JP2012194516A - Colored photosensitive resin composition, patterning process, method for manufacturing color filter, color filter and display device having the same - Google Patents

Abstract

Colored photosensitive resin capable of forming a pattern having high line width sensitivity, excellent linearity, suppressing generation of wrinkles in development, forming a cured film excellent in heat resistance, and having a small luminance decrease after post-baking Provision of the composition.
A binder resin comprising a structural unit selected from (A) a colorant, (B) a structural unit composed of an allyl methacrylate compound in the molecule, and an acrylate compound structural unit having an N-substituted maleimide group, (C A) a polymerizable compound, (D) a photopolymerization initiator comprising an oxime compound having a carbazole structure containing thiophene, and (E) a solvent, wherein (D) the content of the photopolymerization initiator is 5% by mass to 15%. A colored photosensitive resin composition having a mass%.
[Selection figure] None

Description

  The present invention relates to a colored photosensitive resin composition, a pattern forming method, a color filter manufacturing method, a color filter, and a display device including the same.

In recent years, the development of liquid crystal display devices has been expanded from the use of personal computers and monitors having a relatively small screen to the use of televisions requiring a large screen and high image quality.
In television applications, higher image quality, that is, improvement in contrast and color purity is required compared to conventional monitor applications. In order to improve contrast, a finer particle size of a colorant (such as an organic pigment) used in a colored photosensitive resin composition used for forming a color filter is required. Moreover, the higher thing is calculated | required as content rate of the coloring agent (organic pigment) which occupies in solid content of this colored photosensitive resin composition for color purity improvement.

  In response to the above requirements, a pigment dispersion composition having a finer particle diameter and higher dispersibility is required. In order to increase the dispersibility of the pigment, for example, the surface of a phthalocyanine pigment is usually modified with a derivative compound thereof, and dispersion of a low molecular weight resin having a polar functional group that is easily adsorbed on the modified surface A pigment dispersion composition containing a pigment, a surface modifier, and a dispersant is obtained using the agent while achieving dispersibility and dispersion stability of the pigment. Further, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and other components are further added to the obtained pigment dispersion composition to form a photosensitive composition, and a color filter is obtained by using this to obtain a color filter. ing.

When the pigment becomes finer and the pigment content becomes high, there is a problem that when the image pattern is formed by the photolithography method, the line width sensitivity is lowered (the line width is reduced). In TV applications, it is demanded to provide a color filter at a particularly low cost. However, the above-described problem centering on the development process requires that the exposure amount be increased in the exposure process, that is, the exposure time must be increased. As a result, the yield is lowered and the productivity is deteriorated, so improvement has been demanded.
In order to solve the above problems, many attempts have been made to improve the line width sensitivity by improving the photopolymerization initiator used in the photosensitive resin composition for color filters. For example, a photopolymerizable composition using a triazine compound having a specific structure (for example, see Patent Document 1), a color using one or a mixture of two or more benzophenone compounds, acetophenone compounds, and thioxanthone compounds. A filter photoresist (for example, see Patent Document 2) is disclosed.

As another proposal, by defining the average double bond equivalent in the organic compound formed by summing up the binder resin and the polymerizable compound in the colored photosensitive resin composition, and further specifying the molecular weight of the binder resin, A technique for forming a forward tapered shape by firing has been disclosed (see Patent Document 3).
Further, although it is not a colored photosensitive resin composition for exposure with an ultraviolet laser, it has been proposed to prepare a colored resin composition with high sensitivity and wide development latitude by using a binder resin containing an allyl group. (For example, refer to Patent Documents 4 and 5.) It has also been proposed to use a N-phenylmaleimide copolymer as a binder resin to provide a radiation-sensitive composition for blue color filters with good color reproduction (see, for example, Patent Document 6). These techniques are inferior in productivity in an exposure process and a development process using an ultraviolet laser, and cannot ensure sufficient productivity, and therefore cannot reduce the price of the color filter.

  In order to increase the productivity of the exposure process and the development process, it has been proposed to perform pattern formation by exposing with a laser beam (see, for example, Patent Document 7). Unlike mercury lamps that are normally used, lasers are expected to have characteristics that they have high linearity, high output, can be focused, and do not require a mask for pattern formation in the exposure process. Has been. However, even with the above-described prior art, it does not satisfy the characteristics required for the colored photosensitive resin composition, such as a roughened pixel surface in the development process or insufficient line width sensitivity of the pattern. It was. Also, an exposure apparatus that does not use a large photomask has been proposed in terms of reducing the total cost of the color filter. (For example, refer to Patent Documents 8 and 9.) However, no specific material has been presented, and a proposal of a material suitable for these devices has been desired.

  Moreover, in the blue colored photosensitive resin composition, the blue colorant itself has strong absorption in the exposed region, and a highly sensitive initiator has been desired. As such an initiator, use of an oxime-based initiator or a ketoxime-based initiator can be considered, but an initiator that does not cause coloration even after post-baking due to a large decrease in luminance after post-baking due to coloring caused by the initiator. Was requested.

JP-A-6-289611 Japanese Patent Laid-Open No. 9-80225 JP 2007-93811 A Japanese Patent Laid-Open No. 10-20296 International Publication No. 2007/29871 Pamphlet Japanese Patent No. 3632532 JP 2003-287614 A JP 2008-76709 A JP 2008-51866 A

The present invention has a high line width sensitivity, is unlikely to generate reticulation (wrinkle) in development, the cured film has excellent heat resistance, a small luminance drop after post-baking, and forms a colored pattern with excellent linearity It is an object of the present invention to provide a colored photosensitive resin composition for ultraviolet light laser exposure that is suitable for forming a colored photosensitive resin composition, particularly a colored pixel of a color filter.
A further object of the present invention is to provide a pattern forming method for forming a colored pattern excellent in shape and brightness, a method for producing a color filter, and a good pattern shape and brightness using the colored photosensitive resin composition. Another object of the present invention is to provide a color filter having an appropriate coloring pattern and a display device including the color filter.

  As a result of intensive studies, the present inventor has found that the above problems can be solved by the following method.

<1> At least (A) a colorant, (B) (B-1) a structural unit represented by the following general formula (I) in the molecule, (B-2) a structural unit having an N-substituted maleimide group And (B-3) a binder resin containing at least one structural unit selected from the group consisting of structural units represented by the following general formula (II), (C) a polymerizable compound, (D) the following general formula It contains a photopolymerization initiator represented by (III) and (E) a solvent, and the content of the (D) photopolymerization initiator is from 5% by mass to the total solid content of the colored photosensitive resin composition. The colored photosensitive resin composition which is 15 mass%.

In general formula (I), R ^{11 to} R ¹⁵ each independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, or an aryl group, and R ¹⁶ represents a hydrogen atom or a methyl group.

In General Formula (II), R ²¹ represents a hydrogen atom or a methyl group, and R ²² represents an alkylene group having 1 to 6 carbon atoms. R ²³ and R ²⁴ are each independently an alkyl group having 4 or less carbon atoms, either one is a hydrogen atom and the other is an alkyl group having 4 or less carbon atoms, or R ²³ and R ²⁴ are A group that forms a carbocycle by bonding.

In the general formula (III), X ¹ , X ² , and X ³ each independently represent a hydrogen atom, a halogen atom, or an alkyl group, and R ¹ represents —R, —OR, —COR, —SR, —CONRR 'Or -CN, and R ² and R ³ each independently represent -R, -OR, -COR, -SR, or -NRR'. R and R ′ each independently represents an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these groups are substituted with one or more selected from the group consisting of a halogen atom and a heterocyclic group. And one or more carbon atoms constituting the alkyl chain in the alkyl group and the aralkyl group may be replaced with an unsaturated bond, an ether bond, or an ester bond, and R and R ′ are bonded to each other. May form a ring.

<2> The colored photosensitive resin composition according to <1>, further comprising (F) a sensitizer selected from polyfunctional thiol compounds.
<3> The (B) binder resin has (B-1) a structural unit represented by the general formula (I), (B-2) a structural unit having an N-substituted maleimide group in the molecule, and ( B-3) 50 mol% to 90 mol% of at least one structural unit selected from the group consisting of the structural unit represented by the general formula (II) and a structural unit having an acidic group, and weight The colored photosensitive resin composition according to <1> or <2>, which is a resin having an average molecular weight in the range of 10,000 to 100,000.
<4> The colored photosensitive resin composition according to any one of <1> to <3>, which is for ultraviolet laser exposure.

<5> A colored layer forming step of forming a colored layer by applying the colored photosensitive resin composition according to any one of <1> to <4> onto a substrate, and a pattern pattern with respect to the colored layer A pattern forming method comprising: an exposure step of performing exposure with an ultraviolet light laser to cure the exposed portion; and a developing step of removing the uncured portion of the pre-colored layer by development to form a pattern.
<6> The pattern forming method according to <5>, wherein an exposure wavelength of the ultraviolet laser is in a range of 300 nm to 380 nm.

<7> The pattern forming method according to <5> or <6>, wherein the ultraviolet laser is a pulsed laser oscillated at a frequency of 20 Hz to 2000 Hz.
<8> A method for producing a color filter including a step of forming a colored pattern on a substrate by the pattern forming method according to any one of <5> to <7>.
<9> A color filter manufactured by the manufacturing method according to <8>.
<10> A display device comprising the color filter according to <9>.

According to the present invention, a colored pattern having high line width sensitivity, hardly causing reticulation (wrinkle) in development, excellent heat resistance, small luminance decrease after post-baking, and excellent linearity. It is possible to provide a colored photosensitive resin composition capable of forming a color photosensitive resin composition, particularly a colored photosensitive resin composition for ultraviolet laser exposure suitable for forming colored pixels of a color filter.
Further, according to the present invention, a pattern forming method for forming a colored pattern excellent in shape and brightness, a method for producing a color filter, and a pattern shape and brightness using the colored photosensitive resin composition are provided. A color filter having a good coloring pattern and a display device including the color filter can be provided.

Hereinafter, embodiments for carrying out the present invention will be described in detail.
≪Colored photosensitive resin composition≫
The colored photosensitive resin composition of the present invention comprises at least (A) a colorant, (B) (B-1) a structural unit represented by the following general formula (I) in the molecule, and (B-2) N-position. -Binder resin containing a structural unit having a substituted maleimide group and (B-3) at least one structural unit selected from the group consisting of structural units represented by the following general formula (II) (hereinafter referred to as “( B) binder resin ”), (C) a polymerizable compound, (D) a photopolymerization initiator represented by the following general formula (III), and (E) a solvent. The content of the initiator is 5% by mass to 15% by mass with respect to the total solid content of the colored photosensitive resin composition.
Hereinafter, each component of the colored photosensitive resin composition of the present invention will be described in detail.

<(A) Colorant>
The colored photosensitive resin composition of the present invention contains (A) at least one kind of colorant.
The content of the (A) colorant in the colored photosensitive resin composition of the present invention is 15% by mass to 60% by mass with respect to the solid content of the colored photosensitive resin composition. (A) If the content of the colorant is less than 15% by mass, it is necessary to set the film thickness thick in order to obtain a desired hue, which makes it difficult to develop and increases the tact time. Problems arise. On the other hand, when the content of the colorant (A) exceeds 60% by mass, the development time becomes long, and the profile shape becomes an inverted edge shape, which is not preferable.
The solid content of the colored photosensitive resin composition in the present invention is the total content of all components of the colored photosensitive resin composition excluding the solvent (E), which is one of the components of the colored photosensitive resin composition. Point to.
The “solid content” of the colored photosensitive resin composition in the present invention is a curing obtained by forming a coating film having a thickness of 2.0 μm using the colored photosensitive resin composition and drying at 150 ° C. for 60 minutes. It means the components remaining in the film, and the colored photosensitive resin composition of the present invention includes (E) all components of the colored photosensitive resin composition excluding the solvent.
The content of the colorant (A) in the colored photosensitive resin composition of the present invention is more preferably 20% by mass to 50% by mass with respect to the total solid content of the colored photosensitive resin composition, and 25% by mass to 40% by mass. % Is more preferable.

  As the colorant (A), a dye and a pigment can be appropriately selected and used. From the viewpoint of heat resistance and the like, a pigment is more preferable.

(A) The pigment used as the colorant may be an inorganic pigment or an organic pigment, but from the viewpoint of high transmittance, it is preferable to use a pigment having a particle size as small as possible. The average primary particle diameter of the pigment is preferably 0.01 μm to 0.1 μm, and more preferably 0.01 μm to 0.05 μm.
In the colored photosensitive resin composition of the present invention, by using the polymer dispersant described later, the pigment dispersibility and dispersion stability are improved even when the pigment size is small. Even if it is thin, a colored pixel having excellent color purity can be formed.

  Furthermore, in the present invention, among the pigments contained in the colored photosensitive resin composition, the proportion of the pigment having a primary particle size of less than 0.02 μm is less than 10% in the total amount of the pigment, and The proportion of the pigment having a primary particle diameter exceeding 0.08 μm is preferably less than 5% in the total amount of the pigment.

When the ratio of the pigment having a primary particle diameter of less than 0.02 μm is less than 10%, the heat resistance and chromaticity change can be prevented, and the ratio of the pigment having a primary particle diameter exceeding 0.08 μm is 5 When it is less than%, the contrast is good, the time-dependent stability of the colored photosensitive resin composition is good, and further, foreign matter failure can be prevented.
The proportion of the pigment having a primary particle size of less than 0.02 μm is more preferably less than 5% from the viewpoints of heat resistance and chromaticity change prevention.
The proportion of the pigment having a primary particle diameter exceeding 0.08 μm is preferably less than 3% from the viewpoint of improving contrast.

  The primary particle diameter of the pigment can be measured using a TEM (transmission electron microscope). That is, the TEM photograph is subjected to image analysis to examine the particle size distribution. For example, the particle size distribution can be grasped by measuring the total number of particles in the observation sample at 30,000 times to 100,000 times and the number of pigment particles less than 0.02 μm and more than 0.08 μm. More specifically, the pigment powder is observed with a transmission electron microscope at a magnification of 30,000 to 100,000, a photograph is taken, the major axis of 1000 primary particles is measured, and the particle size is less than 0.02 μm. The ratio of primary particles and primary particles having a particle diameter exceeding 0.08 μm is calculated. This operation is performed for a total of three locations by changing the location of the pigment powder, and the results are averaged.

  (A) Examples of inorganic pigments that can be used as a colorant include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium And metal oxides such as magnesium, chromium, zinc, and antimony, and composite oxides of the above metals.

Examples of the organic pigment include:
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279,

  C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 4, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214

C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73,
C. I. Pigment Green 7, 10, 36, 37
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 Cl substituent was changed to OH Stuff, 80,
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42,
C. I. Pigment Brown 25, 28 and the like.

Among these, the pigments that can be preferably used include the following. However, the present invention is not limited to these.
C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,
C. I. Pigment Orange 36, 71,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,
C. I. Pigment Violet 19, 23, 32
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment Green 7, 36, 37.

These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples of combinations are shown below.
For example, the pigment for the red layer (R) may be an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone, or at least one of the pigments and a disazo pigment, isoindoline. Pigments, mixed with yellow pigments such as quinophthalone pigments, or at least one of anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments and perylene pigments, anthraquinone pigments, condensed dis pigments, diketopyrrolo A mixture with a red pigment such as a pyrrole pigment can be used. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and condensed condensed red pigments include C.I. I. Pigment red 242, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Pigment red 254 and C.I. I. Pigment yellow 139 or C.I. I. Mixing with Pigment Red 177 is preferred.
The mass ratio of red pigment to other pigment (red pigment: other pigment) is preferably 100: 5 to 100: 80. If it is 100: 4 or less, it may be difficult to suppress the light transmittance from 400 nm to 500 nm, and the color purity may not be improved. Further, when the ratio is 100: 81 or more, the coloring power may decrease. Particularly, the mass ratio is optimally in the range of 100: 10 to 100: 65. In addition, in the case of the combination of red pigments, it can adjust according to chromaticity.

In addition, as the pigment for the green layer (G), a halogenated phthalocyanine pigment alone or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment may be used. Can be used. For example, C.I. I. Pigment Green 7, 36, 37, 58 and C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred.
The mass ratio of the green pigment to the yellow pigment (green pigment: yellow pigment) is preferably 100: 5 to 100: 150 from the viewpoint of obtaining sufficient color purity and suppressing deviation from the NTSC target hue. : The range of 30-100: 120 is especially preferable.

As the pigment for the blue layer (B), a phthalocyanine pigment can be used alone, or a mixture thereof with a dioxazine purple pigment can be used. For example, C.I. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred. The mass ratio of blue pigment to purple pigment (blue pigment: purple pigment) is preferably 100: 0 to 100: 50, more preferably 100: 5 to 100: 30.
The colored photosensitive composition of the present invention is effective because it is not colored yellow even when the colored layer is heated, particularly when applied to a blue colored photosensitive composition.

  In the present invention, it is particularly preferable to use an organic pigment as a colorant and to coat the pigment with a polymer compound in the pigment miniaturization step or dispersion step. Even in pigments refined by coating the pigment with a polymer compound, the formation of secondary aggregates is suppressed, and the coated pigment with improved dispersibility that can be dispersed in the form of primary particles It is more preferable to use a coating pigment excellent in dispersion stability in which primary particles are stably maintained.

  The coated pigment, which is a preferred embodiment in the present invention, is a pigment coated with a polymer compound. However, the coating is a new surface of a pigment having high surface activity generated by miniaturization. Since a strong coating layer of the polymer compound is formed by a strong electrostatic action, it is considered that a coated pigment having higher dispersion stability can be obtained. That is, in the present invention, the coated polymer compound is hardly released even when the pigment after coating treatment is washed with an organic solvent that dissolves the polymer compound.

  The coated pigment as used in the present invention is one in which pigment particles such as organic pigments are coated with a polymer compound having a polar group such as a heterocyclic ring in the side chain, and the polymer compound is a part of the pigment particle surface or By being firmly coated all over, a higher dispersion stability effect can be obtained, which is different from that obtained by adsorbing a general polymer dispersant to a pigment. This covering state can be confirmed by measuring the free amount (release rate) of the polymer compound by washing with an organic solvent described below. That is, most of the polymer compound simply adsorbed is washed and washed with an organic solvent, specifically, 65% or more is liberated and removed. In the case of a surface-coated pigment as in the present invention, the liberation rate Is very small, 30% or less.

  The release amount (release rate) is calculated by washing the coated pigment with 1-methoxy-2-propanol. That is, 10 g of the pigment was put into 100 ml of 1-methoxy-2-propanol, shaken at room temperature for 3 hours using a shaker, and then the pigment was allowed to settle for 8 hours at 80,000 rpm with a centrifuge. The mass of the solid content of the supernatant is determined by a drying method. The liberation rate (%) is calculated from the ratio between the mass of the solid content and the mass of the polymer compound used for the coating of the pigment.

The said free amount (free rate) about commercially available pigments can be measured by the following method. That is, after dissolving the entire pigment with a solvent that dissolves the pigment (for example, dimethyl sulfoxide, dimethylformamide, formic acid, sulfuric acid, etc.), the polymer compound and the pigment are separated by an organic solvent using the difference in solubility. Thus, it is calculated as “mass of the polymer compound used for the coating treatment of the pigment”. Separately, the pigment was washed with 1-methoxy-2-propanol, and the obtained liberation amount was divided by the “mass of the polymer compound used for the pigment coating treatment” to obtain the liberation rate (%). Ask for.
The smaller the liberation rate, the higher the coverage of the pigment, and the better the dispersibility and dispersion stability. A preferable range of the liberation rate is 30% or less, more preferably 20% or less, and most preferably 15% or less. Ideally 0%.

  The coating treatment is preferably performed at the same time in the step of refining the pigment. Specifically, (i) a pigment, (ii) a water-soluble inorganic salt, and (iii) a small amount that does not substantially dissolve (ii). (Iv) A step of adding a polymer compound and mechanically kneading with a kneader or the like to obtain a mixture (referred to as a salt milling step), throwing the mixture into water, a high speed mixer, etc. It is carried out through a step of stirring to form a slurry, and a step of filtering, washing with water and drying if necessary.

  The salt milling described above will be described more specifically. First, a small amount of (iii) a water-soluble organic solvent is added as a wetting agent to a mixture of (i) an organic pigment and (ii) a water-soluble inorganic salt, and after kneading strongly with a kneader or the like, this mixture is submerged in water. The mixture is stirred and stirred with a high speed mixer or the like to form a slurry. Next, the slurry is filtered, washed with water, and dried if necessary to obtain a finer pigment. In addition, when using it disperse | distributing to an oil-based varnish, it is also possible to disperse | distribute the process pigment (it is called a filter cake) before drying to an oil-based varnish, removing water by the method generally called flushing. When dispersed in an aqueous varnish, the treated pigment does not need to be dried, and the filter cake can be dispersed in the varnish as it is.

By using (iv) at least partly soluble resin (polymer compound) in combination with (iii) organic solvent during salt milling, the surface is further finely coated with (iv) at least partly soluble resin. In addition, a pigment with little aggregation of the pigment at the time of drying is obtained.
Note that (iv) the timing of adding the polymer compound may be added all at the beginning of the salt milling step, or may be added in divided portions. It is also possible to add in the dispersion step.

The polymer compound used for coating the pigment may be anything as long as it has an adsorptive group for the pigment. In particular, a polymer compound having a heterocyclic ring in the side chain is preferable. The binder resin (B) described later in the present invention is also preferable as the polymer compound used for coating the pigment.
Examples of such a polymer compound are disclosed in paragraph numbers [0029] to [0030] of JP-A-2008-83089 and paragraph numbers [0044] to [0047] of JP-A-2009-62457. Things can be used.

Even in the case of using the above-described coated pigment, it is more preferable to disperse the pigment using at least one dispersant and use it as a pigment dispersion composition. By containing this dispersant, the dispersibility of the pigment can be further improved.
As the dispersant, for example, a known pigment dispersant or surfactant can be appropriately selected and used.

  Specifically, many kinds of compounds can be used, for example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether Nonionic surfactants such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; W004, W005, W017 (manufactured by Yusho Co., Ltd.) Anionic surfactants such as EFKA 46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, polymer dispersants such as Disperse Aid 9100 (both manufactured by San Nopco);

Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000 and other Solsperse dispersants (manufactured by Nippon Lubrizol Co., Ltd.); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, manufactured by Asahi Denka Co., Ltd. and Ionette S-20 (manufactured by Sanyo Chemical Co., Ltd.), Disperbyk 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 161, 162, 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (bit Chemie Co., Ltd.) and the like. In addition, an oligomer or polymer having a polar group at the molecular end or side chain, such as an acrylic copolymer.

  The content of the dispersant in the pigment dispersion composition is preferably 1 to 100% by mass and more preferably 3 to 70% by mass with respect to the mass of the pigment described above.

  The pigment derivative is one of polymer compounds used for coating the pigment, and is added to the pigment dispersion composition as necessary. The pigment is introduced into the photosensitive resin composition as fine particles by adsorbing a pigment derivative having a portion having affinity for the dispersant or a polar group to the pigment surface and using it as an adsorption point of the dispersant. The re-aggregation can be prevented, and it is effective for constructing a color filter having high contrast and excellent transparency.

  Specifically, the pigment derivative is a compound in which an organic pigment is used as a base skeleton, and an acidic group, a basic group, or an aromatic group is introduced into a side chain as a substituent. Specific examples of organic pigments include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, and benzoimidazolone pigments. Is mentioned. In general, light yellow aromatic polycyclic compounds such as naphthalene series, anthraquinone series, triazine series and quinoline series which are not called pigments are also included. Examples of the dye derivative include JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, JP-A-8-295810, and JP-A-11. -199796, JP-A-2005-234478, JP-A-2003-240938, JP-A-2001-356210, etc. can be used.

  1 mass%-30 mass% are preferable with respect to the mass of a pigment, and, as for content in the pigment dispersion composition of a pigment derivative, 3 mass%-20 mass% are more preferable. When the content is within the above range, the dispersion can be favorably performed while the viscosity is kept low, the dispersion stability after dispersion can be improved, and the color characteristics with high transmittance can be obtained. When producing a filter, it can be configured to have high contrast with good color characteristics.

  The dispersion method can be performed, for example, by finely dispersing a pigment and a dispersant previously mixed with a homogenizer or the like using a bead disperser using zirconia beads or the like. .

In the present invention, when a dye is used as the (A) colorant, a uniformly dissolved colored photosensitive resin composition is obtained.
(A) There is no restriction | limiting in particular as dye which can be used as a coloring agent, The well-known dye conventionally used as a color filter use can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like.

  The chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, A dye such as xanthene, phthalocyanine, benzopyran, or indigo can be used.

<(B) Structural unit represented by (B-1) general formula (I), (B-2) structural unit having N-substituted maleimide group in the molecule, and (B-3) general formula (II) Binder resin containing at least one structural unit selected from the group consisting of structural units represented by
The colored photosensitive resin composition of the present invention contains (B) at least one binder resin.
(B) The binder resin contains (B-1) a structural unit represented by the following general formula (I), (B-2) a structural unit having an N-substituted maleimide group, and (B-3) in the molecule. ) It contains at least one structural unit selected from the group consisting of structural units represented by the following general formula (II).

[(B-1) Structural Unit Represented by General Formula (I)]
Hereinafter, the structural unit represented by the following general formula (I) is appropriately referred to as “structural unit (B-1)”.

In the general formula ^(I), the R 11 ^{to R 15} each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an aryl ^{group, R 16} represents a hydrogen atom or a methyl group.

R ^{11 to} R ¹⁵ in the general formula (I) are each independently preferably a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 5 to 14 carbon atoms. An atom, a bromine atom, a chlorine atom, a cyano group, an alkyl group having 1 to 7 carbon atoms, or an aryl group having 5 to 10 carbon atoms is more preferable.
The alkyl group may have a substituent, and the alkyl group may be linear, branched, or cyclic, and examples thereof include an alkyl group having 1 to 7 carbon atoms, such as a methyl group and an n-propyl group. , Iso-propyl group, t-butyl group and the like are preferable.
The aryl group may have a substituent, and examples of the substituent include an alkyl group having 1 to 7 carbon atoms or an aryl group having 5 to 14 carbon atoms, preferably a phenyl group, a furyl group, Naphthyl group.

Of these, preferred as the general formula (I) are those in which R ^{11 to} R ¹⁵ are each independently a hydrogen atom, a methyl group, a phenyl group or a halogen atom, and R ¹⁶ is a hydrogen atom or a methyl group.

[(B-2) Structural Unit Having N-Substituted Maleimide Group]
Hereinafter, the structural unit having (B-2) N-substituted maleimide group is appropriately referred to as “structural unit (B-2)”. As a structural unit (B-2), the structural unit shown below is mentioned, for example.

[(B-3) Structural unit represented by general formula (II)]
Hereinafter, the structural unit represented by the following general formula (II) is appropriately referred to as “structural unit (B-3)”.

In General Formula (II), R ²¹ represents a hydrogen atom or a methyl group, and R ²² represents an alkylene group having 1 to 6 carbon atoms. R ²³ and R ²⁴ each independently represent a hydrogen atom or an alkyl group having 4 or less carbon atoms. R ²³ and R ²⁴ may be bonded to each other to form a carbocycle.

Preferred as the general formula (II) is one in which R ²¹ is a hydrogen atom, R ²² is a methylene group or an ethylene group, and R ²³ and R ²⁴ are bonded to each other to form a 6-membered ring.

(B) The binder resin has at least one structural unit selected from the group consisting of the structural unit (B-1), the structural unit (B-2), and the structural unit (B-3) in the molecule. What is necessary is just to have 2 or more types.
When a plurality of the structural units are included, structural units belonging to different groups, such as a combination of the structural unit (B-1) and the structural unit (B-2), may be the same structural unit, for example, the structural unit Different structural units belonging to (B-1) may be used.
The binder resin (B) in the present invention preferably has a structural unit (B-1) among the above structural units.

(B) The binder resin contains (B-1) a structural unit represented by the general formula (I), (B-2) a structural unit containing an N-substituted maleimide group, and (B-3) in the molecule. The total of structural units represented by the general formula (II) is preferably 50 mol% or more and 90 mol% or less, more preferably 50 mol% or more and 80 mol% or less, more preferably 60 mol% or more and 80 mol% or less. It is more preferable that the content is not more than%. When the total amount of the structural units in the binder resin is within the above range, the development latitude is good, the film loss during development after exposure is reduced, and the surface smoothness of the resulting cured film is good.
In particular, it is more preferable that the structural unit (B-1) is contained in an amount of 20 mol% or more and 90 mol% or less. Specifically, the structural unit (B-1) is contained in an amount of 50 mol% or more and 80 mol% or less. An embodiment containing 50 mol% or more and 80 mol% or less of the unit (B-2) and 50 mol% or more and 80 mol% or less of the structural unit (B-3) is preferable.

[Structural unit having acidic group]
Furthermore, (B) binder resin may have a structural unit which has an acidic group in a molecule | numerator.
Examples of the structural unit having an acidic group include structural units derived from a carboxy group-containing unsaturated monomer. Examples of the carboxy group-containing unsaturated monomer include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, Unsaturated dicarboxylic acid such as itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid or the like; trivalent or higher unsaturated polycarboxylic acid or the anhydride thereof; succinic acid mono [2- (meth) Mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl]; ω-carboxypolycaprolactone mono These are mono (meth) acrylates of polymers having a carboxy group and a hydroxyl group at both ends, such as (meth) acrylate.
Among these carboxy group-containing unsaturated monomers, succinic acid mono (2-acryloyloxyethyl) and phthalic acid mono (2-acryloyloxyethyl) are respectively M-5300 and M-5400 (Toagosei ( (Commercially available) under the trade name.
The carboxy group-containing unsaturated monomers may be used alone or in combination of two or more.

Among these, as the structural unit having a preferable acidic group, carboxylic acid, chalcogen analog of carboxylic acid, carbohydrazone acid [RC (═NNH ₂ ) OH], carboxymidic acid [RC (═NH) OH], Sulfonic acid [RS (O) ₂ OH], sulfinic acid [RS (O) OH], sulfenic acid [RSOH], selenonic acid [RSe (O) ₂ OH], selenic acid [RSe (O) OH], selenic acid Structural units derived from analogs of [RSeOH], phosphoric acid and its acid-related compounds, silicic acid, and boric acid, particularly preferred are structural units derived from acrylic acid, methacrylic acid, and phosphoric acid.

  (B) The content of the structural unit having an acidic group in the binder resin is preferably 5 mol% or more and 50 mol% or less, and more preferably 10 mol% or more and 30 mol% or less. Within this range, the surface smoothness and heat resistance during development are good.

(B) The binder resin may contain other structural units in addition to the structural units described above. Examples of other structural units include structural units derived from the following unsaturated monomers.
Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m -Aromatic vinyl compounds such as vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether;
Indenes such as indene and 1-methylindene;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) Acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate Rate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, isobornyl Such as (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate, etc. Saturated carboxylic acid esters;

2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 3-dimethyl Unsaturated carboxylic acid aminoalkyl esters such as aminopropyl (meth) acrylate; unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate; unsaturated carboxylic acid oxetanyl esters such as oxetanyl (meth) acrylate; vinyl acetate, Carboxylic acid vinyl esters such as vinyl propionate, vinyl butyrate and vinyl benzoate;
Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether;
Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide;
Unsaturated amides such as (meth) acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide;
Unsaturated imides such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide;
Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene;
Macromonomers having a mono (meth) acryloyl group at the end of the polymer molecular chain, such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane;
These components derived from unsaturated monomers may be used alone or in combination of two or more.

  Below, the exemplary compounds 1-1 to 1-8 and the exemplary compounds 2 to 40 of (B) binder resin are shown. The (B) binder resin in the present invention is not limited to these exemplary compounds as long as the above requirements are satisfied.

  (B) The weight average molecular weight of the binder resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 50,000, and still more preferably in the range of 10,000 to 40,000. Within this range, the developability and linearity of the pattern formed are good.

  The content of the (B) binder resin in the colored photosensitive resin composition of the present invention is preferably in the range of 10% by mass to 50% by mass, and preferably in the range of 15% by mass to 40% with respect to the solid content of the colored photosensitive resin composition. A range of mass% is more preferred.

  The colored photosensitive resin composition of the present invention may contain a resin having a structure other than the (B) binder resin, which is a specific component in the present invention. (B) As a resin having a structure other than the binder resin, it acts as a binder for the colorant, and when producing a color filter, it is preferably used for a developer used in the development processing step, particularly preferably an alkaline developer. In particular, an acrylic copolymer having a carboxy group is preferable, and an ethylenically unsaturated monomer having one or more carboxy groups and other monomers are not particularly limited. A copolymer with a copolymerizable ethylenically unsaturated monomer is preferred.

In the present invention, as a specific example of a resin that can be used in combination with a structure other than the (B) binder resin,
(Meth) acrylic acid / methyl (meth) acrylate copolymer,
(Meth) acrylic acid / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / methyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
Etc.

Moreover, the resin containing the following epoxy rings or oxetane rings can also be used.
Styrene / methacrylic acid / tricyclomethacrylate methacrylate [5.2.1.0 ^2,6 ] decan-8-yl / glycidyl methacrylate copolymer,
Styrene / acrylic acid / tricycloacrylate [5.2.1.0 ^2,6 ] decan-8-yl / glycidyl acrylate copolymer,
Benzyl methacrylate / methacrylic acid / 3- (methacryloyloxymethyl) oxetane / t-butyl methacrylate copolymer,
Benzyl methacrylate / methacrylic acid / 3- (methacryloyloxymethyl) -3-ethyloxetane / styrene copolymer,

Butadiene / styrene / methacrylic acid / tricyclomethacrylate methacrylate [5.2.1.0 ^2,6 ] decan-8-yl / glycidyl methacrylate copolymer,
Butadiene / methacrylic acid / tricyclomethacrylate methacrylate [5.2.1.0 ^2,6 ] decan-8-yl / glycidyl methacrylate copolymer,
Styrene / methacrylic acid / tricyclomethacrylate [5.2.1.0 ^2,6 ] decan-8-yl / methacrylic acid-6,7-epoxyheptyl copolymer,
Styrene / acrylic acid / maleic anhydride / methacrylic acid-6,7-epoxyheptyl copolymer,
t-butyl methacrylate / acrylic acid / maleic anhydride / methacrylic acid-6,7-epoxyheptyl copolymer,
Styrene / methacrylic acid / methyl methacrylate / glycidyl methacrylate copolymer,
p-methoxystyrene / methacrylic acid / cyclohexyl acrylate / glycidyl methacrylate copolymer.

<(C) Polymerizable compound>
The colored photosensitive resin composition of the present invention contains (C) a polymerizable compound.
The polymerizable compound that can be used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is a compound having at least one terminal ethylenically unsaturated bond, preferably two or more. To be elected. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used.
Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or A dehydration condensation reaction product with a polyfunctional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid. )
In this specification, acrylate and methacrylate are collectively referred to as (meth) acrylate.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include (meth) acrylic acid ester, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1, 3 -Butanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (( (Meth) acryloyloxypropyl) ether, trimethylolethane tri (meth) acrylate, hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, tetraethylene Recall di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipenta Erythritol hexa (meth) acrylate, sorbitol triacrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth) acrylate, sorbitol hexa (meth) acrylate, tri ((meth) acryloyloxyethyl) isocyanurate, polyester (meth) acrylate oligomer , Isocyanuric acid EO-modified tri (meth) acrylate,

  Bisphenol A di (meth) acrylate, modified bisphenol A di (meth) acrylate EO, trimethylolpropane tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, trimethylolethane tri (meth) acrylate Tetraethylene glycol di (meth) acrylate, pentaerythritol diacrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, pentaerythritol tetraacrylate EO modified product, dipenta An erythritol hexaacrylate EO modified body is mentioned as a preferable thing.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, JP-A-59- Those having an aromatic skeleton described in Japanese Patent No. 5241 and JP-A-2-226149, those containing an amino group described in JP-A-1-165613, and the like are also preferably used.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (V) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

General formula (V)
^{_{CH 2 = C (R 4)}} COOCH 2 CH (R 5) OH (V)
(However, R ⁴ and R ⁵ each independently represent H or CH _3. )

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56- Urethane compounds having an ethylene oxide skeleton described in JP 17654, JP-B 62-39417, and JP-B 62-39418 are also suitable. Furthermore, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. Can obtain a photopolymerizable composition having an excellent photosensitive speed.

Other examples include polyester acrylates, epoxy resins and (meth) described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates reacted with acrylic acid. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and vinylphosphonic acid compounds described in JP-A-2-25493 Etc. can also be mentioned. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used.
Moreover, as a commercial item, urethane oligomer UAS-10, UAB-140 (made by Nippon Paper Industries Co., Ltd.), DPHA (made by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600 and AI-600 (manufactured by Kyoeisha Chemical Industry) are preferred.
Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

  A preferred embodiment of the polymerizable compound (C) in the colored photosensitive resin composition of the present invention includes a compound containing 5 to 15 polymerizable groups in the molecule and a compound containing 1 to 4 polymerizable groups in the molecule. Use a mixture. Preferred examples of the compound containing 5 to 15 polymerizable groups in the molecule and the compound containing 1 to 4 polymerizable groups in the molecule include the following compounds.

  Examples of the compound containing 5 to 15 polymerizable groups in the molecule include dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol penta (meth) acrylate, sorbitol hexa (meth) acrylate, And U-6HA, U-15HA, UA-32P, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), TO-2248, 2349, 1382 (manufactured by Toagosei Co., Ltd.). Also, neopentyl glycol oligo (meth) acrylate, 1,4-butanediol oligo (meth) acrylate, 1,6-hexanediol oligo (meth) acrylate, trimethylolpropane oligo (meth) acrylate, pentaerythritol oligo (meth) Compounds containing 5 to 15 (meth) acryl groups in the molecule such as acrylate, urethane (meth) acrylate, and epoxy (meth) acrylate can be mentioned. In the case of such an oligomer, the molecular weight is 1000 to 5000. A range is preferable.

  Examples of the compound containing 1 to 4 polymerizable groups in the molecule include trimethylolpropane tri (meth) acrylate, trimethylolpropane PO (propylene oxide) -modified tri (meth) acrylate, and trimethylolpropane EO (ethylene oxide) -modified tri. (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated penta And erythritol tetra (meth) acrylate.

  In the case of using a mixture of a compound containing 5 to 15 polymerizable groups in the molecule and a compound containing 1 to 4 polymerizable groups in the molecule, the compound containing 5 to 15 polymerizable groups in the molecule and the molecule To the compound containing 1 to 4 polymerizable groups (compound containing 5 to 15 polymerizable groups in the molecule: compound containing 1 to 4 polymerizable groups in the molecule) in terms of mass: 60: The range of 40-95: 5 is preferable, and the range of 70: 30-90: 10 is more preferable.

(C) The total content of the polymerizable compound is preferably 10% by mass to 50% by mass, and preferably 15% by mass to 40% by mass in the total solid content in the colored photosensitive resin composition layer of the present invention. It is more preferable that it is 15 mass%-30 mass%.
(C) When the content of the polymerizable compound is within the above range, the resulting cured film has good heat resistance, and generation of wrinkles during coating film formation or after post-baking is suppressed, and the surface roughness is small. A smooth cured film is formed.

  In the colored photosensitive resin composition of the present invention, the mass ratio ((D) photopolymerization initiator / (C) polymerizable compound) between (C) the polymerizable compound and (D) the photopolymerization initiator described later is 0.00. 1 or more and 2.0 or less, preferably 0.1 or more and 1.0 or less, particularly preferably 0.3 or more and 0.9 or less. By setting it within the above range, the pattern formability is good and the adhesion to the substrate is excellent. Further, the amount of mask thickening after exposure and development is sufficient, and pattern peeling is suppressed.

<(D) Photopolymerization initiator represented by general formula (III)>
The colored photosensitive resin composition of the present invention contains at least one photopolymerization initiator represented by the following general formula (III) (hereinafter, appropriately referred to as (D) a specific initiator). (D) By containing a specific initiator, it hardens | cures with high sensitivity and the coloring after baking of the formed coloring pattern is suppressed.

In the general formula (III), X ¹ , X ² , and X ³ each independently represent a hydrogen atom, a halogen atom, or an alkyl group, and R ¹ represents —R, —OR, —COR, —SR, —CONRR 'Or -CN, and R ² and R ³ each independently represent -R, -OR, -COR, -SR, or -NRR'. R and R ′ each independently represents an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these groups are substituted with one or more selected from the group consisting of a halogen atom and a heterocyclic group. And one or more carbon atoms constituting the alkyl chain in the alkyl group and the aralkyl group may be replaced with an unsaturated bond, an ether bond, or an ester bond, and R and R ′ are bonded to each other. May form a ring.

In the general formula (III), examples of the halogen atom in the case where X ¹ , X ² , and X ³ represent a halogen atom include fluorine, chlorine, bromine, and iodine, and X ¹ , X ² , and X ³ are Examples of the alkyl group in the case of representing an alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, an amyl group, an isoamyl group, and a tertiary amyl group. Group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, tertiary octyl group, nonyl group, isononyl group, decyl group, isodecyl group, vinyl group, allyl group, butenyl group, ethynyl group, propynyl group , Methoxyethyl group, ethoxyethyl group, propyloxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxy Ethyl group, methoxypropyl group, monofluoromethyl group, difluoromethyl group, trifluoromethyl group, trifluoroethyl group, perfluoroethyl group, 2- (benzoxazol-2'-yl) ethenyl group, and the like.
Especially, it is preferable that all of X < ¹ >, X < ² > and X < ³ > represent a hydrogen atom, or X < ¹ > represents an alkyl group and X < ² > and X < ³ > both represent a hydrogen atom.

In the general formula (III), examples of the alkyl group represented by R and R ′ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a secondary butyl group, and a tertiary butyl group. , Amyl group, isoamyl group, tertiary amyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, tertiary octyl group, nonyl group, isononyl group, decyl group, isodecyl group, vinyl group, allyl group Group, butenyl group, ethynyl group, propynyl group, methoxyethyl group, ethoxyethyl group, propyloxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, methoxypropyl group, monofluoromethyl group, difluoro Methyl group, trifluoromethyl group, trifluoroethyl group, perfluoroethyl group , 2- (benzoxazol-2′-yl) ethenyl group and the like.
Examples of the aryl group represented by R and R ′ include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a chlorophenyl group, a naphthyl group, an anthryl group, and a phenanthrenyl group.
Examples of the aralkyl group represented by R and R ′ include benzyl group, chlorobenzyl group, α-methylbenzyl group, α, α-dimethylbenzyl group, phenylethyl group, phenylethenyl group and the like.
Examples of the heterocyclic group represented by R and R ′ include a pyridyl group, a pyrimidyl group, a furyl group, a thiophenyl group, and the like.
Examples of the ring formed by bonding R and R ′ to each other include a piperidine ring and a morpholine ring.

R ² and R ^{3 including} R and R ′ are each independently a methyl group, a hexyl group, a cyclohexyl group, —S—Ph, —S—Ph—Cl, or —S—Ph—. Br is a particularly preferred embodiment.

(D) Among the specific polymerization initiations, in the general formula (III), X ¹ , X ² and X ³ are all hydrogen atoms; R ¹ is an alkyl group, particularly a methyl group; R Those in which ² is an alkyl group, particularly a methyl group; those in which R ³ is an alkyl group, particularly an ethyl group, are particularly suitable as a photopolymerization initiator.

  Accordingly, preferred specific examples of the specific polymerization initiator represented by the general formula (III) include compounds A to F exemplified below. However, the present invention is not limited by the following compounds.

  The specific polymerization initiator represented by the general formula (III) can be synthesized, for example, by the method described in JP-A-2005-220097.

  The compound represented by the general formula (III) used in the present invention has an absorption wavelength in a wavelength region of 250 nm to 500 nm. More preferably, the thing which has an absorption wavelength in the wavelength range of 300 nm-380 nm can be mentioned. In particular, those having high absorbance at 308 nm and 355 nm are preferable.

Content of (D) specific polymerization initiator used by this invention needs to be 5 mass% or more and 15 mass% or less with respect to the total solid of a colored photosensitive resin composition. If the content is less than 5% by mass, the sensitivity will be insufficient, and the target line width will not be achieved. If the content exceeds 15% by mass, the chemical resistance will be insufficient, or the taper shape will be inversely tapered. It is not preferable.
The content is preferably in the range of 5 to 15% by mass, more preferably in the range of 10 to 15% by mass.

In addition to the (D) specific polymerization initiator, the colored photosensitive resin composition of the present invention includes (D) another photopolymerization start having a structure different from that of the specific polymerization initiator as long as the scope of the present invention is not impaired. An agent (hereinafter referred to as (D-2) other photopolymerization initiator) may be contained.
(D) The structure different from the specific polymerization initiator (D-2) As the other photopolymerization initiator, as long as it is a compound that initiates and accelerates the polymerization of the polymerizable compound (C), a conventionally known one is used. Can be used without limitation. Specifically, for example, a lophine photopolymerization initiator, an oxime photopolymerization initiator having a structure different from that of the general formula (III), an organic halogenated compound, an oxydiazole compound, a carbonyl compound, a ketal compound, a benzoin compound, Examples include acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, organic boric acid compounds, disulfonic acid compounds, onium salt compounds, acylphosphine (oxide) compounds, and the like.

  (D-2) Examples of lophine photopolymerization initiators that can be used as other photopolymerization initiators include hexaarylbiimidazole compounds. Examples of the hexaarylbiimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2-chlorophenyl)- 4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) ) Biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2,4- Dichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2,4,6-trichloro) Phenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5 ′ -Tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2'-bis (2-cyanophenyl) -4,4 ', 5.5'-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2' -Bis (2-cyanophenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2'-bis (2-methylphenyl) -4,4', 5 5′-tetrakis (4-methoxycarbonylphenyl) biimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxyca Bonylphenyl) biimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2-ethyl) Phenyl) -4,4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) biimidazole, 2,2′-bis (2-ethylphenyl) -4,4 ′, 5,5′-tetrakis (4 -Ethoxycarbonylphenyl) biimidazole, 2,2'-bis (2-ethylphenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2'-bis (2 -Phenylphenyl) -4,4 ', 5,5'-tetrakis (4-methoxycarbonylphenyl) biimidazole, 2,2'-bis (2-phenylphenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2'-bis (2-phenylphenyl) -4,4', 5,5'-tetrakis (4-phenoxy) Carbonylphenyl) biimidazole,

2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra- (4-methoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra- (3-methoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra- (3,4-dimethoxyphenyl) biimidazole ,

2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′ , 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2, 4,6-tribromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dicyanophenyl) -4,4 ′, 5,5′-tetra Phenylbiimidazole, 2,2′-bis (2,4,6-tricyanophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dimethylphenyl) ) -4,4 ', 5,5'-tetraphenylbiimi Sol, 2,2′-bis (2,4,6-trimethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-diethylphenyl) -4 , 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4,6-triethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 ′ -Bis (2,4-diphenylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4,6-triphenylphenyl) -4,4', 5 , 5′-tetraphenylbiimidazole, 2,2′-bis (2-fluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

  Among these, particularly preferable compounds include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (for example, B-CIM manufactured by Hodogaya Chemical Co., Ltd.), 2 , 2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra- (3,4-dimethoxyphenyl) biimidazole (for example, manufactured by Nippon Sibel Hegner: HABI1311), 2,2′-bis ( 2-methylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (for example, black gold chemical).

(D-2) As an example of another photoinitiator, an aminoacetophenone-type initiator is also mentioned as a suitable thing.
Specific examples of the aminoacetophenone initiator include compounds having a structure represented by the following formula, wherein R ¹ is represented by a hydrogen atom, a methyl group, or an ethyl group. Aminoacetophenone initiators as other photopolymerization initiators are also available as commercial products, for example, IRGACURE (Irg) 369 and IRGACURE (Irg) 379 (both manufactured by Ciba Specialty Chemicals Co., Ltd.) ).

  Also, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, organic boric acid compounds, disulfonic acid compounds, Specific examples of the onium salt compound and the acylphosphine (oxide) compound include: Wakabayashi et al., “Bull Chem. Soc. Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46- 4605, JP 48-36281, JP 55-3070, JP 60-239736, JP 61-169835, JP 61-169837, Kokai 62-58241, JP-A 62-212401 , JP-A-63-70243, JP-Sho 63-298339 discloses, M. P. Hutt “Journal of Heterocyclic Chemistry” 1 (No 3), (1970) ”, Japanese Patent Publication No. 6-29285, US Pat. Nos. 3,479,185, 4,311,783, 4,622, 286, etc., JP-A-62-143044, JP-A-62-1050242, JP-A-9-188865, JP-A-9-188686, JP-A-9-188710, JP-A-2000-131837, JP-A-2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, etc., and Kunz, Martin “Rad Tech'98. Proceeding April 19-22. , 1998, Chicago ”etc. Urate, JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, JP-A-6-175554, JP-A-6-175553, JP-A-9-188710 JP, 6-348011, JP 7-128785, JP 7-140589, JP 7-306527, JP 7-292014, J. Pat. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP 2000-66385 A, JP 2000-80068 A, JP 2004-534797 A, etc. Specific examples of the photopolymerization initiators described are listed.

  In the present invention, the content when (D-2) another photopolymerization initiator is used in combination is preferably 100 parts by mass or less with respect to 100 parts by mass of the specific polymerization initiator (D). . The total amount of photopolymerization initiator [(D) + (D-2)] relative to the total solid content of the colored photosensitive resin composition is preferably in the range of 5% by mass to 20% by mass, and 5% by mass to 15%. The range of mass% is more preferable, and the range of 10 mass% to 15 mass% is still more preferable.

  In addition, when using a compound having no absorption at the exposure wavelength as the (D) specific polymerization initiator or (D-2) other photopolymerization initiator, a compound having an absorption at the exposure wavelength is used as a sensitizer. It is preferable to use it. The sensitizer will be described later.

  In the colored photosensitive resin composition of the present invention, (B) the binder resin is a resin having at least one of the structural units (B-1) and a structural unit having an acidic group in the molecule, and (D) As a specific polymerization initiator, the aspect which contains 5 mass% or more and 15 mass% or less of ketoxime type photoinitiators represented by the said general formula (III) in total solid content is preferable.

<(E) Solvent>
The colored photosensitive resin composition of the present invention contains (E) a solvent and can be prepared using the (E) solvent. The pigment dispersion composition described above is also prepared using the solvent (E).
(E) Solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, lactic acid Methyl, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-oxypropionate, 3-oxypropionic acid 3-oxypropionic acid alkyl esters such as ethyl (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate and ethyl 3-ethoxypropionate), 2-oxypropionic acid 2-oxypropionic acid alkyl esters such as til, ethyl 2-oxypropionate, propyl 2-oxypropionate (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2 -Methyl ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, and 2-ethoxy -2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 1,3-butanediol diacetate etc;

Ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol mono n-propyl ether , Propylene glycol mono n-butyl ether, tripropylene glycol mono n-butyl ether, propylene glycol phenyl ether,
Methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol n-propyl ether acetate, propylene glycol diacetate, Propylene glycol n-butyl ether acetate, propylene glycol phenyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol n-propyl ether acetate, dipropylene glycol n-butyl ether acetate, tripropylene glycol methyl Chromatography ether acetate and the like;

  Alkoxyalkyl acetates such as 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 2 -Ethoxybutyl acetate, 4-ethoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3 -Methyl-4-methoxypentyl acetate and the like;

Ketones such as acetone, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Alcohols such as ethanol, isopropyl alcohol and the like;
Aromatic hydrocarbons such as toluene and xylene are exemplified.

Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl Carbitol acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate and the like are suitable.
(E) A solvent may be used in combination of two or more, in addition to being used alone.

  The colored photosensitive resin composition of the present invention may further contain other components such as (F) a sensitizer, a surfactant, and a thermosetting resin, if necessary.

<(F) Sensitizer>
In the colored photosensitive resin composition of the present invention, it is preferable to use a compound having absorption at the exposure wavelength as a sensitizer to increase the initiation efficiency of the (D) photopolymerization initiator. The exposure of the wavelength that can be absorbed by the sensitizer promotes the radical generation reaction of the (D) photopolymerization initiator component and the polymerization reaction of the polymerizable compound thereby.
Examples of such a sensitizer include a known spectral sensitizing dye or dye, or a dye or pigment that absorbs light and interacts with a photopolymerization initiator.

  Spectral sensitizing dyes or dyes preferred as sensitizers that can be used in the present invention include polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, Rose bengal), cyanines (for example, thiacarbocyanine, oxacarbocyanine), merocyanines (for example, merocyanine, carbomerocyanine), thiazines (for example, thionine, methylene blue, toluidine blue), acridines (for example, acridine orange, Chloroflavin, acriflavine), phthalocyanines (eg, phthalocyanine, metal phthalocyanine), porphyrins (eg, tetraphenylporphyrin, central metal-substituted porphyrin), chlorophylls (eg, chlorophyllin) I le, chlorophyllin, center metal-substituted chlorophyll), metal complexes, anthraquinones (e.g., anthraquinone), squarylium compound (e.g., squarylium), and, following amine compounds, and the like.

  Examples of amine compounds suitable for the sensitizer include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and benzoic acid. 2-dimethylaminoethyl acid, 2-dimethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) Examples include benzophenone and 4,4′-bis (ethylmethylamino) benzophenone, and among them, 4,4′-bis (diethylamino) benzophenone is preferable.

Moreover, a thiol compound is preferably mentioned as another example of a sensitizer.
The thiol compound has effects such as further improving the sensitivity of the photopolymerization initiator to actinic radiation or suppressing polymerization inhibition of the polymerizable compound by oxygen.
Examples of thiol compounds include ethylene glycol bisthiopropionate (EGTP), butanediol bisthiopropionate (BDTP), trimethylolpropane tristhiopropionate (TMTP), pentaerythritol tetrakisthiopropionate (PETP), and the like. Single functional groups such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene, N-phenyl-mercaptobenzimidazole, etc. A functional thiol compound is mentioned.
In particular, a monofunctional thiol compound is preferable from the viewpoint of stability over time and solubility in a solvent.

  The content of the sensitizer in the colored photosensitive resin composition of the present invention is appropriately selected depending on the purpose, but the sensitivity is improved by spectral sensitization, or the curing speed is improved by the balance between polymerization growth rate and chain transfer, From the viewpoints of the above, the range of 0.5% by mass to 10% by mass is preferable and the range of 0.5% by mass to 5% by mass is more preferable with respect to the mass of the total solid content of the photosensitive resin composition.

<Other additives>
The colored photosensitive resin composition of the present invention may contain other additives as necessary in addition to the essential components (A) to (E) and the preferred combination component (F). Good. Hereinafter, optional additives will be described.
(Surfactant)
The colored photosensitive resin composition of the present invention can contain a surfactant.
Since the thixotropy of the coating liquid generally increases when the pigment concentration is increased, the film after the colored photosensitive resin composition layer (colored layer coating film) is formed by applying or transferring the colored photosensitive resin composition onto the substrate Thickness unevenness is likely to occur. In particular, in the formation of a colored photosensitive resin composition layer (colored layer coating film) by the slit coating method, the coating liquid for forming the colored photosensitive resin composition layer is leveled before drying to form a uniform thickness coating film. It is important to. For this reason, it is preferable to contain an appropriate surfactant in the colored photosensitive resin composition. Preferred examples of the surfactant include surfactants disclosed in JP-A Nos. 2003-337424 and 11-133600.
Nonionic surfactants, fluorine-based surfactants, silicon-based surfactants, and the like are added as surfactants for improving coating properties.

  Nonionic surfactants include, for example, polyoxyethylene glycols, polyoxypropylene glycols, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, polyoxypropylene alkyl ethers. Nonionic surfactants such as polyoxypropylene alkyl aryl ethers, polyoxypropylene alkyl esters, sorbitan alkyl esters and monoglyceride alkyl esters are preferred.

  Specifically, polyoxyalkylene glycols such as polyoxyethylene glycol and polyoxypropylene glycol; polyoxyalkylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxypropylene stearyl ether and polyoxyethylene oleyl ether; polyoxy Polyoxyethylene aryl ethers such as ethylene octyl phenyl ether, polyoxyethylene polystyryl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene-propylene polystyryl ether, polyoxyethylene nonylphenyl ether; polyoxyethylene dilaurate , Polyoxyalkylene dialkyl esters such as polyoxyethylene distearate, sorbitan fatty acid ester There are nonionic surfactants such as stealth and polyoxyalkylene sorbitan fatty acid esters.

  Specific examples of these include, for example, the Adeka Pluronic series, the Adecanol series, the Tetronic series (above, manufactured by ADEKA Corporation), the Emulgen series, the Leodol series (above, produced by Kao Corporation), the Eleminor series, the Noni series, Pole series, Octapole series, Dodecapol series, New Pole series (Sanyo Chemicals Co., Ltd.), Pionein series (Takemoto Yushi Co., Ltd.), Nissan Nonion series (Nissho Co., Ltd.), etc. is there. These commercially available products can be used as appropriate. A preferable HLB value is 8 to 20, more preferably 10 to 17.

As the fluorosurfactant, a compound having a fluoroalkyl group or a fluoroalkylene group in at least one of the terminal, main chain and side chain can be suitably used.
Specific commercial products include, for example, MegaFuck F142D, F172, F173, F176, F176, F177, F183, F780, F781, F782, F784, F552, F554, R554, R30, and R08. (Above, manufactured by DIC Corporation), FLORARD FC-135, FC-170C, FC-430, FC-431 (above, manufactured by Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 ( As mentioned above, Asahi Glass Co., Ltd.), Ftop EF351, 352, 801, 802 (above, manufactured by JEMCO).

Examples of the silicone-based surfactant include Torre Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032, and SF-8428. DC-57, DC-190 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (above GE Toshiba Silicone Co., Ltd.).
Among these, the preferred surfactants for the present invention are Megafac F780, F781, F782, F784, F552, and F554 (manufactured by DIC Corporation).

  The addition amount of these surfactants is preferably 5 parts by mass or less, more preferably 2 parts by mass or less, and still more preferably 0.5 parts by mass or less with respect to 100 parts by mass of the colored photosensitive resin composition. Used. When the amount of the surfactant exceeds 5 parts by mass, streaks and surface roughness are likely to occur during coating and drying, and smoothness tends to deteriorate.

(Thermosetting resin)
The colored photosensitive resin composition of the present invention can contain a thermosetting resin such as an epoxy resin or an oxetane resin, if desired.
Examples of the epoxy resin include bisphenol A type compounds, cresol novolac type compounds, biphenyl type compounds, and alicyclic epoxy compounds.

For example, bisphenol A type compounds include Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170 and the like ( In addition to Toto Kasei Co., Ltd., Denacol EX-1101, EX-1102, EX-1103 and the like (Nagase Kasei), Plaxel GL-61, GL-62, G101, G102 (Made by Daicel Chemical) These similar bisphenol F-type compounds and bisphenol S-type compounds can also be mentioned. Ebecryl
Epoxy acrylates such as 3700, 3701, and 600 (manufactured by Daicel UC) can also be used.

  Examples of the cresol novolak type compounds include Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above, manufactured by Tohto Kasei Co., Ltd.), Denacol EM-125, etc. (above, manufactured by Nagase Kasei), Biphenyl Examples of the type compound include 3,5,3 ′, 5′-tetramethyl-4,4′diglycidylbiphenyl and the like.

  Examples of the alicyclic epoxy compound include Celoxide 2021, 2081, 2083, 2085, Epolide GT-301, GT-302, GT-401, GT-403, EHPE-3150 (above, manufactured by Daicel Chemical), Santo Tote ST-3000, ST-4000, ST-5080, ST-5100 and the like (above, manufactured by Tohto Kasei) and the like can be mentioned. In addition, Epototo YH-434 and YH-434L, which are amine type epoxy resins, glycidyl ester in which dimer acid is modified in the skeleton of bisphenol A type epoxy resin can be used.

  Among these epoxy resins, preferably novolak type epoxy compounds and alicyclic epoxy compounds are preferable, and those having an epoxy equivalent of 180 to 250 are particularly preferable. Examples of such a material include Epicron N-660, N-670, N-680, N-690, YDCN-704L (manufactured by DIC Corporation), and EHPE3150 (manufactured by Daicel Chemical Industries).

As the oxetane resin, Aron oxetane OXT-101, OXT-121, OXT-211, OXT-221, OXT-212, OXT-610, OX-SQ, PNOX (manufactured by Toagosei Co., Ltd.) can be used.
The oxetane resin can be used alone or mixed with an acrylic copolymer, an epoxy resin and a maleimide resin. In particular, when used in combination with an epoxy resin, the reactivity due to heat generated by ultraviolet laser exposure is high, which is preferable from the viewpoint of adhesion to the substrate.
As content in the colored photosensitive resin composition of the epoxy resin which concerns on this invention, and an oxetane resin, 0.5-15 mass% is preferable with respect to the total solid of a colored photosensitive resin composition, 1- 10% by mass is preferable from the viewpoint of both solubility in alkali and adhesion to the substrate.

(Organic carboxylic acid)
In order to promote the alkali solubility of the uncured part and further improve the developability of the colored photosensitive resin composition, an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less is added. Can do. Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Phenoxyacetic acid, methoxyphenoxy acetic, hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

(Silane coupling agent)
A silane coupling agent can be used for the colored photosensitive resin composition of this invention from a viewpoint of the adhesive improvement with the further board | substrate.
The silane coupling agent preferably has an alkoxysilyl group as a hydrolyzable group that can be chemically bonded to an inorganic material. In addition, it preferably has a group that interacts or forms a bond with an organic resin and exhibits an affinity, and such a group has a (meth) acryloyl group, a phenyl group, a mercapto group, a glycidyl group, and an oxetanyl group. Among them, those having a (meth) acryloyl group or a glycidyl group are preferable.
That is, the silane coupling agent used in the present invention is preferably a compound having an alkoxysilyl group and a (meth) acryloyl group or an epoxy group, and specifically, a (meth) acryloyl-tri having the following structure. Examples include methoxysilane compounds and glycidyl-trimethoxysilane compounds.

  As the addition amount in the case of using a silane coupling agent, the total solid content in the colored photosensitive resin composition used in the present invention is preferably in the range of 0.2% by mass to 5.0% by mass, 0.5 mass%-3.0 mass% are more preferable.

(Polymerization inhibitor)
In the present invention, it is desirable to add a small amount of a thermal polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the colored photosensitive resin composition.
Examples of the thermal polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6). -T-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt, phenoxazine, phenothiazine and the like.

The addition amount of the thermal polymerization inhibitor is preferably 0.01% by mass to 5% by mass with respect to the colored photosensitive resin composition.
If necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide can be added to prevent polymerization inhibition due to oxygen and can be unevenly distributed on the surface of the photosensitive layer during the drying process after coating. . The addition amount of the higher fatty acid derivative is preferably 0.5% by mass to 10% by mass of the colored photosensitive resin composition.

(Plasticizer)
Furthermore, in the present invention, an inorganic filler, a plasticizer, or the like may be added in order to improve the physical properties of the colored photosensitive resin composition.
Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, and the like (C) polymerizable compound ( B) 10 mass% or less can be added with respect to the total mass with binder resin.

  Although the colored photosensitive resin composition of the present invention can be cured by a conventionally known exposure means, among them, it is cured with high sensitivity by exposure to ultraviolet light and exhibits high adhesion to a substrate. The ultraviolet light exposure means may be either a laser exposure method or a proximity exposure method, but a laser exposure method is preferred from the viewpoint of suppressing surface reticulation. The colored photosensitive resin composition of the present invention can be preferably used for forming a colored pattern of a color filter.

≪Pattern forming method, color filter and manufacturing method thereof≫
The colored photosensitive resin composition and the pattern forming method of the present invention are suitable for a color filter for a liquid crystal display device. Hereinafter, a pattern forming method using the colored photosensitive resin composition of the present invention will be described as a pattern forming method in a method for producing a color filter for a liquid crystal display device, but the present invention is not limited to this method. .

  The pattern forming method of the present invention includes a colored layer forming step of forming a colored layer by applying the colored photosensitive resin composition of the present invention on a substrate, and exposing the colored layer with a pattern-like ultraviolet laser. And an exposure step for forming a latent image and a development step for developing the colored layer on which the latent image is formed to form a pattern. Furthermore, you may provide the process (baking process) of baking the said colored layer and the process (baking process) of baking the developed said colored layer as needed. These processes may be collectively referred to as a pattern formation process.

[Colored layer forming step]
The colored layer forming step in the present invention is a step of forming the colored layer by applying the colored photosensitive resin composition of the present invention on the substrate.
As the substrate, for example, non-alkali glass, soda glass, borosilicate glass, quartz glass used for liquid crystal display devices and the like, and a substrate obtained by attaching a transparent conductive film thereto, a photoelectric conversion element substrate used for a solid-state imaging device, etc. Is mentioned. Furthermore, a plastic substrate can also be used. It is preferable that a black matrix is formed in a lattice shape or the like using these substrates, and a colored pattern is formed in an empty portion of the lattice.

  If necessary, an undercoat layer may be provided on these substrates in order to improve adhesion to the upper layer, prevent diffusion of substances, or planarize the substrate surface. It is preferable that the substrate is large (generally 1 m or more per side) from the standpoint of achieving the effects of the present invention.

As a method for applying the colored photosensitive resin composition of the present invention in order to form a colored layer on a substrate, various methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method, etc. An application method by coating can be applied. Among the coating methods, slit coating is preferable from the viewpoints of accuracy and speed.
Moreover, the provision method which transfers the coating film previously formed by the said application | coating method on the temporary support body on a board | substrate can also be applied.
Regarding the transfer method, the production methods described in paragraph numbers [0023] and [0036] to [0051] of JP-A-2006-23696 and paragraph numbers [0096] to [0108] of JP-A-2006-47592 are used. It can be suitably used in the present invention.

  The thickness of the colored layer in the present invention (for example, coating thickness) is 0.5 μm to 3.0 μm after drying to obtain a sufficient color reproduction region and sufficient panel luminance. It is preferable to form so that it may become, and it is more preferable to set it as 1.5 micrometers-2.5 micrometers.

[Drying process]
After the application of the colored photosensitive resin composition as described above is completed, a drying step of drying the solvent by vacuum drying (VCD) may be performed. Furthermore, the coating layer on the substrate may be heat-dried (prebaked) to obtain a colored layer.
The prebaking temperature of the coating film is preferably 60 ° C to 140 ° C, more preferably 80 ° C to 120 ° C. The pre-bake time is preferably 30 seconds to 300 seconds, and more preferably 80 seconds to 200 seconds.

[Exposure process]
The exposure step in the present invention is a step of forming a latent image by exposing the colored layer with an ultraviolet laser in a pattern and curing the exposed region. By the exposure process of the present invention, (C) the polymerization curing reaction of the polymerizable compound occurs and proceeds by the initiation species generated from the (D) specific polymerization initiator in the patterned exposure region in the colored photosensitive resin composition. At the same time, the allyl group, N-substituted maleimide group, or cyclic imide group present in the molecule of the binder resin (B) due to heat generated by ultraviolet laser exposure causes a thermal reaction, and a curing reaction occurs and proceeds. It is considered that a pattern composed of a cured region and an uncured region is formed by the light and heat dual curing of the exposed region.

  Laser excitation media include crystals, glass, liquids, dyes, gases, etc., and lasers having oscillation wavelengths for known ultraviolet light, such as solid lasers, liquid lasers, gas lasers, and semiconductor lasers, are used from these media. Can do. Among these, a solid laser and a gas laser are preferable from the viewpoint of laser output and oscillation wavelength.

  The exposure wavelength of the ultraviolet laser used in the present invention is preferably in the range of 300 nm to 380 nm, more preferably in the range of 310 nm to 360 nm, particularly 355 nm, in terms of good sensitivity that matches the photosensitive wavelength of the colored photosensitive resin composition. A wavelength laser exposure method is preferred.

Specifically, the Nd: YAG laser third harmonic (355 nm), which is a relatively inexpensive solid output, and the excimer laser XeCl (308 nm), XeF (353 nm) can be suitably used. .
As the exposure amount of the exposure object ^(pattern), in the range of ^{1mJ / cm 2 ~100mJ / cm 2} , the range of 1mJ / cm ² ~50mJ / cm 2 is more preferable. An exposure amount within this range is preferable from the viewpoint of pattern formation productivity.

  The ultraviolet laser used in the present invention is preferably a pulse laser oscillated at a frequency of 20 Hz to 2000 Hz from the viewpoint of productivity.

  There are no particular restrictions on the exposure apparatus that can be used in the present invention, but commercially available ones such as EGIS (buoy technology) or DF2200G (Dainippon Screen Co., Ltd.) can be used. These devices are also preferably used.

  The ultraviolet laser has good light parallelism, and pattern exposure can be performed without using a mask during exposure, but the pattern shape is affected by the shape and profile of the output light. Therefore, it is preferable to expose the pattern using a mask because the linearity of the pattern becomes high.

[Development process]
The developing step in the present invention is a step of developing a colored layer in which a latent image is formed by curing in the exposed area, removing an unexposed portion, and forming a pattern. The exposure area by the ultraviolet laser is cured in a pattern, and in the development process, the unexposed part (uncured part) in the exposure process is removed by elution in an alkaline aqueous solution by performing an alkali development process. The pattern can be formed by leaving only the photocured part.

As the developer, an organic alkali developer, an inorganic alkali developer or a mixture thereof is used.
Examples of the alkali agent used in the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxy. And organic alkaline compounds such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene, and the concentration of these alkaline compounds is 0.001 to 0.001. An alkaline aqueous solution diluted with pure water so as to be 10% by mass, preferably 0.01 to 1% by mass, is preferably used as the developer. In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

The development temperature is preferably 20 ° C to 35 ° C, more preferably 23 ° C to 30 ° C. The development time is preferably 30 seconds to 120 seconds, and more preferably 40 seconds to 90 seconds. Among these, a preferable combination of the development temperature and the development time is, for example, 50 seconds to 100 seconds at a temperature of 25 ° C. and 40 seconds to 80 seconds at a temperature of 30 ° C.
The shower pressure is preferably 0.01 MPa to 0.5 MPa, preferably 0.05 MPa to 0.3 MPa, and preferably 0.1 MPa to 0.3 MPa. By selecting these conditions, it is possible to arbitrarily design the pattern shape to be rectangular or forward tapered.
By using the colored photosensitive resin composition of the present invention, the generation of wrinkles on the pattern generated during development is suppressed, and the formed pattern is excellent in smoothness.

[Post-baking process]
In the present invention, in order to complete the curing of the colored photosensitive resin composition, it is preferable to provide a post-baking step of baking the developed colored layer. Baking is performed by heating a substrate having a pattern after development and rinsing in a continuous or batch manner using heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like. It can be carried out.
As conditions for baking, the temperature is preferably 150 ° C to 260 ° C, more preferably 180 ° C to 260 ° C, and most preferably 200 ° C to 240 ° C. The baking time is preferably 10 minutes to 150 minutes, more preferably 20 minutes to 120 minutes, and most preferably 20 minutes to 90 minutes.

  When forming a colored pattern of a plurality of hues, such as RGB three hues and a light-shielding layer, the cycle of forming the colored layers, exposing, developing, and baking may be repeated for the desired number of hues, or colored for each hue. After the formation of the layer, exposure, and development, the entire hue may be finally baked. As a result, a color filter including colored pixels having a desired hue is produced.

≪Liquid crystal display device≫
The color filter of the present invention is suitable for the production of a liquid crystal display device, and the liquid crystal display device using the color filter produced by the pattern forming method of the present invention can display a high-quality image.
For the definition of display devices and explanation of each display device, refer to “Electronic Display Devices (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Devices (Junaki Ibuki, Industrial Books Co., Ltd.) Issue)). The liquid crystal display device is described in, for example, “Next Generation Liquid Crystal Display Technology (Edited by Tatsuo Uchida, Issued in 1994 by Industrial Research Co., Ltd.)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to various types of liquid crystal display devices described in, for example, the “next generation liquid crystal display technology”.

The color filter for a liquid crystal display device is particularly effective for a color TFT type liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Further, the present invention can be applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS and a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. . These methods are described, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends-(issued in 2001 by Toray Research Center Research Division)".
In addition to the color filter, the liquid crystal display device includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film. The color filter for a liquid crystal display element of the present invention can be applied to a liquid crystal display device composed of these known members.
For example, “'94 Liquid Crystal Display Peripheral Materials and Chemicals Market (Kentaro Shima, CMC 1994)”, “2003 Liquid Crystal Related Market Status and Future Prospects (Volume 2)” (Table Yoshiyoshi Co., Ltd.) Fuji Chimera Research Institute, published in 2003) ”.

  Regarding backlights, SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, 18-24 pages (Yasuhiro Shima), 25-30 pages (Yukiaki Yagi), etc. Are listed.

  When the color filter produced by the pattern forming method of the present invention is used in a liquid crystal display device and combined with a conventionally known three-wavelength tube of a cold cathode tube, a high contrast can be realized. By using a light source (RGB-LED) as a backlight, a liquid crystal display device having high luminance and high color purity and good color reproducibility can be provided.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “%” and “part” are based on mass.

(Synthesis Example 1: Synthesis of alkali-soluble resin 1 having an allyl group)
54 g of 1-methoxy-2-propanol was placed in a 200 mL three-necked flask equipped with a stirring rod provided with stirring blades, a reflux condenser, and a thermometer, and heated to 70 ° C. under a nitrogen stream. A solution obtained by dissolving 10.07 g of allyl methacrylate, 1.93 g of methacrylate and 0.185 g of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator in 54 g of 1-methoxy-2-propanol was used as a plunger. Using a pump, it was dropped into the three-necked flask over 2.5 hours. After completion of dropping, the mixture was further stirred at 70 ° C. for 2 hours. After completion of heating, it was poured into 1 L of water and re-precipitated. The precipitate was filtered and then vacuum dried to obtain 9 g (yield 75%) of the polymer compound.
As a measurement sample of the weight average molecular weight, 0.01 g of the obtained polymer was weighed into a 10 mL volumetric flask, and about 8 mL of tetrahydrofuran was added and dissolved at room temperature. This solution was measured using gel permeation chromatography (GPC). The weight average molecular weight of the alkali-soluble resin 1 (allyl methacrylate / methacrylic acid copolymer, molar ratio = 80/20) was 35,000.

[Example 1]
1-1. Synthesis of Compound A [(D) Specific Polymerization Initiator] <Step 1: Production of Carbazole Derivative 1>
The following carbazole derivative 1 was produced as follows.

  2-thiophenecarbonyl chloride 7.53 g (0.05 mol), N-ethylcarbazole 14.6 g (0.075 mol), zinc chloride 0.34 g (0.0025 mol) and chlorobenzene 100 g were charged at 75 to 90 ° C. For 2 days. Thereafter, 200 g of ethyl acetate and 200 g of water were added to extract the oil layer. Furthermore, after distilling off the solvent, the residue was purified by column chromatography (ethyl acetate: n-hexane = 1: 4 to 1: 2) to give a green viscous liquid (yield 6.5 g, yield 43%, purity 94.95). 3%).

The chemical shift of ¹ H-NMR of the obtained liquid was as follows, and it was confirmed that the liquid was carbazole derivative 1 which was the target product.
8.71 (s: 1H), 8.13 (d: 1H), 8.10 (d: 1H), 7.73 (d: 2H), 7.53 (d: 1H), 7.46 (t : 2H), 7.34 (d: 1H), 7.32 (t: 1H), 4.42 (q: 2H), 1.48 (t: 3H)

<Step 2: Production of acetyl derivative 1>
The following acetyl derivative 1 was produced as follows.

  9.1 g (0.03 mol) of carbazole derivative 1 obtained in Step 1, 9.6 g (0.072 mol) of aluminum chloride and 50 g of chlorobenzene were charged, and 2.62 g (0.033 mol) of acetyl chloride at 0 ° C. ) Was added dropwise over 30 minutes, and the mixture was further stirred at room temperature for 1 hour. Thereafter, 30 g of ethyl acetate and 40 g of water are added to decompose aluminum chloride, and the oily layer is extracted and the solvent is distilled off to obtain a green viscous liquid (yield 9.2 g, yield 89%, purity 94%). Obtained.

The obtained liquid material had the following ¹ H-NMR chemical shift, and it was confirmed that the liquid material was acetyl compound 1 as the target product.
8.77 (s: 1H), 8.74 (s: 1H), 8.17 (d: 1H), 8.12 (d: 1H), 7.74 (d: 2H), 7.52 (d : 2H), 7.22 (t: 1H), 4.44 (q: 2H), 2.74 (s: 3H), 1.50 (t: 3H)

<Step 3: Production of oxime body 1>
The following oxime body 1 was produced as follows.

  10.4 g (0.03 mol) of acetyl compound 1 obtained in Step 2, 9.6 g (0.072 mol) of hydroxylamine hydrochloride and 30 g of dimethylformamide were charged and stirred at 80 ° C. for 2 hours. Thereafter, 30 g of ethyl acetate, 10 g of n-hexane and 50 g of water were added to extract the oil layer. The solvent was distilled off and purification was performed by column chromatography (ethyl acetate: n-hexane = 1: 1 to 1: 3) to obtain a pale yellow solid (yield 3.0 g, yield 28%, purity 94%). It was.

The obtained solid had a chemical shift of ¹ H-NMR as follows, and it was confirmed that the solid was the oxime body 1 as the target product.
8.72 (s: 1H), 8.38 (s: 1H), 8.10 (d: 1H), 7.87 (d: 1H), 7.74 (d: 2H), 7.48 (d : 2H), 7.21 (t: 1H), 4.42 (q: 2H), 2.43 (s: 3H), 1.50 (t: 3H)

<Step 4: Production of Compound A>
A polymerization initiator (Compound A) was produced as follows.

  When 1.82 g (0.005 mol) of oxime 1 obtained in Step 3, 0.61 g (0.006 mol) of acetic anhydride and 15 g of propyl acetate were charged and stirred at 80 ° C. for 2 hours, a solid was precipitated. The solid was filtered off at 30 ° C. and washed with a methanol / propyl acetate mixed solvent to obtain a white solid (yield 1.4 g, yield 70%, purity 98%).

The obtained solid had the following ¹ H-NMR chemical shift, and it was confirmed that the solid was Compound A (specific polymerization initiator), which was the target product.
8.72 (s: 1H), 8.51 (s: 1H), 8.12 (d: 1H), 7.99 (d: 1H), 7.74 (d: 2H), 7.52 (d : 2H), 7.21 (t: 1H), 4.42 (q: 2H), 2.53 (s: 3H), 2.30 (s: 3H), 1.49 (t: 3H)

1-2. Preparation of colored photosensitive resin composition (Preparation of pigment dispersion 1)
Pigment dispersion 1 was prepared as follows. That is, with the composition described below, a homogenizer was used and stirred for 3 hours at a rotation speed of 3,000 rpm to prepare a mixed solution, and further bead dispersion using 0.1 mmφ zirconia beads Dispersion treatment was carried out for 8 hours using a machine Ultra Apex Mill (manufactured by Kotobuki Industries Co., Ltd.)

CI Pigment Blue 15: 6 11.8 parts CI Pigment Violet 23 1.0 parts Disperbyk 161 manufactured by Big Chemie (30% solution) 24 parts Propylene glycol methyl ether acetate (hereinafter referred to as PGMEA)
63.2 parts
100 copies in total

(Preparation of photosensitive resin composition)
A component of the following composition was further added to 39.2 parts of the obtained pigment dispersion 1, and the mixture was stirred and mixed to prepare a blue (B) photosensitive resin composition.
Alkali-soluble resin 1 (allyl methacrylate / methacrylic acid copolymer,
16.4 parts of 20% PGMEA solution with a molar ratio of 80/20 and a weight average molecular weight of 35000) Polymerizable compound: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA) 3.9 parts 1. Compound: Tetramethylolmethane tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK Ester A-TMMT) 0.69 parts Photopolymerization initiator: Compound A (the following structure; compound obtained in the above synthesis example) 74 parts ・ Polyfunctional thiol compound (sensitizer: structure below) 0.55 parts ・ Epoxy compound: (EHPE3150, manufactured by Daicel Chemical Industries, Ltd.) 0.60 part ・ Solvent: PGMEA and 3-ethoxyethyl propionate ( = 80/20 [mass ratio]) 35.9 parts-polymerization inhibitor: p-methoxyphenol 0.001 part-surfactant 1: me Fuck F-554 (manufactured by DIC Corporation) 0.02 parts

[Examples 2-14, Comparative Examples 1-5]
Except that the binder resin, colorant, photopolymerization initiator and sensitizer in the preparation of the colored photosensitive resin composition of Example 1 were changed to the compounds shown in Tables 1 and 2 below, the same manner was carried out. The colored photosensitive resin compositions of Examples 2 to 14 and Comparative Examples 1 to 5 were prepared.
In addition, (B) binder resin in the following Table 1-Table 2 shows the exemplary compound quoted in the description column of the said (B) binder resin by the code | symbol. The structure of the comparative binder resin used in Comparative Example 1 is as shown below.

-Evaluation of colored photosensitive resin composition-
(Formation of patterned pixels)
Examples 1 to 13 and Comparative Examples 1 to 5 colored photosensitive resin compositions obtained as described above were applied to the surface of a non-alkali glass substrate (Corning, 1737, 550 mm × 660 mm) by a slit coater. (Hirata Kiko Co., Ltd., HC-6000) and then pre-baked in a clean oven at 90 ° C. for 120 seconds to form a coating film (colored layer) having a thickness of 2.0 μm. An attached substrate was obtained. (Colored layer formation process)
Next, as a laser exposure apparatus, EGIS (buoy technology Co., Ltd., third harmonic of YAG laser (355 nm), pulse width 6 nS) is used, and the surface of the photosensitive resin composition layer (colored layer) is about 1 mJ / 20 cm ² pulse irradiations were performed through a photomask to cure the exposed portion. (Exposure process).
Thereafter, this substrate was developed with a 1.0% developer (CDK-1) of potassium hydroxide developer CDK-1 (manufactured by FUJIFILM Electronics Materials) using a developing device (manufactured by Hitachi High-Technologies Corporation). 1 part by weight, 99 parts by weight of pure water diluted at 25 ° C.), the shower pressure was set to 0.20 MPa, developed for 50 seconds, washed with pure water, and then air-dried (developing step). Thereafter, post-baking was performed in a clean oven at 220 ° C. for 30 minutes to form a blue stripe pixel array on the substrate.

(Evaluation of line width sensitivity)
Using a mask having a line and space of 20μm width, 20mJ / cm ^2, the gap (gap) between the photosensitive resin composition layer surface and the mask on the substrate with the coating film and 200 [mu] m, at an exposure dose of 20 mJ / cm ² Exposed to form an exposed substrate. The exposed substrate thus obtained was subjected to the above development, washing, air drying, and post-baking treatment. The obtained line pattern was observed with an optical microscope, the line width was measured, and evaluated according to the following criteria.
A: 30 μm or more B: 27 μm or more and less than 30 μm C: 25 μm or more and less than 27 μm D: Less than 25 μm E: No pattern is formed. Or it peels off and cannot be evaluated.

(Evaluation of linearity)
The line pattern obtained by the evaluation of the line width sensitivity was observed with an optical microscope (200 times), and the linearity (roughness) of the line width was visually observed and evaluated according to the following criteria.
Evaluation criteria A: There is no rattling or chipping, and the line is straight.
B: Although some rattlings are observed, the line is almost straight.
C: Line variation of about 2 μm (about 10% with respect to the line width) occurs due to rattling or chipping.
D: Line variation of about 5 μm (20% or more with respect to the line width) occurs due to rattling or chipping.
E: No pattern is formed. Or, there is pattern peeling and evaluation is not possible.

(Evaluation of heat resistance)
The substrate obtained by the evaluation of the line width sensitivity was additionally baked in a clean oven at 240 ° C. for 60 minutes, and the color change (ΔE ^* ab) before and after the additional baking was measured using a spectrophotometer MCPD- manufactured by Otsuka Electronics Co., Ltd. 2000 was used for evaluation. Here, ΔE ^* ab means a color difference in the L ^* a ^* b ^* color system. The change ΔE ^* ab in color difference was measured and evaluated according to the following criteria.
Evaluation criteria 5: ΔE ^* ab is 0 or more and less than 1.0.
4.5: ΔE ^* ab is 1.0 or more and less than 2.0 4: ΔE ^* ab is 2.0 or more and less than 3.0.
3.5: ΔE ^* ab is 3.0 or more and less than 3.5.
3: ΔE ^* ab is 3.5 or more and less than 4.0.
2.5: ΔE ^* ab is 4.0 or more and less than 5.0.
2: ΔE ^* ab is 5.0 or more 1: There is peeling.

(Evaluation of reticulation)
Using a mask with a line and space of 100 μm width, 20 mJ / cm ² , the gap (gap) between the surface of the photosensitive resin composition layer on the coated substrate and the mask is 200 μm, and the exposure amount is 20 mJ / cm ² . Exposed to form an exposed substrate. The exposed substrate thus obtained was subjected to the above development, washing, air drying, and post-baking treatment. The obtained line pattern was observed with an optical microscope (200 times), and the surface roughness was evaluated according to the following criteria.
Evaluation criteria A: The surface is flat and unevenness is not recognized at all.
B: Although slight irregularities are observed on the surface, the entire surface is almost flat.
C: Concavities and convexities are observed in part of the upper, lower, left and right lines.
D: Concavities and convexities are observed throughout the line.
E: Deep unevenness is seen over the entire line.

(Comprehensive evaluation)
Line width sensitivity, linearity, and heat resistance were comprehensively evaluated according to the following criteria. The results are summarized in Table 3. In general, in use, the overall rating is preferably 5 or 4.
Evaluation criteria 5: Very good.
4: Level at which there is no problem in normal use.
3: Level at which normal use is barely acceptable.
2: A level where performance is insufficient and cannot be used normally.
1: At least three items in each evaluation are significantly inferior.

As is apparent from Table 3, the colored photosensitive resin compositions of Examples 1 to 14 according to the present invention have good line width sensitivity, the obtained pattern is excellent in linearity, and the colored pattern is heated. The color change was small, the occurrence of reticulation during development was suppressed, and a good colored pattern was obtained.
On the other hand, Comparative Example 1 using a binder resin having no specific structural unit in the present invention is inferior in line width sensitivity, pattern linearity, heat resistance, and reticulation, and is outside the scope of the present invention. Comparative Example 2 using the oxime ester-based photopolymerization initiator has insufficient heat resistance, and Comparative Examples 3 to 5 using photopolymerization initiators other than the oxime ester-based photopolymerization line have both line width sensitivity and linearity. Both properties and reticulation were significantly inferior to those of the examples.

[Examples 15 to 18]
2-1. Preparation of pigment dispersion (Synthesis Example 2: Synthesis of zinc halide phthalocyanine pigment)
Zinc phthalocyanine was produced from phthalodinitrile and zinc chloride.
Halogenation was performed by mixing 3.1 parts of sulfuryl chloride, 3.7 parts of anhydrous aluminum chloride, 0.46 parts of sodium chloride and 1 part of zinc phthalocyanine at 40 ° C., and dropping 2.2 parts of bromine. The mixture was reacted at 80 ° C. for 15 hours, and then the reaction mixture was poured into water to precipitate a partially brominated zinc phthalocyanine crude pigment. This aqueous slurry was filtered, washed with hot water at 80 ° C., and dried at 90 ° C. to obtain 2.6 parts of a purified partially brominated zinc phthalocyanine crude pigment.

1 part of this partially brominated zinc phthalocyanine crude pigment, 7 parts of crushed sodium chloride, 1.6 parts of diethylene glycol and 0.09 part of xylene were charged into a double arm kneader and kneaded at 100 ° C. for 6 hours. After kneading, it was taken out into 100 parts of water at 80 ° C., stirred for 1 hour, and then filtered, washed with hot water, dried and ground to obtain a partially brominated zinc phthalocyanine pigment.
The obtained partially brominated zinc phthalocyanine pigment has an average composition of ZnPcBr ₁₀ Cl ₄ H ₂ (Pc: phthalocyanine) and contains an average of 10 bromine atoms in one molecule, based on halogen content analysis by mass spectrometry. there were.
The average primary particle size measured with a transmission electron microscope (JEM-2010, manufactured by JEOL Ltd.) was 0.065 μm.

(Synthesis Example 3: Synthesis of polyester resin (i-1))
6.4 g of n-octanoic acid, 200 g of ε-caprolactone and 5 g of titanium (IV) tetrabutoxide were mixed, heated at 160 ° C. for 8 hours, and then cooled to room temperature to obtain a polyester resin (i-1).
The scheme is shown below.

(Synthesis Example 4: Synthesis of Resin (J-1))
10 g of polyethyleneimine (SP-018, number average molecular weight 1,800, manufactured by Nippon Shokubai) and 100 g of the polyester resin (i-1) obtained in Synthesis Example 3 were mixed and heated at 120 ° C. for 3 hours to obtain an intermediate. (J-1B) was obtained. Then, it stood to cool to 65 degreeC, 200 g of PGMEA (solvent) containing 3.8 g of succinic anhydrides was added slowly, and it stirred for 2 hours. Thereafter, PGMEA was added to obtain a 10 mass% PGMEA solution of the resin (J-1). The resin (J-1) has a side chain derived from the polyester resin (i-1) and a carboxy group derived from succinic anhydride.
A synthesis scheme is shown below.

(Preparation of pigment dispersion 2)
-Pigment dispersion 2: Green pigment zinc halide phthalocyanine dispersion-
A partially brominated zinc phthalocyanine pigment obtained in Synthesis Example 2 (hereinafter referred to as PG58 as appropriate) 14.9 was added to a high-speed disperser “TSC-6H” manufactured by Imex Co., Ltd. charged with zirconia beads having a diameter of 0.5 mm. Part, 7.1 parts of BYK-2001 acrylic dispersant “BYK-2001” and 78 parts of PGMEA were charged and stirred at 2000 rpm for 8 hours to partially brominated zinc halide phthalocyanine pigment (green pigment PG58) A dispersion liquid (pigment dispersion liquid 2) was prepared.

(Preparation of pigment dispersion 3)
-Pigment dispersion 3: Yellow pigment Pigment yellow 150 dispersion-
As a pigment, C.I. I. 15 parts of Pigment Yellow 150 (hereinafter appropriately referred to as PY150: average particle diameter 60 nm), 7.5 parts of the resin (J-1) obtained in Synthesis Example 4 and 77.5 parts of PGMEA were added to a bead mill (zirconia beads 0). 3 mm) to mix and disperse for 3 hours to prepare a dispersion (pigment dispersion 3) of yellow pigment PY150.

2-2. Preparation of colored photosensitive resin composition The components of the following composition were added and mixed by stirring to prepare a colored photosensitive resin composition (color resist solution) for green (G) of Example 15.

Green pigment PG58 dispersion (Pigment dispersion 2) 53.42 parts Yellow pigment PY150 dispersion (Pigment dispersion 3) 23.81 parts Polymerizable compounds: Dipentaerythritol hexahexaacrylate and dipenta Mixture of succinic acid derivatives of erythritol pentaacrylate, acid value: 67 mg KOH (trade name: TO-2349, manufactured by Toagosei Co., Ltd.) ... 11.68 parts, photopolymerization initiator: (the following structure: Compound A2) ... 1.536 parts, increase Sensitizer: Multifunctional thiol 1.536 parts (trade name: Karenz MTBD1, Showa Denko)
Alkali-soluble resin 0.109 parts [Allyl methacrylate / methacrylic acid (= 80/20 [molar ratio]) copolymer (weight average molecular weight: 30,000)]
・ Solvent: Propylene glycol monomethyl ether acetate: 57.47 parts ・ Polymerization inhibitor: p-methoxyphenol: 0.005 parts ・ Fluorosurfactant (trade name: manufactured by MegaFac F554 DIC): 0.027 parts / 3 -Ethoxyethyl propionate ... 30.00 parts

(Example 16)
Example 15 is the same as Example 15 except that (F) the polyfunctional thiol (trade name: Karenz MTBD1, Showa Denko) used as the sensitizer was changed to a polyfunctional thiol (trade name: Karenz MTPE1, Showa Denko). In the same manner, a colored photosensitive resin composition (color resist solution) of Example 16 was prepared.
(Example 17) *
In Example 15, (C) (Product name: TO-2349 manufactured by Toa Gosei Co., Ltd.) used as the polymerizable compound was changed to (Product name: M-520 Toa Gosei Co., Ltd.) in the same manner as in Example 15. A colored photosensitive resin composition (color resist solution) of Example 17 was prepared.
M-520 is a mixture of succinic acid derivatives of dipentaerythritol hexahexaacrylate and dipentaerythritol pentaacrylate, and is a polymerizable compound having an acid value of 30 mgKOH.
(Example 18)
In Example 15, (C) used as the polymerizable compound (trade name: TO-2349, manufactured by Toa Gosei Co., Ltd.) was changed to (trade name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., described as “DPHA” in the table below). A colored photosensitive resin composition (color resist solution) of Example 18 was prepared in the same manner as Example 15 except for the above.
(A) Colorant, (B) Binder resin, (C) Polymerizable compound, (D) Photopolymerization initiator and (F) Sensitizer used in the colored photosensitive resin compositions of Examples 15 to 18 Details are shown in the following Table 4. In addition, the (B) binder resin in the following Table 4 shows the exemplified compounds mentioned in the description column of the (B) binder resin by the reference numerals. The proximity exposure is described as “proxy” in Table 4.

-Evaluation of colored photosensitive resin composition-
(Formation of patterned pixels)
Each of the colored photosensitive resin compositions of Examples 15 to 18 obtained as described above was coated on a 550 mm × 650 mm glass substrate (1737, manufactured by Corning) at a coating speed of 100 mm / s using a slit die. After coating with a gap of 100 μm and a coating flow rate of 1.3 ml / s to form a coating film, it is vacuum-dried in a vacuum drying chamber at an ultimate pressure of 0.5 Torr, and dried in an oven at 80 ° C. for 120 seconds (prebaking) ), A colored photosensitive resin composition layer having a thickness of 2.0 μm was formed.
Thereafter, the formed colored photosensitive resin composition layer was subjected to proximity exposure at 20 mJ / cm ² (illuminance 35 mW / cm ² ) Gap 200 μm with an ultrahigh pressure mercury lamp using a stripe pattern having a mask size of 20 μm, and coloring after exposure. The photosensitive resin composition layer is sprayed in a shower form for 40 seconds with a 1% aqueous solution of alkali developer CDK-1 (trade name: manufactured by Fuji Film Electronics Materials Co., Ltd.), and pure water is sprayed in a shower form for 60 seconds. The developer was washed away.
Next, the colored photosensitive resin composition layer that has been exposed and developed as described above is heat-treated in an oven at 230 ° C. for 40 minutes (post-baking) to form colored pixels of the color filter on the glass substrate. A colored pattern was formed, and a green stripe pixel array (color filter) was formed on the glass substrate.

  The formed color filter was evaluated in the same manner as in Example 1 for line width sensitivity, linearity of the formed pattern, heat resistance, development time, reticulation, and comprehensive evaluation. The results are shown in Table 5 below.

  As is apparent from Table 5, the colored photosensitive resin compositions of Examples 15 to 18 according to the present invention have line width sensitivity even when proximity exposure is performed in the exposure step, as in the case of laser exposure. The obtained pattern was excellent in linearity, and even when the colored pattern was heated, the color change was small, the occurrence of reticulation during development was suppressed, and a good colored pattern was obtained.

(Example 19)
3-1. Preparation of colored photosensitive resin composition The components of the following composition were added and mixed by stirring to prepare a green (G) colored photosensitive resin composition (color resist solution) of Example 19.
-Green pigment PG58 dispersion (Pigment dispersion 2) ... 53.42 parts-Yellow pigment PY150 dispersion (Pigment dispersion 3) ... 23.81 parts-Polymerizable compounds: dipentaerythritol hexahexaacrylate and dipentaerythritol A mixture of tall pentaacrylate and a succinic acid derivative of dipentaerythritol pentaacrylate (trade name: TO-2349, manufactured by Toagosei Co., Ltd.)
... 11.68 parts-Photopolymerization initiator: (The following structure: Compound A3) ... 1.636 parts-Sensitizer: Multifunctional thiol ... 1.536 parts (trade name: Karenz MTBD1, Showa Denko)
Alkali-soluble resin 0.109 parts [Allyl methacrylate / methacrylic acid (= 80/20 [molar ratio]) copolymer (weight average molecular weight: 30,000)]
・ Solvent: Propylene glycol monomethyl ether acetate: 57.47 parts ・ Polymerization inhibitor: p-methoxyphenol: 0.005 parts ・ Fluorosurfactant (trade name: manufactured by MegaFac F554 DIC): 0.027 parts / 3 -Ethoxyethyl propionate ... 30.00 parts

(Example 20)
Example 19 Example 19 except that the polyfunctional thiol (trade name: Karenz MTBD1, Showa Denko) used as (F) sensitizer in Example 19 was changed to a polyfunctional thiol (trade name: Karenz MTPE1, Showa Denko). In the same manner, a colored photosensitive resin composition (color resist solution) of Example 20 was prepared.
(Example 21)
In Example 19, (C) (Product name: TO-2349, manufactured by Toa Gosei Co., Ltd.) used as the polymerizable compound was changed to (Product name: M-520 Toa Gosei Co., Ltd.). A colored photosensitive resin composition (color resist solution) of Example 21 was prepared.
(Example 22)
Example 19 is the same as Example 19 except that (C) the polymerizable compound (trade name: TO-2349, manufactured by Toa Gosei Co., Ltd.) is changed to (trade name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.). Then, a colored photosensitive resin composition (color resist solution) of Example 22 was prepared.
(A) colorant, (B) binder resin, (C) polymerizable compound, (D) photopolymerization initiator and (F) sensitizer used in the colored photosensitive resin compositions of Examples 19 to 22 Details are shown in the following Table 6. In addition, the (B) binder resin in the following Table 6 shows the exemplified compounds listed in the description column of the (B) binder resin by their symbols. The proximity exposure is described as “proxy” in Table 6.

-Evaluation of colored photosensitive resin composition-
(Formation of patterned pixels)
Each of the colored photosensitive resin compositions of Examples 19 to 22 obtained as described above was formed into a colored photosensitive resin composition layer in the same manner as in Examples 15 to 17, and was exposed in a pattern. Then, it was developed and post-baked to form a colored pattern constituting colored pixels of the color filter on the glass substrate, and a green stripe pixel array (color filter) was formed on the glass substrate.

  The formed color filter was evaluated in the same manner as in Examples 15 to 17 in terms of line width sensitivity, linearity of the formed pattern, heat resistance, development time, reticulation, and comprehensive evaluation. The results are shown in Table 7 below.

  As is apparent from Table 7, the colored photosensitive resin compositions of Examples 19 to 22 according to the present invention have line width sensitivity similar to Examples 15 to 17 even when the initiator is changed. The obtained pattern was excellent in linearity, and even when the colored pattern was heated, the color change was small, the occurrence of reticulation during development was suppressed, and a good colored pattern was obtained.

Claims (10)

At least (A) a colorant, (B) (B-1) a structural unit represented by the following general formula (I) in the molecule, (B-2) a structural unit having an N-substituted maleimide group, and ( B-3) a binder resin containing at least one structural unit selected from the group consisting of structural units represented by the following general formula (II), (C) a polymerizable compound, (D) the following general formula (III) And (E) a solvent, and the content of the (D) photopolymerization initiator is 5% by mass to 15% by mass with respect to the total solid content of the colored photosensitive resin composition. A colored photosensitive resin composition.

In general formula (I), R ^{11 to} R ¹⁵ each independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, or an aryl group, and R ¹⁶ represents a hydrogen atom or a methyl group.

In General Formula (II), R ²¹ represents a hydrogen atom or a methyl group, and R ²² represents an alkylene group having 1 to 6 carbon atoms. R ²³ and R ²⁴ are each independently an alkyl group having 4 or less carbon atoms, either one is a hydrogen atom and the other is an alkyl group having 4 or less carbon atoms, or R ²³ and R ²⁴ are A group that forms a carbocycle by bonding.

In the general formula (III), X ¹ , X ² , and X ³ each independently represent a hydrogen atom, a halogen atom, or an alkyl group, and R ¹ represents —R, —OR, —COR, —SR, —CONRR 'Or -CN, and R ² and R ³ each independently represent -R, -OR, -COR, -SR, or -NRR'. R and R ′ each independently represents an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these groups are substituted with one or more selected from the group consisting of a halogen atom and a heterocyclic group. And one or more carbon atoms constituting the alkyl chain in the alkyl group and the aralkyl group may be replaced with an unsaturated bond, an ether bond, or an ester bond, and R and R ′ are bonded to each other. May form a ring.   The colored photosensitive resin composition according to claim 1, further comprising (F) a sensitizer selected from polyfunctional thiol compounds.   The (B) binder resin contains (B-1) a structural unit represented by the general formula (I), (B-2) a structural unit having an N-substituted maleimide group, and (B-3) in the molecule. ) Including at least one structural unit selected from the group consisting of the structural unit represented by the general formula (II) at 50 mol% to 90 mol%, and a structural unit having an acidic group, and having a weight average molecular weight. The colored photosensitive resin composition according to claim 1 or 2, which is a resin in the range of 10,000 to 100,000.   The colored photosensitive resin composition according to any one of claims 1 to 3, wherein the colored photosensitive resin composition is for ultraviolet laser exposure. A colored layer forming step of forming a colored layer by applying the colored photosensitive resin composition according to any one of claims 1 to 4 on a substrate;
An exposure process for curing the exposed portion by exposing the colored layer in a pattern-like manner with an ultraviolet laser; and
A development step of removing the uncured portion of the pre-colored layer by development to form a pattern;
A pattern forming method including:   The pattern forming method according to claim 5, wherein an exposure wavelength of the ultraviolet laser is in a range of 300 nm to 380 nm.   The pattern forming method according to claim 5, wherein the ultraviolet laser is a pulse laser oscillated at a frequency of 20 Hz to 2000 Hz.   The manufacturing method of a color filter including the process of forming a colored pattern on a board | substrate by the pattern formation method of any one of Claims 5-7.   A color filter manufactured by the manufacturing method according to claim 8.   A display device comprising the color filter according to claim 9.