyl-modified silicone-based surfactants, and A reactive silicone surfactant or the like can be preferably used.
A commercially available silicone surfactant can be used as the silicone surfactant. Specific examples of commercially available silicone surfactants include Paintad M (manufactured by Dow Corning Toray Co., Ltd.), Topica K1000, Topica K2000, Topica K5000 (all manufactured by Takachiho Sangyo Co., Ltd.), XL-121 (polyether-modified silicone surfactant, manufactured by Clariant), BYK-310 (polyester-modified silicone surfactant, manufactured by BYK-Chemie), and the like.

Moreover, the photosensitive composition may further contain an acid or an acid anhydride in order to finely adjust the solubility in the developer.

Specific examples of acids and acid anhydrides include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid, and cinnamic acid; lactic acid, 2-hydroxybutyric acid, Hydroxymonocarboxylic acids such as 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid and syringic acid Acids; oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid Polyvalent carboxylic acids such as acids, butanetetracarboxylic acid, trimellitic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, 1,2,5,8-naphthalenetetracarboxylic acid; itaconic anhydride, anhydride succinic acid, citraconic anhydride, dodecenylsuccinic anhydride, tricarbanilic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hymic anhydride, 1,2,3,4-butanetetracarboxylic anhydride, acid anhydrides such as cyclopentanetetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis anhydride trimellitate, glycerol tris anhydride trimellitate; can.

Moreover, the photosensitive composition may further contain a known sensitizer in order to improve sensitivity.

The photosensitive composition described above is prepared by mixing and stirring the components described above in a conventional manner. Apparatuses that can be used for mixing and stirring the above components include a dissolver, a homogenizer, a three-roll mill, and the like. After uniformly mixing the above components, the resulting mixture may be filtered using a mesh, membrane filter, or the like.

The above photosensitive composition has excellent storage stability. Therefore, even after a long period of time (for example, two weeks) has passed since the preparation of the photosensitive composition, and even if the photosensitive composition is stored at a relatively high temperature (for example, 40°C), the change in viscosity is suppressed. .

<<Photosensitive dry film and method for producing photosensitive dry film>>
A photosensitive dry film has a base film and a photosensitive layer formed on the surface of the base film, and the photosensitive layer is composed of the aforementioned photosensitive composition.

As the substrate film, one having light transmittance is preferable. Specific examples thereof include polyethylene terephthalate (PET) film, polypropylene (PP) film, polyethylene (PE) film, etc., but polyethylene terephthalate (PET) film is preferred in that it has an excellent balance between light transmittance and breaking strength.

A photosensitive dry film is produced by applying the aforementioned photosensitive composition onto a substrate film to form a photosensitive layer.
When forming the photosensitive layer on the base film, an applicator, bar coater, wire bar coater, roll coater, curtain flow coater, etc. are used to form a film having a thickness of preferably 0.5 μm after drying on the base film. The photosensitive composition is applied to a thickness of 300 μm or more, more preferably 1 μm or more and 300 μm or less, particularly preferably 3 μm or more and 100 μm or less, and dried.
Since the above photosensitive composition has a high solid content concentration, it is suitable for forming a thick photosensitive layer (for example, 70 μm or more).

The photosensitive dry film may further have a protective film on the photosensitive layer. Examples of the protective film include polyethylene terephthalate (PET) film, polypropylene (PP) film, polyethylene (PE) film, and the like.

<<Method for manufacturing patterned resist film and substrate with template>>
A method for forming a patterned resist film on a substrate using the photosensitive composition described above is not particularly limited. Such a patterned resist film is suitably used as an insulating film, an etching mask, a mold for forming a plated model, and the like.
A suitable method is
A lamination step of laminating a photosensitive layer made of a photosensitive composition on a substrate;
an exposure step of exposing the photosensitive layer by position-selectively irradiating it with actinic rays or radiation;
A developing step of developing the photosensitive layer after exposure;
A method for producing a patterned resist film, comprising:
A method for manufacturing a mold-equipped substrate provided with a mold for forming a plated model includes the steps of using a substrate having a metal surface as the substrate and laminating a photosensitive layer on the metal surface of the substrate having the metal surface. In the developing step, the method is the same as the method for producing a patterned resist film, except that a mold for forming a plated modeled article is prepared by development.

The substrate on which the photosensitive layer is laminated is not particularly limited, and conventionally known substrates can be used. can be done. A silicon substrate, a glass substrate, or the like can also be used as the substrate.
A substrate having a metal surface is used as the substrate when manufacturing a substrate with a mold provided with a mold for forming a plated modeled article. Copper, gold, and aluminum are preferable as the metal species constituting the metal surface, and copper is more preferable.

The photosensitive layer is laminated on the substrate, for example, as follows. That is, a photosensitive layer having a desired thickness is formed by applying a liquid photosensitive composition onto a substrate and removing the solvent by heating. The thickness of the photosensitive layer is not particularly limited as long as the resist pattern can be formed with a desired thickness. Although the film thickness of the photosensitive layer is not particularly limited, it is preferably 0.5 μm or more, more preferably 1 μm or more, and still more preferably 10 μm or more. The upper limit of the film thickness is, for example, 300 μm or less.
Since the above photosensitive composition has a high solid content concentration, a thick photosensitive layer can be formed. Therefore, for example, it can be preferably used for forming a plated modeled article.

Methods such as spin coating, slit coating, roll coating, screen printing, and applicator methods can be employed as methods for applying the photosensitive composition onto the substrate. It is preferable to pre-bake the photosensitive layer. The pre-baking conditions vary depending on the type and mixing ratio of each component in the photosensitive composition, the coating film thickness, etc., but are usually 70° C. or higher and 200° C. or lower, preferably 80° C. or higher and 150° C. or lower, for 2 minutes or more and 120° C. minutes or less. Pre-baking may be performed multiple times in two or more steps. For example, after the first stage prebaking is performed at a temperature of 70° C. or more and 120° C. or less, the second stage prebaking may be performed at a temperature higher than that of the first stage.

The photosensitive layer formed as described above is selectively irradiated (exposed) with actinic rays or radiation, such as ultraviolet rays or visible rays having a wavelength of 300 nm or more and 500 nm or less, through a mask of a predetermined pattern. be.

Low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon gas lasers, and the like can be used as radiation sources. Radiation includes microwaves, infrared rays, visible rays, ultraviolet rays, X-rays, γ-rays, electron beams, proton beams, neutron beams, ion beams, and the like. Although the dose of radiation varies depending on the composition of the photosensitive composition, the film thickness of the photosensitive layer, etc., it is, for example, 100 mJ/cm ² or more and 10000 mJ/cm ² or less. Radiation also includes light rays that activate the acid generator (A) to generate acid.

After exposure, the photosensitive layer is heated (PEB) by a known method to promote the diffusion of the acid, and the exposed portions of the photosensitive layer are developed with an alkaline developer or the like. Changes the solubility in liquids.

Next, the exposed photosensitive layer is developed according to a conventionally known method, and unnecessary portions are dissolved and removed to form a mold for forming a predetermined resist pattern or a plated model. At this time, an alkaline aqueous solution is used as the developer.

The repelling of the developer is suppressed in the exposed photosensitive layer formed using the above photosensitive composition. For this reason, for example, a developer can be brought into contact with the entire photosensitive layer, and a mold for forming a resist pattern corresponding to a mask or the like and a plated modeled object can be applied over the entire area where the photosensitive layer is provided. can be formed.
In addition, swelling during development is suppressed in the exposed photosensitive layer formed using the above photosensitive composition. For this reason, for example, the mold for forming the obtained resist pattern or plated modeled article is suppressed from wrinkles, dissolution of unexposed portions, floating and distortion caused by swelling.

Examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5,4,0]-7-undecene, 1,5-diazabicyclo[4,3, Aqueous solutions of alkalis such as 0]-5-nonane can be used. Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the above aqueous solution of alkalis can be used as a developer.

The development time varies depending on the composition of the photosensitive composition, the film thickness of the photosensitive layer, etc., but is usually between 1 minute and 30 minutes. The developing method may be any of a liquid-filling method, a dipping method, a puddle method, a spray developing method, and the like.

After development, for example, washing with running water is performed for 30 seconds or more and 90 seconds or less, and drying is performed using an air gun, an oven, or the like. Thus, a resist pattern patterned into a desired shape is formed on the metal surface of the substrate having the metal surface. Also, in this way, a substrate having a resist pattern on the substrate surface can be manufactured.
In this way, cracks are suppressed in the photosensitive layer formed using the above-described photosensitive composition. Therefore, for example, when the obtained resist pattern is used as a mold for forming a plated modeled article, it is easy to form a plated modeled article having a desired shape.

≪Manufacturing method of plated model≫
By embedding a conductor such as metal by plating in the non-resist part (the part removed by the developer) in the mold of the substrate with the mold formed by the above method, connection terminals such as bumps and metal posts, etc. , Cu rewiring can be formed. The plating method is not particularly limited, and conventionally known various methods can be employed. Solder plating, copper plating, gold plating, and nickel plating solutions are particularly suitable as the plating solution. The remaining template is finally removed using a stripping solution or the like according to conventional methods.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples.

[Examples 1 to 8 and Comparative Examples 1 to 18]
In Examples and Comparative Examples, PAG1 and PAG2 of the following formula were used as the acid generator (A).

In Examples and Comparative Examples, the following B1 to B4 and B'1 to B'16 were used as resins (resin (B)) whose solubility in alkali increases under the action of acid. The lower right number of parentheses in each structural unit in the following structural formula represents the content (% by mass) of the structural unit in the resin. Table 1 below shows the weight average molecular weight Mw and the degree of dispersion (Mw/Mn) of each resin.

In Examples and Comparative Examples, the following C1 and the compound C2 of the following formula were used as the acid diffusion controller (C).
C1: Adekastab LA-63P (1,2,3,4-butanetetracarboxylic acid methyl ester, 1,2,2,6,6-pentamethyl-4-piperidinol, and β,β,β',β'- Reaction product with tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol) (made by ADEKA)

As the alkali-soluble resin (D), the following D1 (novolac resin (condensate of m-cresol and p-cresol)) was used. The weight average molecular weight (Mw) of D1 is 8,000.

In the examples and comparative examples, the sulfur-containing compound E1 of the following formula was used as the sulfur-containing compound (E).

In Examples and Comparative Examples, F1 below was used as the dye (F).
F1: Curcumin

containing acid generator (A), resin (B), acid diffusion controller (C), alkali-soluble resin (D), and dye (F), each of the type and weight part shown in Table 2; 0.1 parts by mass of E1 as a sulfur compound (E) and 0.02 parts by mass of a surfactant (BYK310, manufactured by BYK-Chemie Co.) were mixed with 3-methoxybutyl so that the solid content concentration was 48% by mass. By dissolving in acetate (organic solvent (S)), photosensitive compositions of Examples 1 to 8 and Comparative Examples 1 to 18 were obtained. In addition, the solid content concentration is the component other than the organic solvent (S)), the resin (B), the acid generator (A), the acid diffusion controller (C), the alkali-soluble resin (D), the sulfur-containing compound ( It was determined by dividing the total weight of E), dye (F) and surfactant by the weight of the photosensitive composition.

Using the obtained photosensitive composition, evaluation was performed according to the following methods. Table 2 shows the results.
[Evaluation of resist pattern (developer repellency, swelling and crack resistance)]
The photosensitive compositions of Examples and Comparative Examples were applied onto a copper film of a copper-sputtered silicon wafer substrate (thickness of copper film: 200 nm) using a spinner, and this was heated on a hot plate at 100°C. for 150 seconds and 150° C. for 450 seconds (pre-baking) to obtain a photosensitive layer having a thickness of 100 μm.
After heating (pre-baking), using a mask with a square pattern of 30 μm×30 μm and a projection exposure apparatus Prisma GHI5452 (manufactured by Ultratec), 1.2 times the minimum exposure amount capable of forming a pattern of a predetermined size. The photosensitive layer was selectively exposed with the ghi line at the exposure dose.
The substrate was then placed on a hot plate and subjected to post-exposure baking (PEB) at 100° C. for 3 minutes. Thereafter, a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution (developer, NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) is dropped onto the exposed photosensitive layer and left at 23° C. for 60 seconds ( puddle development), and this was repeated 6 times for development. Thereafter, the substrate was washed with running water for 60 seconds and spin-dried to obtain a substrate with a resist pattern (patterned resist film).
Evaluation of repellency of the developer refers to the case where the developer is not repelled during development and the developer is spread over the entire photosensitive layer, and a square pattern corresponding to the mask is formed over the entire area where the photosensitive layer is provided. ○Evaluation: When the developer was repelled during development and the developer could not spread over the entire surface of the photosensitive layer, resulting in poor formation of the resist pattern (when there was an area where the square pattern was not formed, or when the square pattern was formed but The case where the shape was significantly different from the mask) was evaluated as x.
Swelling evaluation was performed when the photosensitive layer did not swell during development, wrinkles were not observed in the resist pattern obtained, unexposed areas were not dissolved, and lifting and distortion were not observed. ○Evaluated. In addition, when the unexposed portion of the photosensitive layer swells during development, and wrinkles are observed in the resulting resist pattern, when the unexposed portion is dissolved, or when lifting or distortion is observed, x Evaluation.
Crack resistance was evaluated by observing the obtained resist pattern (square pattern), and when cracks were observed at the corners of the square pattern, it was evaluated as x, and when cracks were not observed at the corners of the square pattern. ○Evaluated.

[Evaluation of storage stability]
The viscosities of the photosensitive compositions of Examples and Comparative Examples were measured using an E-type viscometer at 25° C. immediately after preparation and after standing at 40° C. for 2 weeks.
When the ratio V2/V1 between the viscosity V1 immediately after preparation and the viscosity V2 after standing at 40° C. for 2 weeks was less than 1.1, it was evaluated as ◯, and when it was 1.1 or more, it was evaluated as x. Table 2 shows the results.

According to Examples, an acid generator (A) that generates an acid upon exposure to actinic rays or radiation, and a resin (B) that increases solubility in alkali under the action of an acid are contained, and the resin (B) is represented by the formula ( A chemically amplified positive photosensitive composition containing an acrylic resin (B3) containing a structural unit represented by B3-1) and having a solid content concentration of 25% by mass or more and 70% by mass or less has good storage stability. , and the repelling and swelling of the developer can be suppressed, and a thick photosensitive layer having excellent crack resistance can be formed.

On the other hand, according to Comparative Examples, a chemically amplified positive photosensitive composition that does not contain an acrylic resin (B3) containing a structural unit represented by formula (B3-1) as a resin (B) has storage stability. Otherwise, it is found that the formed photosensitive layer repels the developer, swells, or cracks.

Claims (11)

containing an acid generator (A) that generates an acid upon exposure to actinic rays or radiation, and a resin (B) that increases solubility in alkali under the action of acid;
The resin (B) contains an acrylic resin (B3),
The acrylic resin (B3) has the following formula (B3-1):

(In formula (B3-1), R ^b01 is a hydrogen atom or a methyl group, R ^b02 is a single bond or a linking group, R ^b03 is a hydrogen atom or an aliphatic hydrocarbon group, R ^b04 and R ^b05 are each independently a single bond or an aliphatic hydrocarbon group, R ^b04 and R ^b05 are not both single bonds, and R ^b06 and R ^b07 are each independently a hydrogen atom or It is an aliphatic hydrocarbon group, and one of R ^b02 and R ^b03 may be bonded to a carbon atom constituting the main chain of the acrylic resin (B3) to form a ring, and R ^b02 and R ^b03 They may combine to form a ring, R ^b02 and R ^b05 may combine to form a ring, and R ^b06 and R ^b07 may combine to form a ring.)
contains a structural unit represented by
A chemically amplified positive photosensitive composition having a solid content concentration of 25% by mass or more and 70% by mass or less. The structural unit represented by the formula (B3-1) is represented by the following formula (B3-2):

(In formula (B3-2), R ^b01 , R ^b03 , R ^b04 , R ^b05 , R ^b06 , and R ^b07 are the same as those in formula (B3-1) above, and R ^b010 is a single bond or It is a hydrocarbon group, and R ^b05 and R ^b010 may combine to form a ring.)
2. The chemically amplified positive photosensitive composition according to claim 1, which is a structural unit represented by: In the formula (B3-2), R ^b03 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ^b04 and R ^b05 are each independently a single bond or a methylene group, and R ^b06 and R ^b07 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ^b010 is a methylene group. The ratio of the mass of the structural unit represented by the formula (B3-1) to the mass of the acrylic resin (B3) is 5% by mass or more and 50% by mass or less, according to any one of claims 1 to 3 The chemically amplified positive-acting photosensitive composition as described. 5. The chemically amplified positive photosensitive composition according to any one of claims 1 to 4, further comprising a sulfur-containing compound (E) containing a sulfur atom capable of coordinating to a metal. 6. The chemically amplified positive photosensitive composition according to any one of claims 1 to 5, which is used for forming a mold for forming a plated model. The chemically amplified positive photosensitive composition has a viscosity of V1 when measured using an E-type viscometer at 25 ° C., and the chemically amplified positive photosensitive composition is allowed to stand at 40 ° C. for 2 weeks, Claim that V2/V1 is less than 1.1 when the viscosity of the chemically amplified positive photosensitive composition after standing is measured at 25°C using an E-type viscometer and V2 is the viscosity. 7. The chemically amplified positive photosensitive composition according to any one of 1 to 6. The chemically amplified positive photosensitive composition according to any one of claims 1 to 7, comprising a base film and a photosensitive layer formed on the surface of the base film, wherein the photosensitive layer is A photosensitive dry film consisting of A lamination step of laminating a photosensitive layer comprising the chemically amplified positive photosensitive composition according to any one of claims 1 to 7 on a substrate;
an exposure step of position-selectively irradiating the photosensitive layer with actinic rays or radiation;
and a developing step of developing the photosensitive layer after exposure. A lamination step of laminating a photosensitive layer comprising the chemically amplified positive photosensitive composition according to any one of claims 1 to 7 on a substrate having a metal surface;
an exposure step of position-selectively irradiating the photosensitive layer with actinic rays or radiation;
A method for producing a substrate with a template, comprising a developing step of developing the exposed photosensitive layer to prepare a template for forming a plated modeled article. A method for producing a plated modeled article, comprising the step of plating the substrate with a template produced by the method for producing a substrate with a template according to claim 10 to form a plated modeled article in the mold.