CN114556214B - Resin composition, photosensitive resin composition and cured product thereof - Google Patents

Abstract

A resin composition comprising: a polymer containing a structural unit represented by the formula (NB) and a structural unit represented by the formula (1); and a compound having 2 or more (meth) acryloyl groups. In the formula (NB), R ¹、R²、R³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a ₁ is 0, 1 or 2. In the formula (1), R ^p is a group having 2 or more (meth) acryloyl groups.

Description

Resin composition, photosensitive resin composition and cured product thereof

Technical Field

The present invention relates to a resin composition, a photosensitive resin composition and a cured product thereof, and more particularly to a resin composition, a photosensitive resin composition containing the resin composition and a cured product of the photosensitive resin composition.

Background technique

Liquid crystal display devices or solid-state imaging elements usually have color filters or black matrices. The color filter or black matrix is formed on a substrate and has a structure such as a coloring pattern or a protective film. As a method for forming a coloring pattern or a protective film in these structures, a method of forming by photolithography using a photosensitive resin composition has become the mainstream. Various studies have been conducted on photosensitive resin compositions. For example, Patent Document 1 describes a photosensitive resin composition containing an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator, wherein the alkali-soluble resin contains at least a group having an acidic group in a side chain and two or more polymerizable unsaturated groups that are different from each other. In addition, the following is described in the examples of Patent Document 1: a methacrylic acid/allyl methacrylate/glycidol adduct is synthesized as an alkali-soluble resin, and the photosensitive resin composition is prepared using the alkali-soluble resin.

Prior art literature

Patent Literature

Patent document 1: International Publication No. 2012/147706.

Summary of the invention

Technical issues to be solved by the invention

A resin having the property of being cured by a polymerization reaction produced by light is used in the photosensitive resin composition for forming a color filter or a black matrix. The color filter or the black matrix is made by curing the photosensitive resin composition after patterning it by exposure and development. In the photosensitive resin composition, "high sensitivity" is also considered to be a common subject, but with the complexity or popularization of display devices or camera devices, a higher level of high sensitivity is required. The higher the sensitivity of the photosensitive resin composition, the shorter the time required for exposure, thereby improving productivity. In addition, the photosensitive resin composition is required to have excellent processability in the development process using an alkaline developer.

The present inventors have found that by improving the polymer used in the photosensitive resin composition or the formulation of the composition, a photosensitive resin composition having good sensitivity and high alkali solubility and excellent developability can be obtained, thereby arriving at the present invention.

Means for solving technical problems

According to the present invention, there is provided a resin composition comprising: a polymer containing a structural unit represented by formula (NB) and a structural unit represented by formula (1); and a compound having two or more (meth)acryloyl groups.

(In formula (NB), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a ₁ is 0, 1 or 2.)

(In formula (1), R ^p is a group having two or more (meth)acryloyl groups.)

Furthermore, according to the present invention, there is provided a photosensitive resin composition comprising: a polymer containing a structural unit represented by formula (NB) and a structural unit represented by formula (1); a compound having two or more (meth)acryloyl groups; and a photosensitizer.

(In formula (NB), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a ₁ is 0, 1 or 2.)

(In formula (1), R ^p is a group having two or more (meth)acryloyl groups.)

Furthermore, according to the present invention, there is provided a cured product, which is formed from the above-mentioned photosensitive resin composition.

Effects of the Invention

According to the present invention, there is provided a resin composition as a resin material for a photosensitive resin composition having good sensitivity and high alkali solubility and excellent developability.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagram (cross-sectional view) schematically showing an example of the structure of a liquid crystal display device and/or a solid-state imaging element.

Detailed ways

Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. In addition, in all the drawings, the same symbols are marked for the same components, and the description is appropriately omitted. Moreover, all the drawings are for illustration only. The shapes or dimensional ratios of the components in the drawings do not necessarily correspond to actual items. In this specification, the expression "a to b" in the description of the numerical range means greater than a and less than b unless otherwise specified. For example, "5 to 90%" means "greater than 5% and less than 90%".

In the description of the group (group, atomic group) in this specification, the description without the mark of substituted or unsubstituted includes both the group without substitution and the group with substitution. For example, "alkyl" includes not only the group without substitution (unsubstituted alkyl) but also the group with substitution (substituted alkyl).

The term "(meth)acrylic acid" in this specification is a concept including both acrylic acid and methacrylic acid. The same applies to similar terms such as "(meth)acrylate".

In particular, the "(meth)acryloyl group" in the present specification is a concept including an acryloyl group represented by -C(=O)-CH=CH ₂ and a methacryloyl group represented by -C(=O)-C(CH ₃ )=CH ₂ .

(Resin composition)

The resin composition of the present embodiment is used as a resin material for preparing a photosensitive resin composition. The resin composition of the present embodiment contains: a polymer P containing a structural unit described in detail below; and a compound having two or more (meth)acryloyl groups.

(Polymer P)

The polymer P used in the resin composition of the present embodiment contains a structural unit represented by the formula (NB) and a structural unit represented by the formula (1). In addition, these structural units typically constitute the main chain of the polymer P.

In formula (NB), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a ₁ is 0, 1 or 2.

In formula (1), R ^p is a group having two or more (meth)acryloyl groups.

The polymer P used in the resin composition of the present embodiment contains a structural unit represented by formula (1). Thus, the photosensitive resin composition containing the polymer P has excellent sensitivity when applied to photolithography. It is believed that this is because the curing reaction (polymerization reaction) is promoted by two or more (meth)acryloyl groups contained in the structural unit represented by formula (1). In addition, the polymer P contains a structural unit represented by formula (NB). The structural unit (NB) is chemically strong. Therefore, the polymer P containing it as a structural unit has a small weight loss when applied to heat treatment and is stable. Therefore, in order to manufacture a film or filter used in a liquid crystal display device or a solid-state imaging element that requires heat resistance, a photosensitive resin composition containing polymer P can be suitably used.

In one embodiment, the polymer P contains a structural unit represented by formula (2) in addition to the above structural units.

In formula (2), R ^s is a group having one (meth)acryloyl group.

By containing the structural unit represented by formula (2) in addition to the structural unit represented by formula (1), the polymer P has higher sensitivity and high alkali solubility, and can be suitably used in processing by photolithography.

In one embodiment, the polymer P may contain a structural unit represented by formula (3) in addition to the above structural unit. By containing the structural unit represented by formula (3), the polymer P has higher alkali solubility. As a result, the photosensitive resin composition containing the polymer P has excellent developability when provided for photolithography using an alkaline aqueous solution as a developer.

In one embodiment, the polymer P may contain a structural unit represented by formula (MA) in addition to the above structural units. The structural unit represented by formula (MA) generates two carboxyl groups by ring opening in an alkaline developer. Therefore, the polymer P containing the structural unit has excellent developability. When the polymer P contains the structural unit represented by formula (MA), the structural unit represented by formula (MA) in all the structural units of the polymer P is preferably 1 to 10 mol%, more preferably 2 to 7 mol%.

In one embodiment, the polymer P may contain a thioether group (—S—) in addition to the above structure. The thioether group is a group derived from a thiol group-containing compound used as a chain transfer agent when the polymer P is synthesized.

In the structural unit represented by the formula (NB) constituting the polymer P, examples of the organic group having 1 to 30 carbon atoms that can constitute R ¹ to R ⁴ include substituted or unsubstituted linear or branched alkyl groups having 1 to 30 carbon atoms, and more specifically include alkyl groups, alkenyl groups, alkynyl groups, alkylene groups, aryl groups, aralkyl groups, alkaryl groups, cycloalkyl groups, alkoxy groups, heterocyclic groups, and carboxyl groups.

Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl and decyl groups.

Examples of the alkenyl group include an allyl group, a pentenyl group, and a vinyl group.

Examples of the alkynyl group include ethynyl group and the like.

Examples of the alkylene group include a methylene group and an ethylene group.

Examples of the aryl group include tolyl, xylyl, phenyl, naphthyl and anthracenyl.

Examples of the aralkyl group include a benzyl group and a phenethyl group.

Examples of the alkaryl group include tolyl and xylyl groups.

Examples of the cycloalkyl group include adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl.

Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, an n-pentoxy group, a neopentoxy group, and an n-hexyloxy group.

Examples of the heterocyclic group include an epoxy group and an oxetane group.

R ¹ , R ² , R ³ and R ⁴ in the structural unit represented by the formula (NB) are preferably hydrogen or an alkyl group, and more preferably hydrogen.

In addition, hydrogen atoms in the organic groups having 1 to 30 carbon atoms of ^R1 , ^R2 , ^R3 and ^R4 may be substituted with any atomic groups. For example, they may be substituted with fluorine atoms, hydroxyl groups, carboxyl groups, etc. More specifically, as the organic groups having 1 to 30 carbon atoms of ^R1 , ^R2 , ^R3 and ^R4 , fluorinated alkyl groups, etc. may be selected.

In the structural unit represented by formula (NB), _a1 is preferably 0 or 1, and more preferably 0.

The ratio of the structural unit represented by the formula (NB) in all structural units of the polymer P is preferably 10 to 90 mol %, more preferably 30 to 70 mol %, and even more preferably 40 to 60 mol %.

In the present embodiment, the polymer P has a structural unit represented by formula (1), in other words, a structural unit containing two or more (meth)acryloyl groups (—C(═O)—CH═CH ₂ ). This can improve the sensitivity of the polymer P in the exposure process.

In the structural unit represented by formula (1) constituting the polymer P, ^{Rp is} a group containing two or more (meth)acryloyl groups, preferably a group containing 2 to 6 (meth)acryloyl groups, and more preferably a group containing 3 to 5 (meth)acryloyl groups. By optimally setting the number of (meth)acryloyl groups contained in ^Rp , the sensitivity of the polymer P containing it in the exposure process can be further improved. In addition, it is easy to more highly balance the sensitivity and alkali solubility of the polymer P. In addition, the heat resistance of the polymer P can be improved.

R ^p is preferably a group represented by formula (1b) or a group represented by formula (1c). By using such a group, the above-mentioned various effects tend to be easily obtained.

R ^p in formula (1) is preferably a group represented by formula (1b), a group represented by formula (1c) or a group represented by formula (1d). By using such a group, the above-mentioned various effects tend to be easily obtained.

In formula (1b):

k is 2 or 3.

R is a hydrogen atom or a methyl group, and a plurality of Rs may be the same or different.

^X1 is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -ZX- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), and a plurality of ^X1 may be the same or different,

X ¹ ' is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -X'-Z'- (X' is an alkylene group having 1 to 6 carbon atoms, and Z' is -O- or -COO-).

^X2 is a k+1-valent organic group having 1 to 12 carbon atoms.

From the viewpoint of further improving sensitivity (easiness of polymerization) and the like, R is preferably a hydrogen atom.

k may be 2 or 3, but is preferably 3 from the viewpoint of further improving the availability of raw materials and the sensitivity.

When ^X1 is an alkylene group having 1 to 6 carbon atoms, the alkylene group may be linear or branched.

When X ¹ is an alkylene group having 1 to 6 carbon atoms, X ¹ is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and further preferably -CH ₂ -(methylene group).

When ^X1 is a group represented by -ZX- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), the alkylene group having 1 to 6 carbon atoms of X may be linear or branched.

The alkylene group having 1 to 6 carbon atoms represented by X is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and further preferably -CH ₂ -CH ₂ -(ethylene) or -CH ₂ -CH(CH ₃ )-.

When X ¹ ' is an alkylene group having 1 to 6 carbon atoms, its specific embodiment is the same as that of X ¹ .

When X ¹ ' is a group represented by -X'-Z'-, the specific embodiment of X' is the same as that of X described above.

As the k+1-valent organic group having 1 to 12 carbon atoms of ^X2 , there can be mentioned any group obtained by removing k+1 hydrogen atoms from any organic compound. The "any organic compound" here refers to, for example, an organic compound having a molecular weight of 300 or less, preferably 200 or less, and more preferably 100 or less.

^X2 is, for example, a group formed by removing k+1 hydrogen atoms from a linear or branched hydrocarbon having 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms). More preferably, it is a group formed by removing k+1 hydrogen atoms from a linear hydrocarbon having 1 to 3 carbon atoms. In addition, the hydrocarbon here may contain an oxygen atom (for example, an ether bond or a hydroxyl group). Furthermore, the hydrocarbon is preferably a saturated hydrocarbon.

As another embodiment, ^X2 may be a group containing a cyclic structure. Examples of the group containing a cyclic structure include a group containing an alicyclic structure and a group containing a heterocyclic structure (for example, an isocyanuric acid structure).

In formula (1c):

k, R, ^X1 and ^X2 have the same meanings as R, k, ^X1 and ^X2 in formula (1b), respectively. A plurality of Rs may be the same as or different from each other, and a plurality of ^X1s may be the same as or different from each other.

^X3 is a divalent organic group having 1 to 6 carbon atoms.

^X4 and ^X5 are each independently a single bond or a divalent organic group having 1 to 6 carbon atoms.

^X6 is a divalent organic group having 1 to 6 carbon atoms.

Specific embodiments and preferred embodiments of R, k, ^X1 and ^X2 are the same as those described in the general formula (1b).

Examples of the divalent organic group having 1 to 6 carbon atoms for ^X3 and ^X6 include groups obtained by removing two hydrogen atoms from a linear or branched hydrocarbon having 1 to 6 carbon atoms. The hydrocarbon herein may contain an oxygen atom (e.g., an ether bond or a hydroxyl group). The hydrocarbon is preferably a saturated hydrocarbon.

Examples of the divalent organic group having 1 to 6 carbon atoms for ^X4 and ^X5 include linear or branched alkylene groups. The linear or branched alkylene group preferably has 1 to 3 carbon atoms.

In formula (1d):

n is an integer of 2 to 5, and is preferably 2 or 3.

Specific embodiments, preferred embodiments, etc. of R are the same as those described in the general formula (1b).

The ratio of the structural unit represented by the formula (1) in all the structural units of the polymer P is preferably 3 to 40 mol%, more preferably 3 to 30 mol%.

In the structural unit represented by formula (2), ^RS is a group containing only one (meth)acryloyl group. In one embodiment, the polymer P may contain "a structural unit of formula (2) containing only one acryloyl group" in addition to "a structural unit of formula (1) containing two or more (meth)acryloyl groups". By containing these two structural units in the polymer P, it is possible to achieve a higher degree of balance between sensitivity and developability. In particular, in the design of a conventional photosensitive resin composition, when the curability is increased in order to increase the sensitivity, the curing is excessively performed and the developability tends to deteriorate. On the other hand, when the developability is improved, the curing tends to become insufficient. Therefore, the polymer P preferably contains a combination of a structural unit represented by formula (1) and a structural unit represented by formula (2), thereby achieving a good balance between sensitivity and developability.

RS ^is , for example, a group represented by the following formula (2a).

As mentioned above, although embodiment of this invention was described, these are illustrations of this invention, and various structures other than the above-mentioned can also be adopted.

In formula (2a), ^X10 is a divalent organic group, and R is a hydrogen atom or a methyl group.

The total number of carbon atoms of ^X10 is preferably 1-30, more preferably 1-20, and even more preferably 1-10.

In formula (2a), ^X10 is a divalent organic group, and R is a hydrogen atom or a methyl group.

The total number of carbon atoms of ^X10 is preferably 1-30, more preferably 1-20, and even more preferably 1-10.

The divalent organic group represented by ^X10 is preferably an alkylene group, for example. _-CH2- , which is a part of the alkylene group, may be an ether group (-O-). The alkylene group may be linear or branched, and is more preferably linear.

The divalent organic group represented by ^X10 is more preferably a linear alkylene group having a total carbon number of 3 to 6. By appropriately selecting the carbon number of ^X10 (chain length of ^X10 ), the structural unit represented by formula (2) can further easily participate in the crosslinking reaction, thereby improving the sensitivity.

The divalent organic group (for example, an alkylene group) represented by ^X10 may be substituted with any substituent, and examples of the substituent include an alkyl group, an aryl group, an alkoxy group, and an aryloxy group.

Furthermore, the divalent organic group represented by ^X10 may be any group other than an alkylene group. For example, it may be a divalent group formed by linking one or more groups selected from an alkylene group, a cycloalkylene group, an arylene group, an ether group, a carbonyl group, a carboxyl group, and the like.

When the polymer P contains a structural unit represented by the formula (2), the proportion of the structural unit represented by the formula (2) in all the structural units of the polymer P is preferably 5 to 40 mol%, more preferably 10 to 30 mol%.

Furthermore, when the polymer P contains a structural unit represented by formula (1) and a structural unit represented by formula (2), the total content of the structural unit represented by formula (1) and the structural unit represented by formula (2) in the polymer P is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, and further preferably 10 to 40 mol%, based on all the structural units constituting the polymer P.

The content (ratio) of each structural unit contained in the polymer P can be estimated/calculated based on the charge amount (molar amount) of the raw materials used in synthesizing the polymer, the amount of the raw materials remaining after synthesis, the presence and peak area of various spectra (e.g., IR spectrum, ¹ H-NMR spectrum, ¹³ C-NMR spectrum), and the like.

The weight average molecular weight Mw of the polymer P is, for example, 1000 to 20000, preferably 2000 to 18000, more preferably 3000 to 14000, further preferably 3000 to 12000. By appropriately adjusting the weight average molecular weight, the sensitivity or the solubility in the alkaline developer can be adjusted.

Furthermore, the dispersion degree (weight average molecular weight Mw/number average molecular weight Mn) of the polymer P is preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and further preferably 1.0 to 3.0. By appropriately adjusting the dispersion degree, the physical properties of the polymer P can be made homogeneous, so it is preferred. In addition, these values can be obtained by measuring with gel permeation chromatography (GPC) using polystyrene as a standard substance.

The glass transition temperature of polymer P is preferably 150 to 250° C., more preferably 170 to 230° C. The polymer P has a relatively high glass transition temperature by mainly containing the structural unit represented by formula (NB). This is preferred from the viewpoint that the pattern formed on the substrate can be stably present when manufacturing a liquid crystal display device or a solid-state imaging element. In addition, the glass transition temperature can be obtained, for example, by differential thermal analysis (DTA).

(Compound Having Two or More (Meth)Acryloyl Groups (Polyfunctional (Meth)Acrylic Compound))

The resin composition of the present embodiment contains a compound having two or more (meth)acryloyl groups. By containing such a compound, the alkali solubility of the resin composition is improved, and the yellowing of the resin composition is further reduced, so that a cured product with excellent transparency can be obtained. The multifunctional (meth)acrylic compound is preferably 3 to 9 functional, and more preferably 3 to 6 functional. By adding such a (meth)acrylic compound with a functional group to the resin composition, the sensitivity of the obtained resin composition can be improved.

As the compound having two or more (meth)acryloyl groups used in the resin composition of the present embodiment (referred to as "multifunctional (meth)acrylic compound" in this specification), for example, the compound represented by the following formula (1b-p), the compound represented by the formula (1c-p) and the compound represented by the formula (1d-p) can be mentioned, but it is not limited to these. The definitions and specific forms of k, R, ^X1 , ^X1 ' and ^X2 in the formula (1b-p) are the same as those in the above formula (1b). In addition, the definitions and specific forms of k, R, ^X1 , ^X2 , ^X3 , ^X4 , ^X5 and ^X6 in the formula (1c-p) are the same as those in the above formula (1c). Y in the formula (1b-p), the formula (1c-p) and the formula (1d-p) is a hydrogen atom or a (meth)acryloyl group or a combination thereof. n in the formula (1d-p) is an integer of 2 or more, preferably an integer of 2 to 5, and more preferably an integer of 2 to 3. R in the formula (1d-p) is the same as in the above formula (1d).

Specific examples of the polyfunctional (meth)acrylic compound represented by formula (1b-p) include compounds of the following structures, but are not limited thereto. In the following compounds, Y represents a hydrogen atom or a (meth)acryloyl group or a combination thereof.

Specific examples of the polyfunctional (meth)acrylic compound represented by the formula (1c-p) include the following compounds, but are not limited to these.

X: --CH ₂ -CH ₂ -O--, a+b+c: 4～8

X: --CH ₂ -CH ₂ -O--, a+b+c+d+e+f: 6～12

(Compound having one (meth)acryloyl group)

The resin composition of the present embodiment may contain a compound having one (meth)acryloyl group (referred to as a "monofunctional (meth)acrylic compound" in this specification). By containing a monofunctional (meth)acrylic compound, the alkali solubility of the obtained resin composition is improved, and yellowing is further reduced.

Examples of the monofunctional (meth)acrylic compound used in the resin composition of the present embodiment include compounds represented by the following formula (2a-m): In the formula (2a-m), the definitions of ^X10 and R are the same as in the formula (2a).

Specific examples of the compound represented by formula (2a-m) include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 2-(meth)acryloyloxyethyl-2-hydroxyethyl-phthalic acid.

In the resin composition of the present embodiment, the above-mentioned multifunctional (meth) acrylic compound is formulated in an amount such that the peak area derived from the multifunctional (meth) acrylic compound in the gel permeation chromatography (GPC) diagram of the resin composition is, for example, 5 to 150% relative to the peak area of the polymer P. The lower limit of the peak area derived from the multifunctional (meth) acrylic compound relative to the peak area of the polymer P is preferably 10% or more, more preferably 20% or more, further preferably 30% or more, further preferably 40% or more, and particularly preferably 50% or more. The upper limit of the peak area derived from the multifunctional (meth) acrylic compound relative to the peak area of the polymer P is preferably 140% or less, more preferably 135% or less, further preferably 130% or less, further preferably 125% or less, and particularly preferably 120% or less. By formulating the multifunctional (meth) acrylic compound in the above range, the obtained resin composition has excellent alkali solubility.

When a monofunctional (meth)acrylic compound is added to the resin composition of the present embodiment, the amount thereof is added in such an amount that the peak area derived from the monofunctional (meth)acrylic compound in the gel permeation chromatography (GPC) diagram of the resin composition is, for example, 5 to 60% relative to the peak area of the polymer P. The lower limit of the peak area derived from the monofunctional (meth)acrylic compound relative to the peak area of the polymer P is preferably 7% or more, more preferably 9% or more, and further preferably 10% or more. The upper limit of the peak area derived from the monofunctional (meth)acrylic compound relative to the peak area of the polymer P is preferably 55% or less, more preferably 50% or less, and further preferably 45% or less. By adding the monofunctional (meth)acrylic compound in the above range, the obtained resin composition has excellent alkali solubility and improved heat discoloration resistance.

Since the resin composition of the present embodiment has the above-mentioned configuration, the alkali dissolution rate thereof can be, for example, 250 nm/s or more, or preferably 280 nm/s or more.

The resin composition of the present embodiment typically contains an organic solvent and is provided in the form of a liquid or a varnish. As the organic solvent, one or more of a ketone solvent, an ester solvent, an ether solvent, an alcohol solvent, a lactone solvent, a carbonate solvent, etc. can be used.

Specific examples of the organic solvent include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, γ-butyrolactone, N-methylpyrrolidone, cyclohexanone, etc. These may be used alone or in combination of two or more.

The amount of the organic solvent used is not particularly limited, and the organic solvent is used in an amount such that the concentration of the nonvolatile component becomes, for example, 10 to 70% by mass, preferably 15 to 60% by mass.

(Production of Polymer P)

Here, a method for producing the above-mentioned polymer P will be described.

The polymer P can be produced (synthesized) by any method. The polymer P can be produced, for example, by the following steps: step (I): a step of preparing a base polymer containing a structural unit represented by formula (NB) and a structural unit represented by formula (MA); and step (II): a step of reacting the base polymer obtained in step (I) with a compound having a hydroxyl group and two or more (meth)acryloyl groups (hereinafter referred to as "multifunctional (meth)acrylic monomer") in the presence of a basic catalyst to prepare a polymer P containing a structural unit represented by formula (NB) and a structural unit represented by formula (1), and, if necessary, further containing a structural unit represented by formula (MA).

When the polymer P further contains a structural unit represented by formula (2), it can be produced by the following step: in step (II), the base polymer obtained in step (I), a multifunctional (meth)acrylic monomer and a compound having a hydroxyl group and one (meth)acryloyl group (hereinafter referred to as "monofunctional (meth)acrylic monomer") are reacted in the presence of a basic catalyst to prepare a polymer P containing a structural unit represented by formula (NB), a structural unit represented by formula (1), a structural unit represented by formula (2) and, if necessary, a structural unit represented by formula (MA).

When the polymer P further contains a structural unit represented by formula (3), in step (II), a polymer containing a structural unit represented by formula (NB), a structural unit represented by formula (1) and/or a structural unit represented by formula (2), and a structural unit represented by formula (MA) is prepared, and then a step of treating the polymer with water in the presence of a base catalyst is carried out (step (III)).

When the polymer P contains a thioether group, such a polymer P can be produced by using a base polymer into which a thioether group is introduced in step (II). Specifically, the base polymer containing a thioether group can be obtained by producing a base polymer containing a structural unit represented by formula (NB), a structural unit represented by formula (MA) and a thioether group in step (I). The production of the base polymer into which a thioether group is introduced is described in detail below.

When both a polyfunctional (meth)acrylic monomer and a monofunctional (meth)acrylic monomer are used in step (II), it is preferred that the polyfunctional (meth)acrylic monomer is first reacted with the base polymer and then the monofunctional (meth)acrylic monomer is reacted with the obtained reaction mixture.

(Step (I))

The step of preparing a base polymer containing a structural unit represented by formula (NB) and a structural unit represented by formula (MA) in step (I) includes a step of obtaining a target base polymer by polymerizing (addition polymerization) a monomer represented by formula (NBm) and maleic anhydride. In formula (NBm), R ¹ , R ² , R ³ , R ⁴ , and a ₁ have the same definitions as those in formula (NB). The same also applies to preferred embodiments.

When a base polymer into which a thiol group is introduced is prepared in step (I), such a base polymer can be produced by polymerizing (addition polymerization) a monomer represented by formula (NBm) and maleic anhydride in the presence of a thiol group-containing compound. The thiol group introduced into the obtained base polymer is a group derived from a thiol group possessed by the thiol group-containing compound.

Examples of the monomer represented by the formula (NBm) include norbornene, norbornadiene, bicyclo[2.2.1]-hept-2-ene (common name: 2-norbornene), 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-allyl-2-norbornene, 5-(2-propenyl)-2-norbornene, 5-(1-methyl-4-pentenyl)-2-norbornene, 5-ethynyl-2-norbornene, 5-benzyl-2-norbornene, 5-phenethyl-2-norbornene, 2-acetyl-5-norbornene, 5-norbornene-2-carboxylic acid methyl ester, and 5-norbornene-2,3-dicarboxylic anhydride. In the polymerization, the monomer represented by the formula (NBm) may be used alone or in combination of two or more.

As the thiol group-containing compound used for producing the base polymer into which the thiol group is introduced, it is preferred to use a thiol group-containing compound having two or more thiol groups, in other words, a difunctional or higher thiol group-containing compound, and more preferably a trifunctional to hexafunctional thiol group-containing compound. By using such a thiol group-containing compound, the sensitivity of the obtained polymer P can be improved.

Specific examples of the thiol group-containing compound include compounds represented by the following formulae (s-1) to (s-20), but are not limited thereto. The thiol group-containing compound may be used alone or in combination of two or more.

The polymerization method of the monomer represented by formula (NBm) and maleic anhydride is not limited, but free radical polymerization using a free radical polymerization initiator is preferred. As the polymerization initiator, for example, an azo compound, an organic peroxide, etc. can be used.

Specific examples of the azo compound include azobisisobutyronitrile (AIBN), 2,2′-azobis(2-methylpropionic acid)dimethyl ester, and 1,1′-azobis(cyclohexanecarbonitrile) (ABCN).

Examples of the organic peroxide include hydrogen peroxide, di(tert-butyl)peroxide (DTBP), benzoyl peroxide (BPO), and methyl ethyl ketone peroxide (MEKP).

The polymerization initiator may be used alone or in combination of two or more.

As the solvent used in the polymerization reaction, for example, an organic solvent such as diethyl ether, tetrahydrofuran, toluene, methyl ethyl ketone, etc. can be used. The polymerization solvent may be a single solvent or a mixed solvent.

The synthesis of the base polymer containing the structural unit represented by the formula (NB) and the structural unit represented by the formula (MA) can be carried out by dissolving the monomer represented by the formula (NBm), maleic anhydride and a polymerization initiator in a solvent and adding them into a reaction vessel, followed by heating to carry out addition polymerization. The heating temperature is, for example, 50 to 80° C., and the heating time is, for example, 5 to 20 hours.

The molar ratio of the monomer represented by the formula (NBm) to maleic anhydride when charged into the reaction container is preferably 0.5:1 to 1:0.5. From the viewpoint of controlling the molecular structure, the molar ratio is preferably 1:1.

Through such steps, a "base polymer" can be obtained.

In addition, the base polymer may be any of a random copolymer, an alternating copolymer, a block copolymer, a periodic copolymer, etc. A typical example is a random copolymer or an alternating copolymer. In addition, maleic anhydride is generally known as a monomer with strong alternating copolymerizability.

The synthesis of the raw polymer into which the sulfide group is introduced, which contains the structural unit represented by the formula (NB), the structural unit represented by the formula (MA), and the sulfide group, is carried out by dissolving the monomer represented by the formula (NBm), maleic anhydride, and a polymerization initiator in a solvent and charging the solvent into a reaction vessel, and then heating the solvent and performing addition polymerization while dropping the thiol group-containing compound. The heating temperature is, for example, 50 to 80° C., and the heating time is, for example, 5 to 20 hours.

The molar ratio of the monomer represented by the formula (NBm) to maleic anhydride when charged into the reaction container is preferably 0.5:1 to 1:0.5. From the viewpoint of controlling the molecular structure, the molar ratio is preferably 1:1.

Furthermore, from the viewpoint of controlling the sulfide group content in the base polymer into which the sulfide group is introduced and the molecular weight of the base polymer, the amount of the thiol group-containing compound charged is preferably 0.5 to 10 mol %, particularly preferably 1 to 8 mol %, and further preferably 2 to 6 mol %, relative to the total molar amount of the monomer represented by the formula (NBm) and maleic anhydride charged into the reaction container.

After the raw material polymer is synthesized, a step of removing low molecular weight components such as unreacted monomers, oligomers, and residual polymerization initiators may be performed.

Specifically, the organic phase containing the synthesized base polymer and low molecular weight components is concentrated, and then mixed with an organic solvent such as tetrahydrofuran (THF) to obtain a solution. Then, the solution is mixed with a poor solvent such as methanol to precipitate the monomer. The precipitate is filtered and dried, thereby improving the purity of the base polymer.

The base polymer obtained in step (I) is used in the following steps (II) and (III) to produce the polymer P of the present embodiment. In the following description, the case where a base polymer composed of a structural unit represented by formula (NB) and a structural unit represented by formula (MA) is used as the base polymer obtained in step (I), but the same method can be used even when a base polymer into which a sulfide group is introduced is used, and the polymer P obtained in this case contains a sulfide group.

(Step (II))

The base polymer obtained in step (I), the polyfunctional (meth)acrylic monomer, and the optionally contained monofunctional (meth)acrylic monomer are reacted in the presence of a basic catalyst to ring-open a portion of the structural unit represented by formula (MA) contained in the base polymer. When the structural unit represented by formula (1) and the monofunctional (meth)acrylic monomer are used, the structural unit represented by formula (2) is formed, thereby obtaining a polymer P containing the structural unit represented by formula (NB) as well as the structural unit represented by formula (1) and the structural unit represented by formula (2) (when a monofunctional (meth)acrylic monomer is used) and optionally containing the structural unit represented by formula (MA).

More specifically, a solution is first prepared by dissolving a base polymer in an appropriate organic solvent. As the organic solvent, a single solvent or a mixed solvent such as methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), tetrahydrofuran (THF) can be used, but it is not limited to these, and various organic solvents used in the synthesis of organic compounds or polymers can be used.

Next, a multifunctional (meth)acrylic monomer is added to the above solution. A basic catalyst is further added. Then, the solution is appropriately mixed to form a uniform solution, thereby obtaining a polymer containing at least a structural unit of formula (NB) and a structural unit of formula (1) (step (II-i)).

Examples of the polyfunctional (meth)acrylic monomer that can be used include compounds represented by the above formula (1b-p), compounds represented by the formula (1c-p), and compounds represented by the formula (1d-p) wherein Y is a hydrogen atom.

Next, a monofunctional (meth)acrylic monomer is reacted with the polymer obtained in step (II-i) in the presence of a basic catalyst, thereby obtaining a polymer containing at least a structural unit of formula (NB), a structural unit of formula (1), and a structural unit of formula (2) (step (II-ii)).

Only one of step (II-i) and step (II-ii) may be performed, but step (II-i) is preferably performed. When both step (II-i) and step (II-ii) are performed, step (II-ii) is preferably performed after step (II-i).

(Step (III))

When the step (III) is carried out, a step of treating the polymer obtained in the step (II) with water in the presence of a basic catalyst is used. In the step (III), the structural unit represented by the formula (MA) contained in the polymer obtained in the step (II) is ring-opened to form the structural unit represented by the formula (3), thereby producing a polymer P containing the structural unit represented by the formula (NB), the structural unit represented by the formula (1) and/or the structural unit represented by the formula (2), and the structural unit represented by the formula (3). When a part of the structural unit represented by the formula (MA) is ring-opened, and a part of the structural unit of the formula (MA) remains without ring-opening, the polymer P contains the structural unit represented by the formula (MA) in addition to the structural units of the formula (NB), the formula (1) and the formula (2) (when a monofunctional (meth)acrylic monomer is used in the step (II)) and the formula (3).

Examples of the basic catalyst used in step (III) include amine compounds such as triethylamine, pyridine, and dimethylaminopyridine, and nitrogen-containing heterocyclic compounds.

In step (III), water is added to the reaction system containing the polymer obtained in step (II), and the obtained reaction solution is preferably heated at 60 to 80° C. for about 0.25 to 6 hours, thereby the structural unit of formula (MA) contained in the polymer is ring-opened to generate the structural unit represented by formula (3). The basic catalyst can directly use the catalyst remaining in the reaction system obtained in step (II). Therefore, step (III) is preferably implemented by adding water to the reaction mixture in situ without performing any post-treatment on the reaction mixture obtained in step (II).

(Manufacture of resin composition)

The resin composition of the present embodiment can be produced by mixing the above components by a known method. The resin composition of the present embodiment is used as a resin material of a photosensitive resin composition described below.

(Photosensitive resin composition)

The photosensitive resin composition of this embodiment contains the above-mentioned polymer P, a compound having two or more (meth)acryloyl groups (multifunctional (meth)acrylic compound), and a photosensitizer. That is, the photosensitive resin composition of this embodiment contains the above-mentioned resin composition of this embodiment and a photosensitizer. Each component is described below.

The polymer P and the polyfunctional (meth)acrylic compound used in the photosensitive resin composition of the present embodiment are the same as those described above.

As the photosensitizer used in the photosensitive resin composition of the present embodiment, a photoradical polymerization initiator can be mentioned. As the photoradical polymerization initiator, a known compound can be used, for example, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-〔4-(2-hydroxyethoxy)phenyl〕-2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1-{4-〔4-(2-hydroxy-2-methylpropionyl)benzyl〕phenyl}-2-methylpropane-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-(dimethylamino)- Alkyl benzophenone compounds such as 2-〔(4-methylphenyl)methyl〕-1-〔4-(4-morpholinyl)phenyl〕-1-butanone; benzophenone compounds such as benzophenone, 4,4'-bis(dimethylamino)benzophenone, and 2-carboxybenzophenone; benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; thioxanthone compounds such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethylthioxanthone; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxy)- halogenated methylated triazine compounds such as 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine; halogenated methylated oxadiazole compounds such as 2-trichloromethyl-5-(2'-benzofuranyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuranyl)vinyl]-1,3,4-oxadiazole, 4-oxadiazole, 2-trichloromethyl-5-furanyl-1,3,4-oxadiazole; 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2' -biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole and other biimidazole compounds; 1,2-octanedione, 1-〔4-(phenylthio)-2-(O-benzoyl oxime)〕, ethyl ketone, 1-〔9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl〕-1-(O-acetyl oxime) and other oxime ester compounds; bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium and other titanocene compounds; benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; acridine compounds such as 9-phenylacridine, etc. The photoradical polymerization initiator may be used alone or in combination of two or more.

The photoradical polymerization initiator is used in an amount of, for example, 1 to 20 parts by mass, and preferably 3 to 10 parts by mass, based on 1000 parts by mass of the polymer P.

The photosensitive resin composition of the present embodiment has high sensitivity in photolithography by containing the above-mentioned components, and has excellent alkali solubility. Therefore, the photosensitive resin composition has excellent developability and excellent processability in photolithography. In addition, since the yellowing of the photosensitive resin composition is suppressed, the article obtained by curing the photosensitive resin composition has transparency.

As one embodiment, the photosensitive resin composition may contain a colorant. By containing a colorant, it can be preferably used as a material for forming a color filter of a liquid crystal display device or a solid-state imaging element. As the colorant, various pigments or dyes can be used.

As the pigment, an organic pigment or an inorganic pigment can be used.

As organic pigments, azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindolinone pigments, isoindolinone pigments, dioxazine pigments, thioindigo pigments, anthraquinone pigments, quinophthalone pigments, metal complex pigments, diketopyrrolopyrrole pigments, xanthene pigments, pyrromethene pigments, dye lake pigments, etc. can be used.

As inorganic pigments, white/body pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.), colored pigments (chrome yellow, cadmium series, chrome vermilion, nickel titanium, chrome titanium, yellow iron oxide, hematite, zinc chromate, red lead, ultramarine, iron blue, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc.), brightening material pigments (pearlescent pigments, aluminum pigments, bronze pigments, etc.), fluorescent pigments (zinc sulfide, strontium sulfide, strontium aluminate, etc.) can be used.

As the dye, for example, known dyes described in Japanese Patent Application Laid-Open No. 2003-270428, Japanese Patent Application Laid-Open No. 9-171108, Japanese Patent Application Laid-Open No. 2008-50599, etc. can be used.

When the photosensitive resin composition contains a colorant, the photosensitive resin composition may contain only one type of colorant, or may contain two or more types of colorants.

Colorants (especially pigments) can have an appropriate average particle size depending on the purpose or application. When transparency such as a color filter is particularly required, a small average particle size of less than 0.1 μm is preferably used. In addition, when hiding properties such as coatings are required, a large average particle size of more than 0.5 μm is preferably used.

The colorant may be subjected to surface treatment such as rosin treatment, surfactant treatment, resin dispersant treatment, pigment derivative treatment, oxide film treatment, silica coating, wax coating, etc. depending on the purpose or use.

When the photosensitive resin composition contains a colorant, the amount thereof may be appropriately set depending on the purpose or application, but from the viewpoint of achieving both color concentration and dispersion stability of the colorant, the amount is preferably 3 to 70% by mass, more preferably 5 to 60% by mass, and even more preferably 10 to 50% by mass, relative to the total non-volatile components (components other than the solvent) of the photosensitive resin composition.

As one embodiment, the photosensitive resin composition may contain a light-shielding agent. By containing a light-shielding agent, it can be preferably used as a material for forming a black matrix of a liquid crystal display device or a solid-state imaging element.

As the light shielding agent, a known light shielding agent can be used without particular limitation. For example, black pigments such as carbon black, bone black, graphite, iron black, and titanium black can be used as the light shielding agent.

When the photosensitive resin composition contains a light-shielding agent, the photosensitive resin composition may contain only one type of light-shielding agent, or may contain two or more types.

When the photosensitive resin composition contains a light-shielding agent, the amount thereof may be appropriately set depending on the purpose or application. However, from the viewpoint of achieving both light-shielding performance and dispersion stability of the light-shielding agent, the amount is preferably 3 to 70% by mass, more preferably 5 to 60% by mass, and even more preferably 10 to 50% by mass, relative to the total non-volatile components (components other than the solvent) of the photosensitive resin composition.

The photosensitive resin composition typically contains a solvent. As the solvent, an organic solvent can be preferably used. Specifically, one or more of ketone solvents, ester solvents, ether solvents, alcohol solvents, lactone solvents, carbonate solvents, etc. can be used.

Examples of solvents include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, methyl isobutyl carbinol (MIBC), γ-butyrolactone (GBL), N-methylpyrrolidone (NMP), methyl n-amyl ketone (MAK), diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone or a mixture thereof.

The amount of the solvent used is not particularly limited, and the solvent is used in an amount such that the concentration of the nonvolatile component becomes, for example, 10 to 70% by mass, preferably 15 to 60% by mass.

As one embodiment, the photosensitive resin composition may contain a crosslinking agent.

The crosslinking agent is not particularly limited as long as it can crosslink the polymer (can chemically bond to the polymer) by the action of active chemical species generated from the photopolymerization initiator.

Crosslinkers can not only chemically bond with polymers, but also react with each other to form bonds.

The crosslinking agent is preferably a polyfunctional compound having two or more polymerizable double bonds in one molecule, and more preferably a polyfunctional (meth)acrylic compound having two or more (meth)acryloyl groups in one molecule (however, the crosslinking agent does not correspond to the polymer). From the viewpoints of uniform curability and further improvement of sensitivity, it is preferred to use a crosslinking agent having the same type of crosslinking group (polymerizable double bond) as the crosslinking group (polymerizable double bond) possessed by the polymer.

The upper limit of the number of functions (the number of polymerizable double bonds) per molecule of the cross-linking agent is not particularly limited, but is, for example, 8 or less, and preferably 6 or less.

Specific examples of the cross-linking agent include the following.

Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, bisphenol F alkylene oxide di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide addition trimethylolpropane tri(meth)acrylate, ethylene oxide addition Polyfunctional (meth)acrylates such as ditrimethylolpropane tetra(meth)acrylate, ethylene oxide added pentaerythritol tetra(meth)acrylate, ethylene oxide added dipentaerythritol hexa(meth)acrylate, propylene oxide added trimethylolpropane tri(meth)acrylate, propylene oxide added ditrimethylolpropane tetra(meth)acrylate, propylene oxide added pentaerythritol tetra(meth)acrylate, propylene oxide added dipentaerythritol hexa(meth)acrylate, ε-caprolactone added trimethylolpropane tri(meth)acrylate, ε-caprolactone added ditrimethylolpropane tetra(meth)acrylate, ε-caprolactone added pentaerythritol tetra(meth)acrylate, and ε-caprolactone added dipentaerythritol hexa(meth)acrylate.

Ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, propylene glycol trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide added trimethylolpropane trivinyl ether, ethylene oxide added ditrimethylolpropane tetravinyl ether, ethylene oxide added pentaerythritol tetravinyl ether, ethylene oxide added dipentaerythritol hexavinyl ether and other multifunctional vinyl ethers.

(Meth)acrylic acid esters containing a vinyl ether group, such as 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate, 4-vinyloxybutyl (meth)acrylate, 4-vinyloxycyclohexyl (meth)acrylate, 5-vinyloxypentyl (meth)acrylate, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, p-vinyloxymethylphenylmethyl (meth)acrylate, 2-(vinyloxyethoxy)ethyl (meth)acrylate, and 2-(vinyloxyethoxyethoxyethoxy)ethyl (meth)acrylate.

Ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butanediol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether, glycerol triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide addition trimethylolpropane triallyl ether, ethylene oxide addition ditrimethylolpropane tetraallyl ether, ethylene oxide addition pentaerythritol tetraallyl ether, ethylene oxide addition dipentaerythritol hexaallyl ether and other multifunctional allyl ethers.

(Meth)acrylates containing an allyl group, such as allyl (meth)acrylate.

Isocyanurates containing a polyfunctional (meth)acryloyl group such as tris(acryloyloxyethyl)isocyanurate, tris(methacryloyloxyethyl)isocyanurate, alkylene oxide-added tris(acryloyloxyethyl)isocyanurate, and alkylene oxide-added tris(methacryloyloxyethyl)isocyanurate.

Isocyanurates containing a polyfunctional allyl group such as triallyl isocyanurate.

Polyfunctional amine ester (meth)acrylates obtained by reacting a polyfunctional isocyanate such as tolylene diisocyanate, isophorone diisocyanate, or xylene diisocyanate with a hydroxyl group-containing (meth)acrylate such as 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate.

Polyfunctional aromatic vinyls such as divinylbenzene.

Among them, trifunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate, tetrafunctional (meth)acrylates such as pentaerythritol tetra(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate, and hexafunctional (meth)acrylates such as dipentaerythritol hexa(meth)acrylate are preferred.

When the photosensitive resin composition contains a crosslinking agent, the photosensitive resin composition may contain only one crosslinking agent or may contain two or more crosslinking agents. When the photosensitive resin composition contains a crosslinking agent, the amount thereof may be appropriately set according to the purpose or use. As an example, the amount of the crosslinking agent is generally 30 to 70 parts by mass relative to 100 parts by mass of the polymer P, and preferably can be set to about 40 to 60 parts by mass.

The photosensitive resin composition may contain fillers, binder resins other than the above-mentioned polymers, acid generators, heat resistance improvers, developing aids, plasticizers, polymerization inhibitors, ultraviolet absorbers, antioxidants, matting agents, defoaming agents, leveling agents, surfactants, antistatic agents, dispersants, lubricants, surface modifiers, thixotropic agents, thixotropic aids, silane coupling agents, polyvalent phenol compounds and other ingredients according to various purposes or required properties.

(film, color filter, black matrix, liquid crystal display device, and solid-state imaging element)

By using the above-mentioned photosensitive resin composition to form a film, and exposing/developing the film to form a pattern, a film with a pattern can be obtained. The film is suitable for a color filter or a black matrix, etc. That is, by using a photosensitive resin composition containing a colorant to form a pattern, a color filter can be obtained. And, by using a photosensitive resin composition containing a light-shielding agent to form a pattern, a black matrix can be obtained. Then, a liquid crystal display device or a solid-state imaging element with a color filter or a black matrix can be manufactured.

A typical procedure for forming a pattern is described.

(Formation of Photosensitive Resin Film)

For example, the photosensitive resin composition is applied onto an arbitrary substrate and dried as necessary, thereby firstly obtaining a photosensitive resin film.

The substrate to which the composition is applied is not particularly limited, and examples thereof include a glass substrate, a silicon wafer, a ceramic substrate, an aluminum substrate, a SiC wafer, a GaN wafer, and a copper-clad laminate.

The substrate may be an unprocessed substrate or a substrate with electrodes or elements formed on the surface. In order to improve adhesion, the substrate may be subjected to surface treatment.

The method for applying the photosensitive resin composition is not particularly limited, and the composition can be applied by spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, inkjet method, or the like.

The photosensitive resin composition applied on the substrate is typically dried by heating using a hot plate, hot air, an oven, etc. The heating temperature is usually 80 to 140° C., preferably 90 to 120° C. The heating time is usually 30 to 600 seconds, preferably about 30 to 300 seconds.

The thickness of the photosensitive resin film is not particularly limited and may be appropriately adjusted according to the final pattern to be obtained, and is usually 0.5 to 10 μm, preferably 1 to 5 μm. The film thickness can be adjusted by the content of the solvent in the photosensitive resin composition, the coating method, and the like.

(exposure)

The exposure is typically performed by irradiating the photosensitive resin film with active light through an appropriate mask.

As active light, for example, X-rays, electron beams, ultraviolet rays, visible light, etc. can be cited. In terms of wavelength, light of 200 to 500 nm is preferred. From the perspective of pattern resolution or operability, the light source is preferably g-rays, h-rays or i-rays of a mercury lamp, and i-rays are particularly preferred. In addition, two or more light rays can be mixed and used. As an exposure device, a contact aligner, a mirror projection aligner or a stepper is preferred.

The amount of light for exposure may be appropriately adjusted according to the amount of photosensitizer in the photosensitive resin film, and is, for example, about 100 to 500 mJ/cm ² .

In addition, after exposure, the photosensitive resin film may be heated again as needed (post-exposure heating: PostExposure Bake). The temperature is, for example, 70 to 150° C., preferably 90 to 120° C., and the time is, for example, 30 to 600 seconds, preferably 30 to 300 seconds. Post-exposure heating promotes the reaction based on free radicals generated from the photo-radical polymerization initiator, further promoting the curing reaction.

(development)

By developing the exposed photosensitive resin film with an appropriate developer, a pattern can be obtained, and a substrate having a pattern can be manufactured.

In the development step, a suitable developer can be used for development by methods such as dipping, immersion coating, and spin spraying. By development, the exposed portion (in the case of a positive type) or the unexposed portion (in the case of a negative type) of the photosensitive resin film is dissolved and removed to obtain a pattern.

The developer that can be used is not particularly limited, and for example, an alkaline aqueous solution or an organic solvent can be used.

Specific examples of the aqueous alkali solution include (i) aqueous solutions of inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia; (ii) aqueous solutions of organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine; and (iii) aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide.

Specific examples of the organic solvent include ketone solvents such as cyclopentanone, ester solvents such as propylene glycol monomethyl ether acetate (PGMEA) and butyl acetate, and ether solvents such as propylene glycol monomethyl ether.

To the developer, for example, a water-soluble organic solvent such as methanol or ethanol, a surfactant, etc. may be added.

In this embodiment, as the developer, an aqueous alkali solution is preferably used, and tetramethylammonium hydroxide, an aqueous sodium carbonate solution, or an aqueous potassium hydroxide solution is more preferably used.

The concentration of the aqueous alkali solution is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass.

Through the above steps, a pattern can be obtained/a substrate having a pattern can be manufactured, but various treatments may be performed after development.

For example, after development, the pattern and substrate can be cleaned using a rinse solution. Examples of the rinse solution include distilled water, methanol, ethanol, isopropanol, propylene glycol monomethyl ether, etc. These can be used alone or in combination of two or more.

Furthermore, the obtained pattern can be heated to fully cure it. The heating temperature is typically 150 to 400° C., preferably 160 to 300° C., and more preferably 200 to 250° C. The heating time is not particularly limited, and is, for example, in the range of 15 to 300 minutes. The heat treatment can be performed using a hot plate, an oven, a temperature-raising oven capable of setting a temperature program, and the like. The ambient gas used for the heat treatment can be air, or an inert gas such as nitrogen or argon. Furthermore, the heating can be performed under reduced pressure.

FIG. 1 schematically shows an example of the structure of a liquid crystal display device and/or a solid-state imaging element including a color filter and/or a black matrix.

A black matrix 11 and a color filter 12 are formed on the substrate 10. A protective film 13 and a transparent electrode layer 14 are provided on the black matrix 11 and the color filter 12.

The substrate 10 is generally made of a material that allows light to pass, such as glass, polyester, polycarbonate, polyolefin, polysulfone, cyclic olefin polymer, etc. The substrate 10 may be subjected to corona discharge treatment, ozone treatment, chemical treatment, etc. as necessary.

The substrate 10 is preferably made of glass.

The black matrix 11 is composed of, for example, a cured product of a photosensitive resin composition containing a light-shielding agent.

There are generally three colors of red, green, and blue as the color filter 12. The color filter 12 is composed of a cured product of a photosensitive resin composition containing a colorant corresponding to each color.

The embodiments of the present invention are described above, but these are examples of the present invention, and various configurations other than the above can be adopted. In addition, the present invention is not limited to the above embodiments, and modifications and improvements within the scope of achieving the purpose of the present invention are included in the present invention.

[Example]

Embodiments of the present invention will be described in detail based on Examples and Comparative Examples. However, the present invention is not limited to Examples.

The compounds used in the Examples may be represented by the following abbreviations or trade names.

MA: maleic anhydride.

NB: 2-Norbornene.

MEK: Methyl Ethyl Ketone.

4-HBA: 4-hydroxybutyl acrylate.

A-TMM-3LM-N: A mixture of the following two compounds, the amount of the left compound in the mixture measured by gas chromatography is about 57% (manufactured by Shin-Nakamura Chemical Co., Ltd.).

A-9550: A mixture of the following two compounds, the amount of the left compound in the mixture estimated from the hydroxyl value is about 50% (manufactured by Shin-Nakamura Chemical Co., Ltd.).

VISCOAT#802: A mixture of tripentaerythritol acrylate, monopentaerythritol acrylate, dipentaerythritol acrylate, and polypentaerythritol acrylate represented by the following formula (manufactured by Osaka Organic Chemical Industry Co., Ltd.).

n＝1：10-20%.

n＝2：55-65%.

n＝3：5-15%.

＜Synthesis of base polymer＞

(Synthesis of Base Polymer 1)

588.36 g (6.0 mol) of maleic anhydride, 564.90 g (6.0 mol) of 2-norbornene, and 55.26 g (0.24 mol) of dimethyl 2,2'-azobis(2-methylpropionate) were weighed and placed in a reaction vessel of appropriate size equipped with a stirrer and a cooling tube, and these were dissolved in a mixed solvent consisting of 1716.8 g of methyl ethyl ketone and 188.3 g of toluene to prepare a solution.

The solution was passed through nitrogen for 30 minutes to remove oxygen, and then heated at 65°C for 1.5 hours while stirring, and then further heated at 80°C for 6 hours to polymerize maleic anhydride and 2-norbornene to prepare a polymerization solution.

The obtained polymerization solution was added dropwise to 14230.2 g of methanol to precipitate a white solid. The obtained white solid was further washed with 3557.5 g of methanol and then vacuum dried at 120° C. to obtain 1027.2 g of a polymer (raw polymer 1) having a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride.

The obtained polymer was measured by gel permeation chromatography (GPC). As a result, the weight average molecular weight Mw was 7236 and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.83.

(Synthesis of Base Polymer 2)

In a reaction container equipped with a stirrer, a cooling tube and a dropping funnel, 602.56 g of a 75% toluene solution of 2-norbornene (451.92 g, 4.8 mol in terms of 2-norbornene), maleic anhydride (MAN, 470.69 g, 4.8 mol) and 2281.74 g of methyl ethyl ketone (MEK) were added and stirred and dissolved. Next, the dissolved oxygen in the system was removed by nitrogen bubbling and the temperature was raised. When the internal temperature reached 80°C, a solution prepared by dissolving 2,2'-dimethyl azobisisobutyrate (Wako Pure Chemical Industries, Ltd., trade name: V-601, 44.21 g, 0.19 mol) and pentaerythritol tetrakis(3-mercaptopropionate) (PEMP (the thiol-containing compound of the above formula (s-2)), 93.82 g, 0.19 mol) in 193.4 g of MEK was added over 1 hour. After that, the reaction was further allowed to proceed at 80°C for 7 hours. Next, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was added dropwise to 3686.4 g of methanol to precipitate a white solid. The obtained white solid was further washed with 3686.4 g of methanol and then vacuum dried at 120° C. to obtain 910.1 g of a polymer (base polymer 2) containing a structural unit derived from 2-norbornene, a structural unit derived from maleic anhydride, and a thioether group.

The obtained polymer was measured by gel permeation chromatography (GPC). As a result, the weight average molecular weight Mw was 3500 and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.62.

<Preparation of resin composition>

A resin composition containing a polymer P and a polyfunctional (meth)acrylic compound was prepared by the following method.

(Preparation Example 1)

A polymer P1 was prepared in which the MA unit of the base polymer 1 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound and water. The details are described below.

First, 99.71 g of MEK was added to 60.00 g of the base polymer 1 (0.312 mol in terms of MA) to prepare a dissolving solution. Next, 38.75 g of A-TMM-3LM-N was added to the dissolving solution, and then 18.00 g of triethylamine (0.178 mol) was added, and the mixture was reacted at a temperature of 70° C. for 2 hours. Then, 56.27 g of 4-HBA (0.390 mol) was further added, and the mixture was reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution.

Next, without performing post-treatment on the obtained reaction solution, 6.00 g (0.333 mol) of water was added to the reaction solution, and the mixture was reacted at 70° C. for 0.5 hour.

The obtained reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution to remove the aqueous phase from the reaction solution. Thereafter, the polymer was purified by the following steps.

• The polymer was reprecipitated with excess toluene.

The operation of washing the polymer powder obtained by reprecipitation with an excess amount of toluene was repeated twice.

The polymer powder after the above washing twice was washed with an excess amount of water three times.

The obtained reaction product was dried at 40°C for 12 hours.

As described above, 60.20 g of a polymer P1 was obtained in which the structural unit derived from maleic anhydride in the base polymer was ring-opened with A-TMM-3LM-N, 4-HBA and water.

(Preparation Example 2)

A resin mixture containing a polymer P2 in which the MA unit of the base polymer 1 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound and water was prepared. The details are described below.

First, 99.71 g of MEK was added to 60.00 g of the base polymer 1 (0.312 mol in terms of MA) to prepare a dissolving solution. Next, 38.75 g of A-TMM-3LM-N was added to the dissolving solution, and then 18.00 g of triethylamine (0.178 mol) was added, and the mixture was reacted at a temperature of 70° C. for 2 hours. Then, 56.27 g of 4-HBA (0.390 mol) was further added, and the mixture was reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution.

Next, without performing post-treatment on the obtained reaction solution, 6.00 g (0.333 mol) of water was added to the reaction solution, and the mixture was reacted at 70° C. for 0.5 hour.

The obtained reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution to remove the aqueous phase from the reaction solution. Furthermore, liquid-liquid extraction was performed in the following steps, followed by solvent replacement.

Liquid-liquid extraction: The reaction solution was diluted with MEK, and then water was added to remove the aqueous phase from the reaction solution. The same operation was then performed once more.

·Solvent replacement: The obtained reaction mixture was subjected to solvent removal at 50°C under reduced pressure using a rotary evaporator. The solid content concentration of the polymer solution was confirmed to be 27±2% by mass in the measurement based on a heated drying moisture meter, and the solvent removal operation was interrupted. Thereafter, PGMEA was added to make the solid content concentration 18% by mass and mixed until uniform. By the same operation, the solvent was removed under reduced pressure at 50°C, and after the solid content concentration was adjusted to 27±2% by mass in the measurement based on a heated drying moisture meter, the operation of further adding PGMEA to make the solid content concentration 18% by mass and mixing until uniform was repeated 2 times. Thereafter, the solvent was removed or PGMEA was added to make the solid content concentration 30±3% by mass and stirred until uniform. Through the above operation, the solvent used in the reaction was removed and the solvent was replaced with PGMEA.

Through the above, a polymer P2 containing the structural units derived from maleic anhydride in the base polymer subjected to ring-opening using A-TMM-3LM-N, 4-HBA and water, and a resin mixture (resin composition) 2 containing residual (free) A-TMM-3LM-N and residual (free) 4-HBA was obtained.

The obtained resin composition 2 was analyzed by gel permeation chromatography to measure the amount of polymer P2, free multifunctional (meth)acrylic compound and free monofunctional (meth)acrylic compound contained in the composition, and the weight average molecular weight and polydispersity of polymer P2. The results are shown in Table 1. In addition, the amount of free (meth)acrylic compound is expressed as the ratio (%) of the peak area of free (meth)acrylic compound to the peak area of polymer P in the gel permeation chromatography (GPC) chart of the resin mixture.

In addition, the measurement conditions of gel permeation chromatography are as follows.

As a GPC measurement apparatus, HLC-8320GPC EcoSEC manufactured by TOSOH CORPORATION was used. The column temperature was set to 40.0°C, and the pump flow rate was set to 0.350 mL/min.

Peak position (holding time)

Polymer P: a peak detected before 20 minutes (a peak with a shorter retention time and a larger molecular weight than A-TMM-3LM-N and 4-HBA).

A-TMM-3LM-N: The sum of two peaks at 20.0 to 20.6 minutes and 20.6 to 21.5 minutes.

4-HBA: 21.7~22.4 minutes.

· Measurement conditions: The analysis was performed using a differential refractive index detector (RI detector).

(Preparation Example 3)

A resin mixture containing a polymer P3 in which the MA unit of the base polymer 1 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound and water was prepared. The details are described below.

First, 99.71 g of MEK was added to 60.00 g of the base polymer 1 (0.312 mol in terms of MA) to prepare a dissolving solution. Next, 38.75 g of A-TMM-3LM-N was added to the dissolving solution, and then 18.00 g of triethylamine (0.178 mol) was added, and the mixture was reacted at a temperature of 70° C. for 2 hours. Then, 56.27 g of 4-HBA (0.390 mol) was further added, and the mixture was reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution.

Next, without performing post-treatment on the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the mixture was reacted at 70° C. for 2 hours.

The obtained reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution, thereby removing the aqueous phase from the reaction solution. Further, liquid-liquid extraction was performed by the same steps as in Preparation Example 2, followed by solvent replacement to obtain a resin composition 3. The obtained resin composition 3 was subjected to GPC measurement to measure the amount of polymer P3, free multifunctional (meth) acrylic acid compound and free monofunctional (meth) acrylic acid compound contained in the composition, and the weight average molecular weight and polydispersity of polymer P3. The results are shown in Table 1.

(Preparation Example 4)

A resin mixture containing a polymer P4 in which the MA unit of the base polymer 1 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound and water was prepared. The details are described below.

First, 100.30 g of MEK was added to 60.00 g of the base polymer 1 (0.312 mol in terms of MA) to prepare a dissolving solution. Next, 58.12 g of A-TMM-3LM-N was added to the dissolving solution, and then 18.00 g of triethylamine (0.178 mol) was added, and the mixture was reacted at a temperature of 70° C. for 2 hours. Then, 56.27 g of 4-HBA (0.390 mol) was further added, and the mixture was reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution.

Next, without performing post-treatment on the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the mixture was reacted at 70° C. for 2 hours.

The obtained reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution, thereby removing the aqueous phase from the reaction solution. Further, liquid-liquid extraction was performed by the same steps as in Preparation Example 2, followed by solvent replacement to obtain a resin composition 4. The obtained resin composition 4 was subjected to GPC measurement to measure the amount of polymer P4, free multifunctional (meth) acrylic acid compound and free monofunctional (meth) acrylic acid compound contained in the composition, and the weight average molecular weight and polydispersity of polymer P4. The results are shown in Table 1.

(Preparation Example 5)

A resin mixture containing a polymer P5 in which the MA unit of the base polymer 2 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound and water was prepared. The details are described below.

First, 99.71 g of MEK was added to 60.00 g of the base polymer 2 (0.312 mol in terms of MA) to prepare a dissolving solution. Next, 38.75 g of A-TMM-3LM-N was added to the dissolving solution, and then 18.00 g of triethylamine (0.178 mol) was added, and the mixture was reacted at a temperature of 70° C. for 2 hours. Then, 56.27 g of 4-HBA (0.390 mol) was further added, and the mixture was reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution.

Next, without performing post-treatment on the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the mixture was reacted at 70° C. for 2 hours.

The obtained reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution, thereby removing the aqueous phase from the reaction solution. Further, liquid-liquid extraction was performed by the same steps as in Preparation Example 2, followed by solvent replacement to obtain a resin composition 5. The obtained resin composition 5 was subjected to GPC measurement to measure the amount of polymer P5, free multifunctional (meth) acrylic acid compound and free monofunctional (meth) acrylic acid compound contained in the composition, and the weight average molecular weight and polydispersity of polymer P5. The results are shown in Table 1.

(Preparation Example 6)

A resin mixture containing a polymer P6 in which the MA unit of the base polymer 2 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound and water was prepared. The details are described below.

First, 100.30 g of MEK was added to 60.00 g of the base polymer 2 (0.312 mol in terms of MA) to prepare a dissolving solution. Next, 58.12 g of A-TMM-3LM-N was added to the dissolving solution, and then 18.00 g of triethylamine (0.178 mol) was added, and the mixture was reacted at a temperature of 70° C. for 2 hours. Then, 56.27 g of 4-HBA (0.390 mol) was further added, and the mixture was reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution.

Next, without performing post-treatment on the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the mixture was reacted at 70° C. for 2 hours.

The obtained reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution, thereby removing the aqueous phase from the reaction solution. Further, liquid-liquid extraction was performed by the same steps as in Preparation Example 2, followed by solvent replacement to obtain a resin composition 6. The obtained resin composition 6 was subjected to GPC measurement to measure the amount of polymer P6, free multifunctional (meth) acrylic acid compounds and free monofunctional (meth) acrylic acid compounds contained in the composition, and the weight average molecular weight and polydispersity of polymer P6. The results are shown in Table 1.

(Preparation Example 7)

A resin mixture containing a polymer P7 in which the MA unit of the base polymer 2 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound and water was prepared. The details are described below.

First, 102.43 g of MEK was added to 60.00 g of the base polymer 2 (0.312 mol in terms of MA) to prepare a dissolving solution. Next, 116.24 g of A-TMM-3LM-N was added to the dissolving solution, and then 18.00 g of triethylamine (0.178 mol) was added, and the mixture was reacted at a temperature of 70° C. for 2 hours. Then, 56.27 g of 4-HBA (0.390 mol) was further added, and the mixture was reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution.

Next, without performing post-treatment on the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the mixture was reacted at 70° C. for 2 hours.

The obtained reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution, thereby removing the aqueous phase from the reaction solution. Further, liquid-liquid extraction was performed by the same steps as in Preparation Example 2, followed by solvent replacement to obtain resin composition 7. GPC measurement was performed on the obtained resin composition 7 to measure the amount of polymer P7, free multifunctional (meth) acrylic acid compound and free monofunctional (meth) acrylic acid compound contained in the composition, and the weight average molecular weight and polydispersity of polymer P7. The results are shown in Table 1.

(Preparation Example 8)

A resin mixture containing a polymer P8 in which the MA unit of the base polymer 1 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound and water was prepared. The details are described below.

First, 97.74 g of MEK was added to 60.00 g of base polymer 1 (0.312 mol in terms of MA) to prepare a dissolving solution. Next, 58.12 g of A-TMM-3LM-N was added to the dissolving solution, and then 18.00 g of triethylamine (0.178 mol) was added, and the mixture was reacted at a temperature of 70° C. for 2 hours. Then, 27.00 g of 4-HBA (0.187 mol) was further added, and the mixture was reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution.

Next, without performing post-treatment on the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the mixture was reacted at 70° C. for 2 hours.

The obtained reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution, thereby removing the aqueous phase from the reaction solution. Further, liquid-liquid extraction was performed by the same steps as in Preparation Example 2, followed by solvent replacement to obtain a resin composition 8. The obtained resin composition 8 was subjected to GPC measurement to measure the amount of polymer P8, free multifunctional (meth) acrylic acid compounds and free monofunctional (meth) acrylic acid compounds contained in the composition, and the weight average molecular weight and polydispersity of polymer P8. The results are shown in Table 1.

(Preparation Example 9)

A resin mixture containing polymer P9 was prepared in which the MA unit of base polymer 2 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound and water. The details are described below.

First, 99.86 g of MEK was added to 60.00 g of the base polymer 2 (0.312 mol in terms of MA) to prepare a dissolving solution. Next, 58.12 g of A-TMM-3LM-N was added to the dissolving solution, and then 18.00 g of triethylamine (0.178 mol) was added, and the mixture was reacted at a temperature of 70° C. for 2 hours. Then, 40.51 g of 4-HBA (0.281 mol) was further added, and the mixture was reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution.

Next, without performing post-treatment on the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the mixture was reacted at 70° C. for 2 hours.

The obtained reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution, thereby removing the aqueous phase from the reaction solution. Further, liquid-liquid extraction was performed by the same steps as in Preparation Example 2, followed by solvent replacement to obtain a resin composition 9. The obtained resin composition 9 was subjected to GPC measurement to measure the amount of polymer P9, free multifunctional (meth) acrylic acid compound and free monofunctional (meth) acrylic acid compound contained in the composition, and the weight average molecular weight and polydispersity of polymer P9. The results are shown in Table 1.

(Preparation Example 10)

A resin mixture containing a polymer P10 in which the MA unit of the base polymer 2 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound and water was prepared. The details are described below.

First, 100.03 g of MEK was added to 60.00 g of the base polymer 2 (0.312 mol in terms of MA) to prepare a dissolving solution. Next, 58.12 g of A-TMM-3LM-N was added to the dissolving solution, and then 18.00 g of triethylamine (0.178 mol) was added, and the mixture was reacted at a temperature of 70° C. for 2 hours. Then, 27.00 g of 4-HBA (0.187 mol) was further added, and the mixture was reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution.

Next, without performing post-treatment on the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the mixture was reacted at 70° C. for 2 hours.

The obtained reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution, thereby removing the aqueous phase from the reaction solution. Further, liquid-liquid extraction was performed by the same steps as in Preparation Example 2, followed by solvent replacement to obtain a resin composition 10. The obtained resin composition 10 was subjected to GPC measurement to measure the amount of polymer P10, free multifunctional (meth) acrylic acid compound and free monofunctional (meth) acrylic acid compound contained in the composition, and the weight average molecular weight and polydispersity of polymer P10. The results are shown in Table 1.

(Preparation Example 11)

A polymer P11 was prepared in which the MA unit of the base polymer 2 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound and water. The details are described below.

First, 99.93 g of MEK was added to 60.00 g of the base polymer 2 (0.312 mol in terms of MA) to prepare a dissolving solution. Next, 77.49 g of A-TMM-3LM-N was added to the dissolving solution, and then 18.00 g of triethylamine (0.178 mol) was added, and the mixture was reacted at a temperature of 70° C. for 2 hours. Then, 56.27 g of 4-HBA (0.390 mol) was further added, and the mixture was reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution.

Next, without performing post-treatment on the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the mixture was reacted at 70° C. for 2 hours.

The obtained reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution to remove the aqueous phase from the reaction solution. Furthermore, liquid-liquid extraction was performed by the same steps as in Preparation Example 2, followed by solvent replacement to obtain a resin composition 11. Thereafter, the resin composition 11 was purified by the following steps.

• The polymer was reprecipitated with excess toluene.

The operation of washing the polymer powder obtained by reprecipitation with an excess amount of toluene was repeated twice.

The polymer powder after the above washing twice was washed with an excess amount of water three times.

The obtained reaction product was dried at 40°C for 12 hours.

As described above, 34.35 g of a polymer P11 in which the structural unit derived from maleic anhydride in the base polymer 2 was ring-opened with A-TMM-3LM-N, 4-HBA and water was obtained.

(Preparation Example 12)

A resin mixture containing a polymer P12 in which the MA unit of the base polymer 2 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound and water was prepared. The details are described below.

First, 99.93 g of MEK was added to 60.00 g of the base polymer 2 (0.312 mol in terms of MA) to prepare a dissolving solution. Next, 77.49 g of A-TMM-3LM-N was added to the dissolving solution, and then 18.00 g of triethylamine (0.178 mol) was added, and the mixture was reacted at a temperature of 70° C. for 2 hours. Then, 56.27 g of 4-HBA (0.390 mol) was further added, and the mixture was reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution.

Next, without performing post-treatment on the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the mixture was reacted at 70° C. for 2 hours.

The obtained reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution, thereby removing the aqueous phase from the reaction solution. Further, liquid-liquid extraction was performed by the same steps as in Preparation Example 2, followed by solvent replacement to obtain a resin composition 12. The obtained resin composition 12 was subjected to GPC measurement to measure the amount of polymer P12, free multifunctional (meth) acrylic acid compounds and free monofunctional (meth) acrylic acid compounds contained in the composition, and the weight average molecular weight and polydispersity of polymer P12. The results are shown in Table 1.

(Preparation Example 13)

To the resin composition 3 obtained by the same method as in Preparation Example 3, the "additives" described in Table 1 were added in the amounts shown in the "additive amounts" described in Table 1 to prepare a resin composition 13. Here, the additive amounts are defined as weight ratios relative to the solid content of the resin composition 3 (the total amount of the polymer P3 and the polyfunctional (meth) acrylic compound).

The obtained resin composition 13 was subjected to GPC measurement to measure the amount of polymer P3, free polyfunctional (meth)acrylic compound and free monofunctional (meth)acrylic compound contained in the composition, and the weight average molecular weight and polydispersity of polymer P3. The results are shown in Table 1.

In addition, the measurement conditions of gel permeation chromatography are as follows.

As a GPC measurement apparatus, HLC-8320GPC EcoSEC manufactured by TOSOH CORPORATION was used. The column temperature was set to 40.0°C, and the pump flow rate was set to 0.350 mL/min.

Peak position (holding time)

Polymer P: a peak detected before 19.3 minutes (a peak with a shorter retention time and a larger molecular weight than A-TMM-3LM-N, A-9550, and 4-HBA).

Polyfunctional (meth)acrylic compounds (A-TMM-3LM-N and A-9550): The sum of two peaks at 19.3 to 19.8 minutes and 19.8 to 21.0 minutes.

4-HBA: 21.7~22.4 minutes.

· Measurement conditions: The analysis was performed using a differential refractive index detector (RI detector).

(Preparation Example 14)

To the resin composition 12 obtained by the same method as in Preparation Example 12, the "additives" described in Table 1 were added in the amounts shown in the "additive amounts" described in Table 1 to prepare a resin composition 14. Here, the additive amounts are defined as weight ratios relative to the solid content of the resin composition 12 (the total amount of the polymer P12 and the polyfunctional (meth) acrylic compound).

The obtained resin composition 14 was subjected to GPC measurement to measure the amount of polymer P12, free polyfunctional (meth)acrylic compound and free monofunctional (meth)acrylic compound contained in the composition, and the weight average molecular weight and polydispersity of polymer P12. The results are shown in Table 1.

In addition, the measurement conditions of gel permeation chromatography are as follows.

As a GPC measurement apparatus, HLC-8320GPC EcoSEC manufactured by TOSOH CORPORATION was used. The column temperature was set to 40.0°C, and the pump flow rate was set to 0.350 mL/min.

Peak position (holding time)

Polymer P: a peak detected before 19.5 minutes (a peak with a shorter retention time and a larger molecular weight than VISCOAT#802, A-TMM-3LM-N, and 4-HBA).

Polyfunctional (meth)acrylic compound (A-TMM-3LM-N and VISCOAT#802): The sum of two peaks at 19.5 to 20.6 minutes and 20.6 to 21.5 minutes.

4-HBA: 21.7~22.4 minutes.

· Measurement conditions: The analysis was performed using a differential refractive index detector (RI detector).

(Preparation Example 15)

A polymer P13 was prepared in which the MA unit of the base polymer 1 was ring-opened with a monofunctional (meth)acrylic acid compound. The details are described below.

First, 18.44 g of MEK was added to 10.00 g (0.052 mol in terms of MA) of base polymer 1 to prepare a dissolving solution, and then 9.38 g (0.065 mol) of 4-HBA was added to the dissolving solution, followed by 3.00 g (0.030 mol) of triethylamine, and the mixture was reacted at 70° C. for 6 hours to prepare a reaction solution.

The obtained reaction solution was diluted with MEK and treated with an aqueous citric acid solution, thereby removing the aqueous phase from the reaction solution. Thereafter, the polymer was purified by the following steps.

• Reprecipitate the polymer with excess water.

The polymer powder obtained by reprecipitation was washed with an excess of water twice. The obtained reaction product was dried at 40° C. for 12 hours.

As described above, 9.5 g of a polymer P13 in which the structural unit derived from maleic anhydride in the base polymer was ring-opened with 4-HBA was obtained.

The obtained polymer P13 was subjected to GPC measurement to measure the weight average molecular weight and polydispersity of the polymer P13. The results are shown in Table 1.

Furthermore, the disappearance of the peak of the monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P13. Thus, it was confirmed that the obtained polymer P13 did not contain any unreacted monofunctional (meth)acrylic compound.

(Preparation Example 16)

A polymer P14 was prepared in which the MA unit of the base polymer 2 was ring-opened with a monofunctional (meth)acrylic acid compound. The details are described below.

First, 18.44 g of MEK was added to 10.00 g (0.052 mol in terms of MA) of base polymer 2 to prepare a dissolving solution, and then 9.38 g (0.065 mol) of 4-HBA was added to the dissolving solution, followed by 3.00 g (0.030 mol) of triethylamine, and the mixture was reacted at 70° C. for 6 hours to prepare a reaction solution.

The obtained reaction solution was diluted with MEK and treated with an aqueous citric acid solution, thereby removing the aqueous phase from the reaction solution. Thereafter, the polymer was purified by the following steps.

• Reprecipitate the polymer with excess water.

The polymer powder obtained by reprecipitation was washed with an excess of water twice. The obtained reaction product was dried at 40° C. for 12 hours.

As described above, 8.7 g of a polymer P14 in which the structural unit derived from maleic anhydride in the base polymer was ring-opened with 4-HBA was obtained.

The obtained polymer P14 was subjected to GPC measurement to measure the weight average molecular weight and polydispersity of the polymer P14. The results are shown in Table 1.

Furthermore, the disappearance of the peak of the monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P14. Thus, it was confirmed that the obtained polymer P14 did not contain any unreacted monofunctional (meth)acrylic compound.

(Preparation Example 17)

A resin composition 17 containing a polymer P15 in which the MA unit of the base polymer 2 was ring-opened with a monofunctional (meth)acrylic compound was prepared. The details are described below.

First, 18.44 g of MEK was added to 10.00 g (0.052 mol in terms of MA) of base polymer 2 to prepare a dissolving solution, and then 9.38 g (0.065 mol) of 4-HBA was added to the dissolving solution, followed by 3.00 g (0.030 mol) of triethylamine, and the mixture was reacted at 70° C. for 6 hours to prepare a reaction solution.

The obtained reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution, thereby removing the aqueous phase from the reaction solution. Further, liquid-liquid extraction was performed by the same steps as in Preparation Example 2, followed by solvent replacement to obtain a resin composition 17. The obtained resin composition 17 was subjected to GPC measurement to measure the polymer P15 contained in the composition, the amount of free monofunctional (meth) acrylic acid compounds, and the weight average molecular weight and polydispersity of the polymer P15. The results are shown in Table 1.

The following Table 1 also shows the components used in each synthesis example and their charged amounts (in terms of maleic anhydride (MA)).

(Examples 1 to 12, Comparative Examples 1 to 5)

In each of the Examples and Comparative Examples, the alkali solubility of the polymer P or the resin composition obtained in the above-mentioned Preparation Example was evaluated. In addition, a photosensitive resin composition was prepared using the polymer P or the resin composition, and its performance was evaluated.

＜Evaluation＞

[Developability Evaluation] (Dissolution Rate of Polymer P in Alkaline Developer)

The polymer P1 obtained in Preparation Example 1, the polymer P11 obtained in Preparation Example 11, the polymer P13 obtained in Preparation Example 15, and the polymer P14 obtained in Preparation Example 16 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a solution having a solid content concentration of 30% by mass.

Next, the above solution or the resin compositions 2 to 10, 12 to 14, 17 obtained in Preparation Examples 2 to 10, 12 to 14, 17 were spin-coated on the wafer, the PGMEA was dried, and then pre-baked at 100° C. for 2 minutes to produce a resin film with a film thickness of 2 μm ± 0.2.

The resin film together with the wafer was immersed in a 2% sodium carbonate aqueous solution at a temperature of 23° C., and the dissolution rate of the resin film was measured.

The dissolution rate was calculated by visually observing the immersed wafer, measuring the time until the resin film was dissolved and the interference pattern was no longer visible, and dividing the film thickness by the time. The results are shown in Table 2. If the alkali dissolution rate is 180 nm/s or more, it can be used as a photosensitive material without any problem, if it is 300 nm/s or more, it can be considered that the developability is good, and if it is 500 nm/s or more, it can be considered that the developability is particularly good.

[Evaluation of Sensitivity of Photosensitive Resin Composition 1 (Exposure Amount at Which Residual Film Ratio Becomes 95% or More)]

First, the following components were dissolved in propylene glycol monomethyl ether acetate (PGMEA) so that the total solid content concentration would be 30% by mass, thereby obtaining a photosensitive resin composition.

Polymer P1 (polymer P1 of Preparation Example 1), polymer P11 (polymer P11 of Preparation Example 11), polymer P13 (polymer P13 of Preparation Example 15) or polymer P14 (polymer P14 of Preparation Example 16) or resin compositions 2 to 10, 12 to 14, 17: 100 parts by mass.

(Here, the resin compositions 2 to 10, 12 to 14, and 17 were weighed so that the solid content (the total amount of the polymers P2 to P10, P12, and P15 and the polyfunctional (meth)acrylic compound) was 100 parts by mass.)

· Multifunctional acrylate (dipentaerythritol hexaacrylate): 50 parts by mass.

Photopolymerization initiator (Ingacure OXE01 manufactured by BASF): 5 parts by mass.

· Adhesion aid (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403): 1 part by mass.

Surfactant (DIC Corporation, F-556): 0.5 parts by mass.

The obtained photosensitive resin composition was spin-coated on a 3-inch silicon wafer treated with HMDS (hexamethyldisilazane) and baked on a hot plate at 100° C. for 120 seconds to obtain a thin film A with a thickness of 3.0 μm (±0.3 μm).

The film A was exposed to g+h+i rays at an exposure dose of 100 mJ/cm ² using a g+h+i ray mask aligner (PLA-501F) manufactured by Canon Inc. through a mask having a grayscale with a light shielding rate of 1 to 100%.

After exposure, the film was developed in a 2.0 mass % sodium carbonate aqueous solution at 23° C. for 60 seconds (with wafer immersion), thereby obtaining a film B exposed and developed at exposure doses of 1 to 100 mJ/cm ^2.

The residual film ratio was calculated from the film thicknesses of the thin films A and B obtained by the above method using the following formula.

Residual film rate (%) = (thickness of film B at each exposure amount/thickness of film A) × 100

Then, the exposure amount at which the residual film rate became 95% or more was taken as the sensitivity of each photosensitive resin composition. The results are shown in Table 2. If the exposure amount at which the residual film rate became 95% or more was 60 mJ/cm ² or less, it could be used as a photosensitive material without any problem.

[Evaluation of sensitivity of resin composition 2 (residual film ratio after exposure at low exposure dose)]

(Residual film rate at 5mJ/ ^cm2 exposure)

The photosensitive resin composition prepared in the sensitivity evaluation 1 was spin-coated on a 3-inch silicon wafer treated with HMDS (hexamethyldisilazane) and baked on a hot plate at 100° C. for 120 seconds to obtain a film A with a thickness of 3.0 μm (±0.3 μm).

The film A was exposed to g+h+i rays at an exposure dose of 5 mJ/cm ² using a g+h+i ray mask aligner (PLA-501F) manufactured by Canon Inc. through a mask having a grayscale with a light shielding rate of 1 to 100%.

After the exposure, the film was developed in a 2.0 mass % sodium carbonate aqueous solution at 23° C. for 60 seconds (along with the wafer immersion), whereby a film B was obtained.

The residual film ratio was calculated from the film thicknesses of the thin films A and B obtained by the above method using the following formula.

Residual film rate (%) = (thickness of film B at each exposure amount/thickness of film A) × 100

(Residual film rate at exposure dose of 10mJ/ ^cm2 )

The photosensitive resin composition prepared in the sensitivity evaluation 1 was spin-coated on a 3-inch silicon wafer treated with HMDS (hexamethyldisilazane) and baked on a hot plate at 100° C. for 120 seconds to obtain a film A with a thickness of 3.0 μm (±0.3 μm).

The film A was exposed to g+h+i rays at an exposure dose of 10 mJ/cm ² using a g+h+i ray mask aligner (PLA-501F) manufactured by Canon Inc. through a mask having a grayscale with a light shielding rate of 1 to 100%.

After the exposure, the film was developed in a 2.0 mass % sodium carbonate aqueous solution at 23° C. for 60 seconds (along with the wafer immersion), whereby a film B was obtained.

The residual film ratio was calculated from the film thicknesses of the thin films A and B obtained by the above method using the following formula.

Residual film rate (%) = (thickness of film B at each exposure amount/thickness of film A) × 100

The results are shown in Table 2.

When the residual film ratio is 50% or more, the sensitivity can be regarded as good, and when the residual film ratio is 80% or more, the sensitivity can be regarded as particularly good.

[Yellow Index]

The photosensitive resin composition prepared in the above sensitivity evaluation 1 was spin-coated on EAGLE XG glass (manufactured by Corning Incorporated Co., Ltd., thickness 0.5 mm) and baked on a hot plate at 100° C. for 120 seconds to obtain a thin film with a thickness of about 3.0 μm (±0.1 μm).

Next, the film was exposed to g+h+i rays at an exposure dose of 100 mJ/cm ² using a g+h+i ray mask aligner (PLA-600F) manufactured by Canon Inc.

After the exposure, the film was developed in a 2.0 mass % sodium carbonate aqueous solution at 23° C. for 60 seconds (along with the wafer immersion), thereby obtaining a film exposed and developed at an exposure dose of 100 mJ/cm ² .

The film was heated at 230° C. in air for 30 minutes. After cooling the film at room temperature in air, the film was heated again at 230° C. in air for 30 minutes. The same operation was repeated, and the heating treatment in air for 30 minutes was performed three times in total.

The yellow index (YI) of the film obtained by the above method was measured three times by changing the measurement position using a colorimeter CR-5 (manufactured by Konica Minolta, Inc.), and the average value was taken as the value of YI. The measurement type was transmission measurement, and 100% calibration used uncoated EAGLE XG glass (manufactured by Corning Incorporated Co., Ltd., thickness 0.5 mm). The results are shown in Table 2. The smaller the value of the yellow index, the better the heat discoloration resistance. If it is 1.35 or less, it can be used as a photosensitive material without any problem.

The results of the developability evaluation and the sensitivity evaluation are summarized below.

The photosensitive resin composition of the embodiment has a good alkali dissolution rate and thus has excellent developability. The photosensitive resin composition of the embodiment has a high residual film rate when exposed at an exposure dose of 10 mJ/ ^cm2 , in other words, it is cured at a low exposure dose and can be said to have high sensitivity. Therefore, the photosensitive resin composition of the embodiment has a good balance between high sensitivity and low yellowness index.

＜Color filter production＞

A colored photosensitive resin composition was prepared by further adding an appropriate amount of pigment dispersion NX-061 (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd., green) to the photosensitive resin composition prepared in Examples 1 to 12.

This is formed into a film on a substrate, and subjected to exposure, alkali development treatment, etc., to form a green color filter.

Furthermore, a blue or red color filter can be formed by using NX-053 (blue) or NX-032 (red) or the like manufactured by the same company instead of NX-061 as the pigment dispersion liquid.

＜Making Black Matrix＞

A black photosensitive resin composition was prepared by further adding an appropriate amount of carbon black dispersion NX-595 (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.) to the photosensitive resin composition prepared in Examples 1 to 12.

This is formed into a film on a substrate, and subjected to exposure, alkali development treatment, etc., to form a black matrix.

This application claims the benefit of priority based on Japanese patent application No. 2019-189162 filed on October 16, 2019 and Japanese patent application No. 2020-005974 filed on January 17, 2020, and all the disclosures of these applications are hereby incorporated by reference in their entirety.

Claims (19)

1. A resin composition, comprising:

A polymer containing a structural unit represented by the formula (NB), a structural unit represented by the formula (1), and a structural unit represented by the formula (2); and

A compound having 2 or more (meth) acryloyl groups,

In the formula (NB), R ¹、R²、R³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, a ₁ is 0, 1 or 2,

In the formula (1), R ^p is a group having 2 or more (meth) acryloyl groups,

In formula (2), R ^s is a group having 1 (meth) acryloyl group.

2. The resin composition according to claim 1, wherein,

The weight average molecular weight of the polymer is 1000 to 20000.

3. The resin composition according to claim 1 or 2, wherein,

In the Gel Permeation Chromatography (GPC) diagram of the resin composition, the peak area of the compound having 2 or more (meth) acryloyl groups is 5% or more and 150% or less relative to the peak area of the polymer.

4. The resin composition according to any one of claim 1 to 3, wherein,

The polymer further comprises a structural unit represented by the formula (3),

5. The resin composition according to any one of claim 1 to 4, wherein,

The polymer further comprises a structural unit represented by the formula (MA),

6. The resin composition according to any one of claims 1 to 5, wherein,

The resin composition further contains a compound having 1 (meth) acryloyl group.

7. The resin composition according to claim 6, wherein,

In the Gel Permeation Chromatography (GPC) diagram of the resin composition, the peak area of the compound having 1 (meth) acryloyl group is 5% or more and 60% or less with respect to the peak area of the polymer.

8. The resin composition according to any one of claims 1 to 7, wherein,

The alkali dissolution rate of the resin composition is 250nm/s or more.

9. The resin composition according to any one of claims 1 to 8, wherein,

The resin composition further contains an organic solvent.

10. The resin composition according to claim 9, wherein,

The solvent is at least 1 selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, gamma-butyrolactone, N-methylpyrrolidone and cyclohexanone.

11. The resin composition according to any one of claim 1 to 10, wherein,

The resin composition is used to form a color filter or a black matrix.

12. A photosensitive resin composition, which comprises:

a polymer containing a structural unit represented by the formula (NB), a structural unit represented by the formula (1), and a structural unit represented by the formula (2);

a compound having 2 or more (meth) acryloyl groups; and

The light-sensitive agent is used as a light-sensitive agent,

In the formula (NB), R ¹、R²、R³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, a ₁ is 0, 1 or 2,

In the formula (1), R ^p is a group having 2 or more (meth) acryloyl groups,

In formula (2), R ^s is a group having 1 (meth) acryloyl group.

13. The photosensitive resin composition according to claim 12, wherein,

The weight average molecular weight of the polymer is 1000 to 20000.

14. The photosensitive resin composition according to claim 12 or 13, wherein,

In the Gel Permeation Chromatography (GPC) diagram of the photosensitive resin composition, the peak area of the compound having 2 or more (meth) acryloyl groups is 5% to 150% of the peak area of the polymer.

15. The photosensitive resin composition according to any one of claims 12 to 14, wherein,

The polymer further comprises a structural unit represented by the formula (3),

16. The photosensitive resin composition according to any one of claims 12 to 15, wherein,

The polymer further comprises a structural unit represented by the formula (MA),

17. The photosensitive resin composition according to any one of claims 12 to 16, wherein,

The photosensitive resin composition further contains a compound having 1 (meth) acryloyl group.

18. The photosensitive resin composition according to claim 17, wherein,

In the Gel Permeation Chromatography (GPC) diagram of the photosensitive resin composition, the peak area of the compound having 1 (meth) acryloyl group is 5% or more and 60% or less with respect to the peak area of the polymer.

19. A cured product formed from the photosensitive resin composition according to any one of claims 12 to 18.