JP2021162861A - Photosensitive resin composition and cured film thereof, and color filter having the cured film - Google Patents

Abstract

To provide a photosensitive resin composition and its cured film which can reduce reflectance with a simple method and can achieve both high light-shielding property and high precision pattern formation, and a color filter having the cured film.SOLUTION: A photosensitive resin composition contains a polymerizable unsaturated group-containing alkali-soluble resin (i) that is obtained by reacting a dicarboxylic acid or a tricarboxylic acid or an acid monoanhydride thereof, and a tetracarboxylic acid or an acid dianhydride thereof with respect to a reactant of an epoxy compound having two or more phenyl glycidyl ether groups in a molecule and an unsaturated group-containing monocarboxylic acid, and has a weight average molecular weight of 2,500 or more, a (meth)acrylate resin (ii) that has a carboxy group and a polymerizable unsaturated group in a side chain and has a weight average molecular weight of 6,000 or more, as resin components, and a light-shielding material (iii) selected from the group consisting of a black organic pigment, a black inorganic pigment and a mixed color organic pigment, as an essential component.SELECTED DRAWING: None

Description

The present invention relates to a photosensitive resin composition, a cured film thereof, and a color filter having the cured film.

Generally, a flat panel display such as a liquid crystal display is provided with an antireflection layer in order to reduce the reflection of light incident from the outside. The antireflection layer mainly includes an Anti-Glare (AG) film (anti-glare film) and an Anti-Reflection (AR) film (anti-reflection film). The AG film can prevent reflection by forming irregularities on the surface of the hard coat resin layer to scatter the reflected light, and further utilizing internal scattering due to the difference in the refractive index between the hard coat resin and the particles. However, the contrast is lowered due to the scattering of the reflected light on the surface, and the resolution is lowered due to the internal scattering of the transmitted light from the backlight. On the other hand, in the AR film, mainly two types of layers having different refractive indexes are alternately laminated, and the reflected light can be reduced by utilizing the interference of light. Recently, there is also a moth-eye method in which the surface of an AR film is formed with fine irregularities in which the refractive index continuously changes by nanoimprinting or the like. The AR film can suppress a decrease in contrast due to scattered light on the surface and a decrease in resolution due to internal scattering, and is the mainstream as an antireflection layer.

Further, in recent years, high contrast and high definition are required by downsizing and high resolution of the display, and reduction of reflectance and improvement of surface smoothness are also required in the antireflection layer. In particular, mobile information terminals, digital signage, in-vehicle displays, etc., which are expected to be used outdoors, have a great influence on visibility, and therefore, the required characteristics of the antireflection layer are high. Although the visibility of the display has been greatly improved by improving the antireflection layer, it is required to reduce the reflectance in each component other than the antireflection layer.

Examples of the components other than the antireflection layer include color filters used in liquid crystal displays. The color filter includes a coloring material constituting the pixel, a black matrix for partitioning the pixel, a protective film for protecting the pixel, and the like. In particular, many of the coloring materials used for the black matrix have a high refractive index, which has a large effect on the reflectance of the color filter. As a method of reducing the reflectance of the black matrix, reduction of the amount of the coloring material can be mentioned, but the contrast of the image tends to be lowered because the light-shielding property is lowered.

In addition, organic electroluminescence displays have been put on the market as self-luminous displays that do not use color filters, and in recent years, development of displays that use micro LEDs and quantum dots for pixels has also progressed. Generally, these self-luminous displays do not use a color filter, but if the reflectance of the partition wall that partitions the pixels is high, the visibility tends to decrease.

Patent Document 1, Patent Document 2 and Patent Document 3 disclose a black matrix in which two layers having different optical densities (a layer having a high light-shielding property and a layer having a high light-shielding property) are laminated.

Patent Document 4 discloses a colored cured film having a low reflectance (reflectance on the surface side of the colored cured film) opposite to the substrate.

Japanese Unexamined Patent Publication No. 2014-157179 Japanese Unexamined Patent Publication No. 2014-30368 International Publication No. 2014/136738 Japanese Unexamined Patent Publication No. 2018-141849

According to the findings of the present inventors, the methods disclosed in Patent Document 1, Patent Document 2 and Patent Document 3 are visually recognizable because the refractive index of the black matrix with respect to the light entering from the substrate side on which the color filter is formed is low. Expected to improve sex. However, since a layer having a high light-shielding property is formed on the substrate and then a layer having a high light-shielding property is laminated, the manufacturing process of the color filter becomes complicated, which may lead to productivity.

Further, in the colored cured film disclosed in Patent Document 4, since silica particles are present on the surface of the colored cured film, irregularities may occur on the surface of the colored cured film. Therefore, the irregularity on the surface reduces the specular reflection but increases the diffuse reflection, and the increase in the diffuse reflection may cause whitening or dullness, resulting in deterioration of the texture.

The present invention has been made in view of this point, and is a photosensitive resin composition capable of reducing reflectance by a simple method and achieving both high light-shielding property and high-definition pattern formation, and curing thereof. An object of the present invention is to provide a film and a color filter having the cured film.

As a result of diligent studies to solve the above problems, the present inventors can reduce the reflectance by a simple method by using two kinds of resins having a specific structure, and have high light-shielding property and high definition. We have found a photosensitive resin composition capable of achieving both pattern formation.

That is, the photosensitive resin composition of the present invention has a dicarboxylic acid, a tricarboxylic acid, or a reaction product of an epoxy compound having two or more phenylglycidyl ether groups in the molecule and an unsaturated group-containing monocarboxylic acid. A polymerizable unsaturated group-containing alkali-soluble resin (i) having a weight average molecular weight of 2500 or more obtained by reacting an acid monoanhydride and a tetracarboxylic acid or an acid dianhydride thereof, and a carboxy group and polymerizable side chains. A light-shielding material (iii) containing an unsaturated group and having a weight average molecular weight of 6000 or more (meth) acrylate resin (ii) as a resin component, and selected from the group consisting of black organic pigments, black inorganic pigments or mixed color organic pigments. ) Is included as an essential ingredient.

Further, the cured film of the present invention is obtained by curing the above-mentioned photosensitive resin composition.

Further, the color filter of the present invention has the cured film as a black matrix.

According to the present invention, a photosensitive resin composition, a cured film thereof, and a color filter having the cured film, which can reduce the reflectance by a simple method and can achieve both high light-shielding property and high-definition pattern formation. Can be provided.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. In the present invention, when the first decimal place is 0 for the content of each component, the notation after the decimal point may be omitted.

The photosensitive resin composition according to the embodiment of the present invention is a dicarboxylic acid or tricarboxylic acid or tricarboxylic acid with respect to a reaction product of an epoxy compound having two or more phenylglycidyl ether groups in the molecule and an unsaturated group-containing monocarboxylic acid. A polymerizable unsaturated group-containing alkali-soluble resin (i) having a weight average molecular weight of 2500 or more obtained by reacting an acid or an acid monoanhydride thereof, and a tetracarboxylic acid or an acid dianhydride thereof, and carboxy on the side chain. It contains a (meth) acrylate resin (ii) having a group and a polymerizable unsaturated group and having a weight average molecular weight of 6000 or more as a resin component, and is selected from the group consisting of black organic pigments, black inorganic pigments or mixed color organic pigments. It contains a light-shielding material (iii) as an essential component.

The components (i) to (iii) will be described below.

(Alkali-soluble resin containing polymerizable unsaturated group)
The polymerizable unsaturated group-containing alkali-soluble resin having a weight average molecular weight of 2500 or more, which is the component (i) according to the embodiment of the present invention, is represented by the following general formula (1).

(In the formula (1), R ₁ is an independent hydrocarbon group having 2 to 4 carbon atoms, R ₂ is an independent hydrocarbon group having 1 to 3 carbon atoms, and R ₃ is an independent hydrocarbon group. a hydrogen atom or a methyl group, X is a divalent organic radical independently carbon atoms which may contain a hetero element therein 1~20, -CO -, - SO 2 -, - C ( CF ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -Si (CH ₃ ) _2- , -O-, Fluolene-9,9-diyl group represented by the general formula (2) Alternatively, it is a single bond, Y is a tetravalent carboxylic acid residue, Z is an independent hydrogen atom or a substituent represented by the general formula (3), but at least one of Z is general. It is a substituent represented by the formula (3), G is a hydrogen atom independently or a substituent represented by the general formula (4), and a is a number of 0 to 10 independently. The average value of a in one molecule is also a number of 0 to 10, and the average value of a in the composition is also a number of 0 to 10. b is an independently number of 0 to 4, and one molecule. The average value of b in the composition is also a number of 0 to 4, and the average value of b in the composition is also a number of 0 to 4. n is an integer having an average value of 1 to 20.)

In formulas (3) and (4), R ₄ and R ₆ are hydrogen atoms or methyl groups, R ₅ and R ₇ are hydrocarbon groups having 2 to 4 carbon atoms, and L is divalent or trivalent. It is a carboxylic acid residue, where c and f are numbers 0 or 1, d and e are numbers 0, 1 or 2, and d + e is a number 1 or 2.)

Polymerizable unsaturated group-containing alkali-soluble resin (i) having a weight average molecular weight of 2500 or more represented by the general formula (1) (hereinafter, also simply referred to as "alkali-soluble resin represented by the general formula (1)". ) Will be described.

First, a bisphenol type epoxy compound (a-1) having two or more phenylglycidyl ether groups in one molecule represented by the following general formula (8) (hereinafter, simply, an epoxy represented by the general formula (8)). (Also referred to as "compound") is reacted with an unsaturated group-containing monocarboxylic acid (for example, (meth) acrylic acid) to obtain a diol containing a polymerizable unsaturated group. In addition, "(meth) acrylic acid" is a general term for acrylic acid and methacrylic acid, and means one or both of them.

(In the formula (8), R ₁ is an independent hydrocarbon group having 2 to 4 carbon atoms, R ₂ is an independent hydrocarbon group having 1 to 3 carbon atoms, and X is an independent hydrocarbon group. Divalent organic groups having 1 to 20 carbon atoms, which may contain a hetero element inside, -CO-, -SO _2- , -C (CF ₃ ) _2- , -CH _2- , -C (CH) ₃ ) _2- , -Si (CH ₃ ) _2- , -O-, a fluorene-9,9-diyl group represented by the general formula (2) or a single bond, where a is 0 to 10 independently. , And b is independently a number from 0 to 4.)

The epoxy compound represented by the general formula (8) is an epoxy compound having two phenylglycidyl ether groups in one molecule, which is obtained by reacting bisphenols with epichlorohydrin. Since this reaction generally involves oligomerization of the diglycidyl ether compound, it contains an epoxy compound containing two or more bisphenol skeletons.

Examples of the above bisphenols include bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, bis (4-hydroxy-3,5-dichlorophenyl) ketone, and bis (4-hydroxyphenyl) ketone. Hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dichlorophenyl) sulfone, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy) -3,5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3,5-dimethylphenyl) ) Dimethylsilane, bis (4-hydroxy-3,5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dichlorophenyl) methane, bis (4-hydroxy-3, 5-Dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3) , 5-Dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, bis (4-hydroxyphenyl) ether, bis (4-Hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl) ether, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy) -3-Methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy) -3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene Includes 4-hydroxy-3,5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene, 4,4'-biphenol, 3,3'-biphenol and the like.

Examples of unsaturated group-containing monocarboxylic acids that react with the epoxy compound represented by the general formula (8) include acrylic acid and methacrylic acid, succinic anhydride, maleic anhydride, and phthalan anhydride, in addition to acrylic acid and methacrylic acid. A compound obtained by reacting an acid monoanhydride such as an acid is included.

A known method can be used for the reaction between the epoxy compound represented by the general formula (8) and the unsaturated group-containing monocarboxylic acid. For example, Japanese Patent Application Laid-Open No. 4-355450 describes a diol containing a polymerizable unsaturated group by using about 2 mol of (meth) acrylic acid with respect to 1 mol of an epoxy compound having two epoxy groups. It is stated that it can be obtained. In the present invention, the reactant obtained by the above reaction is a diol (d) containing a polymerizable unsaturated group represented by the general formula (9) (hereinafter, simply, a diol represented by the general formula (9)). Also called).

(In the formula (9), R ₁ is an independent hydrocarbon group having 2 to 4 carbon atoms, R ₂ is an independent hydrocarbon group having 1 to 3 carbon atoms, and R ₃ is an independent hydrocarbon group. a hydrogen atom or a methyl group, X is a divalent organic radical independently carbon atoms which may contain a hetero element therein 1~20, -CO -, - SO 2 -, - C ( CF ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -Si (CH ₃ ) _2- , -O-, fluorene-9,9-diyl group represented by the general formula (2) Or it is a single bond, where a is independently a number 0-10 and b is independently a number 0-4.)

Examples of the divalent organic group having 1 to 20 carbon atoms include a divalent hydrocarbon group, a divalent group having one or two carboxy groups in the side chain of the hydrocarbon group, and the like. The hydrocarbon group may have an ether-bonding oxygen atom or an ester bond inside.

Examples of the divalent hydrocarbon group include linear or linear groups such as methylene group, ethylene group, propylene group, isopropylidene group, sec-butylene group, methylisobutylene group, hexylene group, decylene group and dodecylene group. Includes hydrocarbon groups with branched chains. Further, examples of the divalent group having an ester bond inside the hydrocarbon group include divalent organic groups represented by the general formulas (10) to (12).

(In equation (10), h is an integer of 1 to 20.)

(In equation (11), i is an integer of 2 to 20, and j is an integer of 0 to 10.)

(In equation (12), k is an integer from 0 to 18, and l is an independent integer from 1 to 10.)

Further, the hydroxy group in the molecule of the diol represented by the general formula (9), which is a reaction product of the epoxy compound represented by the general formula (8) and the unsaturated group-containing monocarboxylic acid, is reacted. (A) Examples of dicarboxylic acids or tricarboxylic acids or their acid monoanhydrides include chain hydrocarbon dicarboxylic acids or tricarboxylic acids or their acid monoanhydrides, alicyclic hydrocarbon dicarboxylic acids or tricarboxylic acids or theirs. Acid monoanhydride, aromatic dicarboxylic acid or tricarboxylic acid, or their acid monoanhydride and the like are included.

Examples of the above chain hydrocarbon dicarboxylic acid or tricarboxylic acid or their acid monoanhydrides include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citralinic acid, malonic acid, glutaric acid, Includes citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, and their acid monoanhydrides. Further included are dicarboxylic acids or tricarboxylic acids into which any of these substituents have been introduced, their acid monoanhydrides and the like.

Examples of the alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid or their acid monoanhydride include cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornandicarboxylic acid, methyltetrahydrophthalic acid, Acid monoanhydrides such as methyl-3,6-endomethylenetetrahydrophthalic acid, chlorendic acid and hexahydrotrimeric acid are included. Furthermore, dicarboxylic acids or tricarboxylic acids into which any of these substituents have been introduced, their acid monoanhydrides, and the like are also included.

Examples of the above aromatic dicarboxylic acid or tricarboxylic acid or their acid unianoxides include phthalic acid, isophthalic acid, trimellitic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid and their acids. Contains anhydrides. Further included are dicarboxylic acids or tricarboxylic acids into which any of these substituents have been introduced and their acid monoanhydrides.

Among the above dicarboxylic acids or tricarboxylic acids or their acid monoanhydrides, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid and trimellitic acid are preferable, and succinic acid and itaconic acid. , Tetrahydrophthalic acid is more preferred. Further, among the above dicarboxylic acids or tricarboxylic acids, it is preferable to use those acid monoanhydrides. As the above-mentioned acid monoanhydride of dicarboxylic acid or tricarboxylic acid, only one kind thereof may be used alone, or two or more kinds thereof may be used in combination.

Further, the hydroxy group in the molecule of the diol represented by the general formula (9), which is a reaction product of the epoxy compound represented by the general formula (8) and the unsaturated group-containing monocarboxylic acid, is reacted. (B) Examples of tetracarboxylic acid or acid dianhydride thereof include chain hydrocarbon tetracarboxylic acid, alicyclic hydrocarbon tetracarboxylic acid, aromatic tetracarboxylic acid, acid dianhydride thereof and the like. Is done.

Examples of the chain hydrocarbon tetracarboxylic acid include a chain into which a butane tetracarboxylic acid, a pentane tetracarboxylic acid, a hexane tetracarboxylic acid, and a substituent such as an alicyclic hydrocarbon group and an unsaturated hydrocarbon group have been introduced. Formula hydrocarbon Tetracarboxylic acid and the like are included.

Examples of the alicyclic hydrocarbon tetracarboxylic acid include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptantetracarboxylic acid, norbornantetracarboxylic acid, and chain hydrocarbon groups, non-existent. An alicyclic tetracarboxylic acid or the like into which a substituent such as a saturated hydrocarbon group has been introduced is included.

Examples of aromatic tetracarboxylic acids include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, naphthalene. -2,3,6,7-Tetracarboxylic acid and the like are included.

Among the above tetracarboxylic acids, biphenyl tetracarboxylic acid, benzophenone tetracarboxylic acid and diphenyl ether tetracarboxylic acid are preferable, and biphenyl tetracarboxylic acid and diphenyl ether tetracarboxylic acid are more preferable. Further, in the case of tetracarboxylic acid or its acid dianhydride, it is preferable to use the acid dianhydride. As for the above-mentioned tetracarboxylic acid or acid dianhydride thereof, only one kind thereof may be used alone, or two or more kinds thereof may be used in combination.

(A) Dicarboxylic acid or tricarboxylic acid or their acid monoanhydride to react with the hydroxy group in the molecule of the diol represented by the above general formula (9), and (b) Tetracarboxylic acid or its acid dianhydride. The molar ratio (a) / (b) with the substance is preferably 0.01 or more and 10.0 or less, and more preferably 0.02 or more and less than 3.0. When the molar ratio (a) / (b) is 0.01 or more and 10.0 or less, the optimum molecular weight for obtaining a photosensitive resin composition having good photopatterning properties can be obtained. The smaller the molar ratio (a) / (b), the larger the molecular weight and the lower the alkali solubility.

Further, the reaction between the epoxy compound represented by the general formula (8) and the unsaturated group-containing monocarboxylic acid, and the diol represented by the general formula (9) obtained by the reaction and the polybasic acid or its acid anhydride. The reaction with the substance is not particularly limited, and a known method can be adopted.

The weight average molecular weight (Mw) of the alkali-soluble resin represented by the general formula (1) synthesized by the above reaction is 2500 or more, preferably 2500 or more and 100,000 or less, and 2500 or more and 25,000 or less. More preferred. The larger the weight average molecular weight (Mw) is, the more phase separation is performed with the (meth) acrylate resin (described later), and a thin layer (10 to 100 nm) is formed on the outermost layer side (the surface not in contact with the substrate) of the cured film. Therefore, the reflectance can be reduced without providing an antireflection film or the like on the outermost layer (the surface not in contact with the base material) of the cured film. Further, the smaller the weight average molecular weight (Mw) is, the more it is possible to suppress the decrease in the adhesion of the pattern during alkaline development, and it is easy to adjust the solution viscosity of the photosensitive resin composition suitable for coating, and the alkali. It does not take too much time to develop.

The acid value of the alkali-soluble resin represented by the general formula (1) is preferably 30 mgKOH / g or more and 200 mgKOH / g or less, more preferably 40 mgKOH / g or more and 140 mgKOH / g or less, and 80 mgKOH or less. More preferably, it is / g or more and 120 mgKOH / g or less. When the acid value of the alkali-soluble resin is 30 mgKOH / g or more, the residue is less likely to remain during alkaline development. Further, when it is 200 mgKOH / g or less, the penetration of the alkaline developer does not become too fast, so that peeling development can be suppressed.

The weight average molecular weight (Mw) of the alkali-soluble resin represented by the general formula (1) can be measured by, for example, gel permeation chromatography (GPC) "HLC-8220 GPC" (manufactured by Tosoh Corporation). The acid value of the alkali-soluble resin represented by the general formula (1) can be measured using, for example, a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

Regarding the alkali-soluble resin represented by the general formula (1) of the component (i), only one type may be used alone, or two or more types may be used in combination.

The mass of the alkali-soluble resin represented by the general formula (1) is the total of the alkali-soluble resin represented by the general formula (1) and the (meth) acrylate resin (described later) represented by the general formula (13). It is preferably 40 to 99% by mass, more preferably 40 to 90% by mass, further preferably 40 to 80% by mass, and further preferably 50 to 80% by mass with respect to the mass. It is preferably 65 to 80% by mass, and particularly preferably 65 to 80% by mass. When the mass of the alkali-soluble resin is 40 to 99% by mass, the reflectance can be reduced while maintaining high-definition pattern formation.

((Meta) acrylate resin)
The (meth) acrylate resin having a carboxy group and a polymerizable unsaturated group in the side chain and having a weight average molecular weight of 6000 or more, which is the component (ii) according to the embodiment of the present invention, is, for example, the following general formula (13). ). The general formula (13) is a random copolymer containing m, o, and p of each unit, respectively.

(In the formula (13), R ₈ , R ₁₀ , and R ₁₁ are independently hydrogen atoms or methyl groups, R ₉ is a hydrocarbon group having 1 to 20 carbon atoms, and R ₉ is an ether inside. It may contain a sex oxygen atom or a urethane bond. R ₁₂ is independently a divalent hydrocarbon group having 2 to 10 carbon atoms, g is independently a number of 0 or 1, and m. , O and p are independently arbitrary integers.)

A (meth) acrylate resin (ii) having a carboxy group and a polymerizable unsaturated group in the side chain represented by the general formula (13) and having a weight average molecular weight of 6000 or more (hereinafter, simply referred to as "general formula (13)". A method for producing (also referred to as "represented (meth) acrylate resin") will be described.

The (meth) acrylate resin represented by the general formula (13) according to the embodiment of the present invention is represented by the (meth) acrylate represented by the general formula (5) and the general formula (6) ( It is derived from a polyvalent carboxylic acid compound represented by the following general formula (14), which is obtained by copolymerizing meta) acrylic acid. The general formula (14) is a random copolymer containing m and o units of each unit.

(In the formula (5), R ₈ is a hydrogen atom or a methyl group, R ₉ is a hydrocarbon group having 1 to 20 carbon atoms, and R ₉ contains an ether oxygen atom or a urethane bond inside. May be good.)

(In formula (6), R ₁₀ is a hydrogen atom or a methyl group.)

(In the formula (14), R ₈ and R ₁₀ are hydrogen atoms or methyl groups, R ₉ is a hydrocarbon group having 1 to 20 carbon atoms, and R ₉ has an ether oxygen atom or urethane bond inside. It may be included. O and m are arbitrary integers.)

_{Examples of the hydrocarbon group of R 9} represented by the general formula (5) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a hexyl group, an octyl group, an isooctyl group and a decyl group. , Dodecyl group, tetradecyl group, linear hydrocarbon group such as eicosyl group, cyclohexyl group, norbornyl group, isobornyl group, tricyclodecylmethyl group, decahydronaphthyl group, substituent represented by the following general formula (15). Includes aliphatic ethers such as cyclic aliphatic hydrocarbon groups such as, methoxyethyl group and 2- (methoxyethoxy) ethyl group, and aliphatic urethanes such as 2- (ethoxycarbonylamino) ethyl group.

(In formula (15), R ₁₃ is a hydrogen atom or a methyl group.)

Among the above hydrocarbon groups, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a cyclohexyl group, a norbornyl group, an isobornyl group and a tricyclodecylmethyl group are preferable, and a methyl group and an ethyl group are used. More preferably, it is a group, a cyclohexyl group, a norbornyl group, an isobornyl group, or a tricyclodecylmethyl group.

Regarding the (meth) acrylate represented by the general formula (5), only one type may be used alone, or two or more types may be used in combination. Further, as for the (meth) acrylic acid represented by the general formula (6), only one type may be used alone, or two or more types may be used in combination.

The polyvalent carboxylic acid represented by the general formula (14) is a component derived from the (meth) acrylate represented by the general formula (5) and a (meth) acrylic acid represented by the general formula (6). It is a copolymer in which the constituent components derived from the above are basically randomly bonded. The copolymerization method is not particularly limited, and a known copolymerization method can be adopted.

The repeating unit (m) of the component derived from the (meth) acrylate represented by the general formula (5) and the (meth) represented by the general formula (6) in the polyvalent carboxylic acid represented by the general formula (14). ) The repeating unit (o) of the component derived from acrylic acid is the sum of the numbers of m and o in consideration of reacting the (meth) acrylate having an epoxy group represented by the general formula (7). When is 100, m is preferably 20 to 70, and more preferably 30 to 60. Further, o is preferably 30 to 80, more preferably 40 to 70. Note that m and o are independently arbitrary integers. By setting m to 20 to 70 and o to 30 to 80, it is possible to achieve both solubility and curability in an alkaline developer.

Then, by reacting a part of the carboxy group of the polyvalent carboxylic acid compound represented by the general formula (14) with a (meth) acrylate having an epoxy group represented by the general formula (7), the present invention is made. A (meth) acrylate resin represented by the general formula (13) according to one embodiment can be obtained. The bonding order of the above constituent components is not particularly regular, and the copolymer is basically randomly bonded.

(In formula (7), R ₁₁ is a hydrogen atom or a methyl group, R ₁₂ is a divalent hydrocarbon group having 2 to 10 carbon atoms, and g is a number of 0 or 1.)

In the general formula (13), a component derived from the (meth) acrylate compound represented by the general formula (5), a component derived from the (meth) acrylic acid compound represented by the general formula (6), and a general component. 3 of the constituent components in which the (meth) acrylate having an epoxy group represented by the general formula (7) is added to a part of the carboxy groups of the constituent components derived from the (meth) acrylic acid represented by the formula (6). The bonding order of the constituents of the species is not particularly regular, and it is basically a copolymer in which the three constituents are bonded randomly.

The solvent used when reacting a (meth) acrylate having an epoxy group represented by the general formula (7) with a part of the carboxy group in the polyvalent carboxylic acid represented by the general formula (14) is Although not particularly limited, it is preferable that the solvent has a boiling point higher than the reaction temperature.

Examples of the above solvents include cellosolvent solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, high boiling point ethers such as ethyl carbitol acetate, butyl carbitol acetate, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate and butyl acetate. Alternatively, an ester solvent, a ketone solvent such as cyclohexanone and diisobutyl ketone, and the like are included.

The catalyst used is not particularly limited, and for example, ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride described in JP-A-9-325494, triphenylphosphine, and tris (2,6-dimethoxyphenyl) are used. Phosphines such as phosphine are included.

A (meth) acrylate resin represented by the general formula (13) is obtained by reacting a polyvalent carboxylic acid represented by the general formula (14) with a (meth) acrylate having an epoxy group represented by the general formula (7). The reaction temperature at the time of producing the above is preferably 20 to 140 ° C, more preferably 40 to 130 ° C.

Further, a (meth) acrylate having an epoxy group represented by the general formula (7) when producing a (meth) acrylate resin represented by the general formula (13) and a poly acrylate represented by the general formula (14). The charging ratio of the valent carboxylic acid can be arbitrarily changed for the purpose of adjusting the acid value and curability of the (meth) acrylate resin represented by the general formula (13). At this time, the charging ratio of the epoxy group in the (meth) acrylate having the epoxy group represented by the general formula (7) to the carboxy group in the polyvalent carboxylic acid represented by the general formula (14) is 10 to 50. It is preferably mol%, more preferably 30 to 50 mol%.

Further, the number of each repeating unit (m, o, p) when the sum of the repeating units (m, o, p) in the (meth) acrylate resin represented by the general formula (13) is 100 is It can be changed arbitrarily for the purpose of adjusting the acid value and curability. The repeating unit (m) is preferably 20 to 70, more preferably 30 to 60, and the repeating unit (o) is preferably 5 to 70, preferably 10 to 50. More preferably, the repeating unit (p) is preferably 10 to 75, and more preferably 20 to 60. When m is 20 to 70, it is possible to suppress a decrease in the content of the polymerizable double bond and a decrease in the adhesion and hardness of the cured film. Further, when o is 10 to 50, the water absorption rate of the cured film does not become too high, so that the solubility in an organic solvent is improved. Further, when p is 10 to 40, the volume shrinkage at the time of curing does not become too large, so that the adhesion to the substrate and the flatness of the surface can be improved.

The weight average molecular weight (Mw) of the (meth) acrylate resin represented by the general formula (13) is 6000 or more, preferably 6000 or more and 1,000,000 or less, and more preferably 10,000 or more and 100,000 or less. The larger the weight average molecular weight (Mw) is, the more phase separation is performed with the above-mentioned alkali-soluble resin to form a thin layer (10 to 100 nm) on the outermost layer side (the surface not in contact with the substrate) of the cured film. , The reflectance can be easily reduced even if the antireflection film or the like is not provided on the outermost layer (the surface not in contact with the base material) of the cured film. Further, as the weight average molecular weight (Mw) is smaller, it is possible to suppress a decrease in adhesion, a decrease in curability, and a deterioration in appearance due to the phase separation.

The acid value of the (meth) acrylate resin represented by the general formula (13) is preferably 30 mgKOH / g or more and 200 mgKOH / g, and more preferably 40 mgKOH / g or more and 140 mgKOH / g or less. When the acid value of the (meth) acrylate resin is 30 mgKOH / g or more, the residue is less likely to remain during alkaline development. Further, when it is 200 mgKOH / g or less, the penetration of the alkaline developer does not become too fast, so that peeling development can be suppressed.

The weight average molecular weight (Mw) and acid value of the (meth) acrylate resin represented by the general formula (13) are measured by the same device as the measuring device used for the alkali-soluble resin represented by the general formula (1). can do.

The mass of the (meth) acrylate resin represented by the general formula (13) is the total mass of the alkali-soluble resin represented by the general formula (1) and the (meth) acrylate resin represented by the general formula (13). It is preferably 1 to 60% by mass, more preferably 10 to 60% by mass, further preferably 20 to 60% by mass, and further preferably 20 to 50% by mass with respect to the mass. It is preferably 20 to 35% by mass, and particularly preferably 20 to 35% by mass. Further, when the mass of the (meth) acrylate resin is 1 to 60% by mass, the crosslinked structure is sufficiently formed, so that the cured film after curing is less likely to become brittle. From the viewpoint of more effectively obtaining the effect of lowering the reflectance by phase separation, it is preferable that the mass ratio of the (meth) acrylate resin represented by the general formula (13) is higher. Further, from the viewpoint of suppressing deterioration of the surface texture due to the phase separation, the mass ratio of the (meth) acrylate resin represented by the general formula (13) is preferably 50% by mass or less, preferably 35% by mass. More preferably, it is less than%.

(Shading material)
The light-shielding material which is the component (iii) according to the embodiment of the present invention is selected from the group consisting of black organic pigments, black inorganic pigments or mixed color organic pigments.

As the light-shielding material that can be used in the present invention, known light-shielding components can be used without particular limitation as long as they are dispersed with an average particle size of 1 to 1000 nm. The average particle size of the light-shielding material can be measured by, for example, a laser diffraction / scattering method particle size distribution meter or a dynamic light scattering method particle size distribution meter.

Examples of the black organic pigment include perylene black, cyanine black, aniline black, lactam black, and the like.

Examples of the black inorganic pigment include carbon black, chromium oxide, iron oxide, titanium black and the like.

Examples of the above-mentioned mixed color organic pigments include azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindolin pigments, dioxazine pigments, slene pigments, perylene pigments, perinone pigments, quinophthalone pigments, and di. A mixed pigment obtained by mixing at least two color pigments selected from organic pigments such as ketopyrrolopyrrole pigment and thioindigo pigment to make them pseudo-blackened is included.

Depending on the function of the target photosensitive resin composition, only one type of the light-shielding material may be used alone, or two or more types may be used in combination. For example, carbon black, titanium black, a black organic pigment or the like can be used as the light-shielding resist used in the production of the black matrix of the color filter, and red or orange as the colored resist used in the production of the pixel of the color filter. , Yellow, green, blue, purple organic pigments, etc. can be used, and as the solder resist used for producing the insulating film of the printed wiring board, organic pigments, inorganic pigments, inorganic fillers, etc. can be used, and the touch panel. Carbon black, titanium black, black organic pigments, white pigments and the like can be used as the decorative resist used in the design of the front glass of the above, and transparent fillers such as silica can be used as the transparent resist having high hardness and high durability. , Each can be appropriately selected and used.

In addition, examples of organic pigments that can be used when a mixed color organic pigment is used as the component (iii) include, but are not limited to, those having the following numbers in the color index name.
Pigment Red 2, 3, 4, 5, 9, 12, 14, 22, 23, 31, 38, 112, 122, 144, 146, 147, 149, 166, 168, 170, 175, 176, 177, 178 179, 184, 185, 187, 188, 202, 207, 208, 209, 210, 213, 214, 220, 221, 242, 247, 253, 254, 255, 256, 257, 262, 264, 266, 272 , 279 etc. Pigment Orange 5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81 etc. Pigment Yellow 1, 3, 12, 13 etc. , 14, 16, 17, 55, 73, 74, 81, 83, 93, 95, 97, 109, 110, 111, 117, 120, 126, 127, 128, 129, 130, 136, 138, 139, 150 , 151, 153, 154, 155, 173, 174, 175, 176, 180, 181, 183, 185, 191, 194, 199, 213, 214, etc. Pigment Green 7, 36, 58, etc. Pigment Blue 15, 15 : 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60, 80, etc. Pigment Violet 19, 23, 37, etc.

The content of the light-shielding material can be arbitrarily determined depending on the desired degree of light-shielding, but is preferably 20 to 80% by mass, preferably 40 to 70% by mass, based on the solid component in the photosensitive resin composition. More preferably.

When a black organic pigment such as aniline black, cyanine black, or lactam black, or a black inorganic pigment such as carbon black or titanium black is used as the light-shielding material, the mass is 40 to 60 with respect to the solid component in the photosensitive resin composition. % Is particularly preferable. When the content of the light-shielding material is 20% by mass or more with respect to the solid component in the photosensitive resin composition, sufficient light-shielding property can be obtained. Further, when the content of the light-shielding material is 80% by mass or less with respect to the solid component in the photosensitive resin composition, the content of the photosensitive resin serving as the original binder does not decrease, which is desirable. Development characteristics and film forming ability can be obtained.

The light-shielding material is usually mixed with other compounding components as a light-shielding material dispersion dispersed in a solvent, and in that case, a dispersant can be added. The dispersant that can be used is not particularly limited, and known compounds used for dispersing pigments (light-shielding materials) (compounds commercially available under the names of dispersants, dispersion wetting agents, dispersion accelerators, etc.) and the like are used. can do.

Examples of the dispersant include a cationic polymer-based dispersant, an anionic polymer-based dispersant, a nonionic polymer-based dispersant, and a pigment derivative-type dispersant (dispersion aid). In particular, the dispersant has a cationic functional group such as an imidazolyl group, a pyrrolyl group, a pyridyl group, a primary, secondary or tertiary amino group as an adsorption point to the colorant, and has an amine value of 1 to 100 mgKOH /. g, a cationic polymer-based dispersant having a number average molecular weight (Mn) in the range of 1000 to 100,000 is preferable. The content of this dispersant is preferably 1 to 35% by mass, more preferably 2 to 25% by mass, based on the total mass of the light-shielding material. High-viscosity substances such as resins generally have the effect of stabilizing dispersion, but those that do not have the ability to promote dispersion are not treated as dispersants. However, it does not limit its use for the purpose of stabilizing the dispersion.

(Photopolymerizable monomer)
The photosensitive resin composition according to the embodiment of the present invention preferably contains a photopolymerizable monomer having at least two polymerizable unsaturated groups as the component (iv).

Examples of the photopolymerizable monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and tetramethylene glycol di (meth). Acrylate, Glyoxide Di (meth) Acrylate, Trimethylol Propantri (Meta) Acrylate, Trimethylol Etantri (Meta) Acrylate, Pentaerythritol Di (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Pentaerythritol Tetra (Meta) Acrylate , Dipentaerythritol tetra (meth) acrylate, glycerol tri (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene (Meta) acrylic acid esters such as alkylene oxide-modified hexa (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate, and dendritic polymers having (meth) acrylic group as compounds having an ethylenic double bond. Is included. Only one type of these monomers may be used alone, or two or more types may be used in combination.

Further, the photopolymerizable monomer can play a role of cross-linking the molecules of the alkali-soluble resin, and in order to exert this function, it must have at least two ethylenically unsaturated bonds. Is preferable, and those having three or more ethylenically unsaturated bonds are more preferable. Further, the acrylic equivalent obtained by dividing the molecular weight of the monomer by the number of (meth) acrylic groups in one molecule is preferably 50 to 300 g / eq, and the acrylic equivalent is more preferably 80 to 200 g / eq. The photopolymerizable monomer does not have a free carboxy group.

In addition, a dendritic polymer having a (meth) acryloyl group can be used as the compound having an ethylenically unsaturated bond. Examples of the dendritic polymer include a dendritic polymer obtained by adding a polyvalent mercapto compound to a part of carbon-carbon double bonds in the (meth) acryloyl group of a polyfunctional (meth) acrylate. .. Specifically, a dendritic polymer obtained by reacting a (meth) acryloyl group of a polyfunctional (meth) acrylate represented by the general formula (16) with a polyvalent mercapto compound represented by the general formula (17), or the like. Is included.

(In formula (16), R ₁₄ is a hydrogen atom or a methyl group, and R ₁₅ is the remainder of donating n hydroxy groups out of k hydroxy groups of _{R 16} (OH) _{k to the ester bond in the formula.} Partial. Preferred R ₁₆ (OH) _k is a polyhydric alcohol based on a non-aromatic linear or branched hydrocarbon skeleton having 2 to 8 carbon atoms, or multiple molecules of the polyhydric alcohol. It is a polyhydric alcohol ether that is linked via an ether bond by dehydration condensation of alcohol, or is an ester of these polyhydric alcohols or polyhydric alcohol ethers and hydroxyic acid.)

(In formula (17), R ₁₇ is a single bond or a 2 to 6 valent C1 to C6 hydrocarbon group, r _{is 2 when R 17} is a single bond, and R ₁₇ is 2 to 6 valent. When it is the basis of, it is an integer of 2 to 6.)

Further, q shown in the general formula (16) and r shown in the general formula (17) independently represent an integer of 2 to 20, but q ≧ r.

Examples of the polyfunctional (meth) acrylate represented by the general formula (16) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethyl propantri (meth) acrylate, and ethylene oxide-modified trimethylol. Propanetri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate Etc. (meth) acrylic acid esters are included. Only one of these compounds may be used alone, or two or more of these compounds may be used in combination.

Examples of the polyvalent mercapto compound represented by the above general formula (17) include trimethylolpropane tri (mercaptoacetate), trimethylolpropane tri (mercaptopropionate), pentaerythritol tetra (mercaptoacetate), and pentaerythritol tri. (Mercaptoacetate), pentaerythritol tetra (mercaptopropionate), dipentaerythritol hexa (mercaptoacetate), dipentaerythritol hexa (mercaptopropionate) and the like are included. Only one of these compounds may be used alone, or two or more of these compounds may be used in combination.

The blending ratio of the component (i) and the component (iv) is preferably 50/50 to 90/10, preferably 60/40 to 80/20, in terms of weight ratio (i) / (iv). More preferred. When the compounding ratio of the component (i) is 50/50 or more, the cured product after curing is less likely to become brittle, and the acid value of the coating film is less likely to decrease in the unexposed portion, so that it is soluble in an alkaline developer. The decrease can be suppressed. Therefore, problems such as jagged pattern edges and non-sharpening are unlikely to occur. Further, when the compounding ratio of the component (i) is 90/10 or less, the ratio of the photoreactive functional group in the resin is sufficient, so that a desired crosslinked structure can be formed. In addition, since the acid value of the resin component is not too high, the solubility in the alkaline developer in the exposed area is unlikely to be high, so that the formed pattern becomes thinner than the target line width and the pattern is missing. It can be suppressed.

(Photopolymerization initiator)
The photosensitive resin composition according to the embodiment of the present invention preferably contains a photopolymerization initiator as the component (v).

Examples of the photopolymerization initiator include acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and p-tert-butylacetophenone. Benzophenones such as benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone; benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether; 2- (o-chlorophenyl)- 4,5-Phenylbiimidazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) biimidazole, 2- (o-fluorophenyl) -4,5-diphenylbiimidazole, 2-( Biimidazole compounds such as o-methoxyphenyl) -4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole , 2-Trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole, etc. Halomethylthiazole compounds; 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- Phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-chlorophenyl) -4,6-bis (trichloromethyl-1,3,5-triazine, 2- (4-4-) Methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2 -(4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4,5-trimethoxystyryl) -4,6-bis (trichloromethyl)- Halomethyl-S-triazine compounds such as 1,3,5-triazine, 2- (4-methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine; 1,2-octane Dione, 1- [4- (Phenylthio) phenyl]-, 2- (O-benzoyloxime), 1- (4-phenylsulfanylphenyl) Butane-1,2-dione-2-oxime-O-benzoate, 1- (4-methylsulfanylphenyl) butane-1,2-dione-2-oxime-O-acetate, 1- (4-methylsulfanylphenyl) ) Butane-1-one oxime-O-acetate, 4-ethoxy-2-methylphenyl-9-ethyl-6-nitro-9H-carbazolo-3-yl-O-acetyloxime, etanone, 1- [9-ethyl- O-acyloxime compounds such as 6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime); benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2, Sulfur compounds such as 4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone; anthracinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone; azobisisobuty Organic peroxides such as lonitrile, benzoyl peroxide, and oxime peroxide; thiol compounds such as 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole, and tertiary amines such as triethanolamine and triethylamine. Etc. are included. As these photopolymerization initiators, only one kind thereof may be used alone, or two or more kinds thereof may be used in combination.

In particular, in the case of a photosensitive resin composition containing a colorant, it is preferable to use O-acyloxygen compounds (including ketooxygen). Examples of a group of compounds that can be preferably used include O-acyloxime-based photopolymerization initiators represented by the general formula (18) and the general formula (19). Among these compound groups, an O-acyloxime-based photopolymerization initiator having a molar extinction coefficient of 10,000 or more at 365 nm is used when the colorant is used at a high pigment concentration and when a cured film pattern is formed. Is preferable. The term "photopolymerization initiator" as used in the present invention is used to include a sensitizer. The molar extinction coefficient can be measured using, for example, an ultraviolet-visible near-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Corporation).

(In formula (18), R ₁₈ and R ₁₉ independently represent an alkyl group of C1 to C15, an aryl group of C6 to C18, an arylalkyl group of C7 to C20 or a heterocyclic group of C4 to C12, and R ₂₀ represents an alkyl group of C1 to C15, an aryl group of C6 to C18, and an arylalkyl group of C7 to C20. Here, the alkyl group and the aryl group are an alkyl group of C1 to C10, an alkoxy group of C1 to C10, and C1. The alkanoyl group of ~ C10 may be substituted with a halogen, the alkylene moiety may contain an unsaturated bond, an ether bond, a thioether bond, an ester bond, and the alkyl group may be linear, branched, or cyclic. It may be any of the alkyl groups of.)

(In the formula (19), R ₂₁ and R ₂₂ are independently linear or branched alkyl groups having 1 to 10 carbon atoms, or cycloalkyl groups having 4 to 10 carbon atoms, cycloalkylalkyl. It is a group or an alkylcycloalkyl group, or a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms. R ₂₃ is independently linear or branched with 2 to 10 carbon atoms. of an alkyl or alkenyl group, -CH 2 in the alkyl or alkenyl group _-. some of the groups may be substituted by -O- group further in groups of these R ₂₁ to R ₂₃ A part of the hydrogen atom may be replaced with a halogen atom.)

The content of the photopolymerization initiator of the component (v) is preferably 3 to 30 parts by weight, preferably 5 to 20 parts by weight, based on a total of 100 parts by weight of each of the components (i) and (iv). Is more preferable. When the compounding ratio of the component (v) is 3 parts by weight or more, the sensitivity is good and a sufficient photopolymerization rate can be obtained. When the compounding ratio of the component (v) is 30 parts by weight or less, it is possible to have an appropriate sensitivity, so that a desired pattern line width and a desired pattern edge can be obtained.

(Photosensitive resin composition)
The dispersion liquid used for the photosensitive resin composition can be prepared by mixing and dispersing the above-mentioned components (i) to (v) by an appropriate method.

(solvent)
In the photosensitive resin composition of the present invention, it is preferable to use a solvent as the component (vi) in addition to the components (i) to (v). Examples of solvents include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol and propylene glycol; terpenes such as α- or β-terpineol; acetone, methyl ethyl ketone, cyclohexanone and N-methyl-2-pyrrolidone. Ketones such as; aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene; cellosolve, methylcellosolve, ethyl cellosolve, carbitol, methylcarbitol, ethylcarbitol, butylcarbitol, propylene glycol monomethyl ether, propylene glycol Glycol ethers such as monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate. , Carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and other acetic acid esters are included. By dissolving and mixing these alone or in combination of two or more, a uniform solution-like composition can be obtained.

Further, in the photosensitive resin composition of the present invention, if necessary, a resin other than the component (i) such as an epoxy resin, a curing agent, a curing accelerator, a thermal polymerization inhibitor and an antioxidant, a plasticizer, a filler. , Leveling agents, antifoaming agents, surfactants, coupling agents and other additives can be blended.

Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, hindered phenolic compounds and the like.

Examples of the above-mentioned plasticizer include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate and the like.

Examples of the filler include glass fiber, silica, mica, alumina and the like.

Examples of the antifoaming agent and the leveling agent include silicone-based, fluorine-based, and acrylic-based compounds. Examples of surfactants include fluorine-based surfactants, silicone-based surfactants and the like.

Examples of the coupling agent include 3- (glycidyloxy) propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltriethoxysilane and the like.

The photosensitive resin composition of the present invention contains the alkali-soluble resin which is the component (i) in the solid component (the solid component contains a monomer which becomes a solid component after curing) excluding the solvent which is the component (vi). , (Ii) component (meth) acrylate resin, (iii) component light-shielding material, (iv) component photopolymerizable monomer, and (v) component photopolymerization initiator. It is preferably contained in an amount of 80% by mass or more, and more preferably 90% by mass or more. The amount of the solvent varies depending on the target viscosity, but is preferably 40 to 90% by mass with respect to the total amount.

The photosensitive resin composition of the present invention can be obtained by mixing the components (i) to (v) and any additive.

Further, the cured film obtained by curing the photosensitive resin composition of the present invention is, for example, a solution of the photosensitive resin composition applied to a substrate or the like, the solvent is dried, and light (including ultraviolet rays, radiation, etc.) is emitted. Obtained by irradiating and curing. A desired pattern can be obtained by providing a portion exposed to light and a portion not exposed to light using a photomask or the like, curing only the portion exposed to light, and dissolving the other portion with an alkaline solution.

Further, the cured film obtained by curing the photosensitive resin composition of the present invention can be used as a black matrix in a color filter. For example, a cured film having a film thickness of 1.0 to 2.0 μm is formed on a transparent substrate, and after the cured film is formed, red, blue, and green pixels are formed by photolithography, or in the cured film. It is produced by injecting red, blue and green inks in an inkjet process.

Further, the cured film obtained by curing the photosensitive resin composition of the present invention can also be used as a black column spacer for a liquid crystal display device. For example, using a single black resist, a plurality of portions having different film thicknesses can be prepared, one of which functions as a spacer and the other of which functions as a black matrix.

Each step of the method of forming a cured film by coating and drying the photosensitive resin composition according to the embodiment of the present invention will be specifically exemplified.

As a method of applying the photosensitive resin composition to the substrate, any of known methods such as a solution dipping method, a spray method, a roller coater machine, a land coater machine, a slit coat machine and a spinner machine shall be adopted. Can be done. By these methods, a film is formed by applying to a desired thickness and then removing the solvent (pre-baking). Pre-baking is performed by heating in an oven, hot plate, etc., vacuum drying, or a combination thereof. The heating temperature and heating time in the prebake can be appropriately selected depending on the solvent used, but are preferably carried out at 80 to 120 ° C. for 1 to 10 minutes, for example.

As the radiation used for exposure, for example, visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like can be used, and the wavelength range of the radiation is preferably 250 to 450 nm. Further, as a developing solution suitable for this alkaline development, for example, an aqueous solution of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide or the like can be used. These developers can be appropriately selected according to the characteristics of the resin layer, but it is also effective to add a surfactant if necessary. The development temperature is preferably 20 to 35 ° C., and a fine image can be precisely formed by using a commercially available developing machine, an ultrasonic cleaner, or the like. After alkaline development, it is usually washed with water. As the developing method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid filling) developing method and the like can be applied.

After developing in this way, heat treatment (post-baking) is performed at 180 to 250 ° C. for 20 to 100 minutes. This post-baking is performed for the purpose of enhancing the adhesion between the patterned cured film (cured film) and the substrate. This is done by heating in an oven, hot plate, etc., similar to pre-baking. The patterned cured film (cured film) of the present invention is formed through each step by a photolithography method. Then, polymerization or curing (which may be collectively referred to as curing) is completed by heat, and a cured film having a desired pattern can be obtained. The curing temperature at this time is preferably 160 to 250 ° C.

In the cured film obtained by the above method, the polymerizable unsaturated group-containing alkali-soluble resin and the (meth) acrylate resin are phase-separated, and the cured film is thin on the outermost layer (the surface not in contact with the substrate) on the cured film side. Form a layer. As a result, the reflectance can be easily increased without using a resin having a lowered refractive index and without separately providing an antireflection film or the like on the outermost layer (the surface not in contact with the base material) of the formed cured film. A reduced cured film can be obtained.

Further, since the color filter of the present invention has a cured film formed by curing the photosensitive resin composition of the present invention as a black matrix, good visibility can be obtained.

Hereinafter, embodiments of the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited thereto.

Although it will be described from the synthesis example of the alkali-soluble resin represented by the general formula (1) which is the component (i) and the (meth) acrylate resin represented by the general formula (13) which is the component (ii). The evaluation of the resin in the synthetic example was carried out as follows unless otherwise specified. When the same model is used for various measuring devices, the device manufacturer name is omitted from the second place. Further, in the examples, the glass substrates used for producing the substrate with the cured film for measurement are all glass substrates that have been subjected to the same treatment.

[Solid content concentration]
_{A glass filter [weight: W 0} (g)] is impregnated with 1 g of the resin solution obtained in the synthesis example, _{weighed [W 1} (g)], and heated at 160 ° C. for 2 hours, and then weight [W _2]. (G)] was calculated from the following mathematical formula (1).
Solid content concentration (% by weight) = 100 × (W _2- W ₀ ) / (W _1- W ₀ ) (1)

[Acid value]
The resin solution was dissolved in dioxane and titrated with a 1/10 N-KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[Molecular weight]
Gel Permeation Chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgelSuper H-2000 (2) + TSKgelSuper H-3000 (1) + TSKgelSuper H-4000 (1) + TSKgelSuper Measured at H-5000 (1 bottle) (manufactured by Tosoh Corporation), temperature: 40 ° C., speed: 0.6 ml / min), and weight average as standard polystyrene (manufactured by Tosoh Corporation, PS-oligoene kit) conversion value. The molecular weight (Mw) was determined.

The abbreviations used in the synthesis example and the comparative synthesis example are as follows.
BPFE: Compound of fluorene-9,9-diyl group (reaction product of 9,9-bis (4-hydroxyphenyl) fluorene and epichlorohydrin (epoxy equivalent 250 g / eq))
AA: Acrylic acid BPDA: 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride THPA: Tetrahydrophthalic anhydride TEAB: Tetraethylammonium bromide PGMEA: Propropylene glycol monomethyl ether acetate MAA: Methacrylic acid MMA: Methacrylic acid Methyl CHMA: Cyclohexyl methacrylate GMA: Glycydyl methacrylate AIBN: Azobisisobutyronitrile TPP: Triphenylphosphine

[Synthesis Example 1]
(Alkali-soluble resin)
BPFE (224.00 g, 0.45 mol), AA (64.57 g, 0.90 mol), PGMEA (43.27 g) and TEAB (0) in a 1000 ml four-necked flask with a return condenser. .94 g) and 2,6-di-tert-butyl-p-cresol (0.10 g) were charged and reacted at 100 to 105 ° C. for 20 hours with stirring. Next, PGMEA (246.32 g), BPDA (65.90 g, 0.225 mol), THPA (34.08 g, 0.225 mol) were charged, and the mixture was stirred at 120 to 125 ° C. under heating for 6 hours. , Alkali-soluble resin (i) (solid content concentration: 56.5% by mass, weight average molecular weight (Mw): 3600, acid value (solid content conversion): 99.5 mgKOH / g) was obtained.

[Synthesis Example 2]
((Meta) acrylate resin)
MAA (61.98 g, 0.72 mol), MMA (43.25 g, 0.43 mol) and CHMA (48.45 g, 0.45 mol) in a 1000 ml four-necked flask with a nitrogen inlet tube and a reflux condenser. 29 mol), AIBN (7.09 g), and diethylene glycol dimethyl ether (432 g) were charged and stirred at 80 to 85 ° C. under a nitrogen stream for 8 hours for polymerization. Further, in the four-necked flask, GMA (73.69 g, 0.52 mol), TPP (1.76 g), 2,6-di-tert-butyl-p-cresol (0.10 g), and (Meta) acrylate resin (ii) -1 (solid content concentration: 35.5% by mass, weight average molecular weight (Mw): 21500, acid value (solid content conversion)). : 50 mgKOH / g) was obtained.

[Synthesis Example 3]
((Meta) acrylate resin)
MAA (61.98 g, 0.72 mol), MMA (43.25 g, 0.43 mol) and CHMA (48.45 g, 0.45 mol) in a 1000 ml four-necked flask with a nitrogen inlet tube and a reflux condenser. 29 mol), AIBN (21.28 g), and diethylene glycol dimethyl ether (458 g) were charged and stirred at 80 to 85 ° C. under a nitrogen stream for 8 hours for polymerization. Further, in the four-necked flask, GMA (73.69 g, 0.52 mol), TPP (1.76 g), 2,6-di-tert-butyl-p-cresol (0.10 g), and (Meta) acrylate resin (ii) -2 (solid content concentration: 35.6% by mass, weight average molecular weight (Mw): 6500, acid value (solid content conversion)). : 52 mgKOH / g) was obtained.

[Comparative composition example]
((Meta) acrylate resin)
In a 1000 ml four-necked flask with a nitrogen inlet tube and a reflux condenser, MMA (84.10 g, 0.84 mol), CHMA (141.41 g, 0.84 mol), AIBN (8.28 g), and Diethylene glycol dimethyl ether (430 g) and diethylene glycol dimethyl ether (430 g) were charged, and the mixture was stirred at 80 to 85 ° C. under a nitrogen stream for 8 hours to obtain (meth) acrylate resin (ii) -3 (solid content concentration: 35.3% by mass, weight average molecular weight (Mw)). ): 19300) was obtained.

The photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 and 2 were prepared in the blending amounts shown in Table 1 (numerical values are mass%). The ingredients used in the table are as follows.

(I): Alkali-soluble resin obtained in Synthesis Example 1 (solid content concentration 56.5% by mass)
(Ii) -1: (Meta) acrylate resin obtained in Synthesis Example 2 (solid content concentration 35.5% by mass)
(Ii) -2: The (meth) acrylate resin obtained in Synthesis Example 3 (solid content concentration: 35.3% by mass)
(Ii) -3: (Meta) acrylate resin obtained in the comparative synthesis example (solid content concentration 35.6% by weight)
(Iii): PGMEA dispersion liquid having 20.0% by mass of carbon black and 5.0% by mass of a polymer dispersant (solid content 25.0%, average secondary particle size of carbon black 162 nm).
(Iv): Dipentaerythritol hexaacrylate (v): Irgacure OXE02 (manufactured by BASF Japan, "Irgacure" is a registered trademark of the company)
(Vi): Propylene glycol monomethyl ether acetate

[evaluation]
The following evaluations were carried out using the photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 and 2. Further, the glass substrate used for producing the cured film for evaluation is a glass substrate that has been subjected to the same treatment.

(Preparation of cured film for evaluation of adhesion and linearity)
The surface of the photosensitive resin composition shown in Table 1 was ^{washed by irradiating the surface with ultraviolet rays having a wavelength of 254 nm and an illuminance of 1000 mJ / cm 2} in advance with a low-pressure mercury lamp, and a 125 mm × 125 mm glass substrate “# 1737” (manufactured by Corning Inc.). It is applied on (hereinafter referred to as "glass substrate") using a spin coater so that the film thickness after heat curing treatment is 1.5 μm, and prebaked at 90 ° C. for 1 minute using a hot plate to cure the film. Was produced. Next, an ultraviolet ray having a wavelength of 365 nm was irradiated and exposed using a high-pressure mercury lamp having an i-line illuminance of 30 mW / cm ^{2 through a negative photomask for pattern formation.}

The exposed cured film was developed at 23 ° C. with a 0.15% sodium carbonate aqueous solution, and then main-cured (post-baked) at 230 ° C. for 30 minutes using a hot air dryer to obtain adhesion and adhesion. A cured film for linearity evaluation was obtained.

[Adhesion evaluation]
(Evaluation method)
The pattern line width after the main curing (post-baking) was confirmed with an optical microscope "ECLIPSE LV100" (manufactured by Nikon Corporation).

(Evaluation criteria)
◯: A pattern having an L / S (line width / space width) of 20 μm / 20 μm or more is formed without residue ×: A pattern having an L / S (line width / space width) of less than 20 μm / 20 μm is formed. No or noticeable pattern hemming or residue

[Linearity evaluation]
(Evaluation method)
The fine line pattern linearity of the cured film after the main curing (post-baking) was confirmed with an optical microscope "ECLIPSE LV100".

(Evaluation criteria)
◯: No peeling or chipping of the fine line pattern on the glass substrate or jagged edges of the pattern ×: Peeling or chipping of the fine wire pattern on the glass substrate and jagged edges of the pattern are observed.

(Preparation of cured film for reflectance, optical density and appearance evaluation)
The photosensitive resin composition shown in Table 1 is applied onto a glass substrate using a spin coater so that the film thickness after the heat curing treatment is 1.5 μm, and is applied to a glass substrate at 90 ° C. for 1 minute using a hot plate. A cured film was prepared by prebaking. Next, exposure was carried out by irradiating ultraviolet rays having a wavelength of 365 nm using a high-pressure mercury lamp having an i-line illuminance of 30 mW / cm ^{2 without using a negative photomask for pattern formation.}

The exposed cured film was developed at 23 ° C. with a 0.15% sodium carbonate aqueous solution, and then main-cured (post-baked) at 230 ° C. for 30 minutes using a hot air dryer to obtain reflectance. A cured film for optical density and appearance evaluation was obtained.

[Reflectance evaluation]
(Evaluation method)
For a substrate with a cured film for reflectance evaluation, use an ultraviolet-visible near-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Co., Ltd.) at an incident angle of 2 ° on the cured film side (opposite to the glass substrate). ) Was measured.

(Evaluation criteria)
⊚: The reflectance of the cured film surface is 5.5 or less. ◯: The reflectance of the cured film surface is more than 5.5 and 6.5 or less. Δ: The reflectance of the cured film surface is more than 6.5 and 7.5. X: The reflectance of the surface of the cured film is more than 7.5.

[Appearance evaluation]
The whitening of the cured film for appearance evaluation, surface unevenness, and the presence or absence of foreign matter were visually observed.

(Evaluation criteria)
⊚: Whitening, color unevenness, or foreign matter is not confirmed at all ○: Whitening, color unevenness, or foreign matter is observed in the area of 1/4 or less of the surface Δ: Whitening, color unevenness in the area of 1/3 or less of the surface , Or foreign matter is observed ×: Whitening, color unevenness, or foreign matter is observed throughout

[Optical density evaluation]
(Evaluation method)
The optical density (OD) of the cured film prepared in the same manner as the cured film for evaluating the optical density (OD) was evaluated using a Macbeth transmission densitometer. Further, the film thickness of the cured film formed on the substrate was measured, and the value obtained by dividing the value of the optical density (OD) by the film thickness was defined as OD / μm.

The optical density (OD) was calculated by the following mathematical formula (1).
Optical density (OD) = -log ₁₀ T (1)
(T indicates transmittance)

The above evaluation results are shown in Table 2.

As is clear from the results of Examples 1 to 5 and Comparative Examples 1 and 2, a photosensitive resin composition containing the alkali-soluble resin (i) of the present invention and the (meth) acrylate resin (ii) is used. As a result, it was found that the reflectance on the cured film side can be reduced, and both high light-shielding property and high-definition pattern formation can be achieved at the same time.

Further, it was found that by using two different types of resins, it is possible to obtain a photosensitive resin composition which can reduce the reflectance by a simple method and can achieve both high light-shielding property and high-definition pattern formation. rice field.

According to the photosensitive resin composition of the present invention, it is possible to provide a photosensitive resin composition having high light-shielding property and low reflectance, a cured film using the same, and a color filter. Further, when the cured film of the present invention is formed on a transparent substrate, it can contribute to the realization of low reflection on the coated surface side of the cured film, so that it is a cured film for sensors such as various display devices and solid-state image sensors. It is useful for.

Claims (7)

Dicarboxylic acid or tricarboxylic acid or their acid monoanhydride, and tetracarboxylic acid or its acid, with respect to the reaction product of the epoxy compound having two or more phenylglycidyl ether groups in the molecule and the unsaturated group-containing monocarboxylic acid. A polymerizable unsaturated group-containing alkali-soluble resin (i) having a weight average molecular weight of 2500 or more obtained by reacting the dianoxide and the like.
A (meth) acrylate resin (ii) having a carboxy group and a polymerizable unsaturated group in the side chain and having a weight average molecular weight of 6000 or more,
As a resin component,
A photosensitive resin composition containing a light-shielding material (iii) selected from the group consisting of black organic pigments, black inorganic pigments, or mixed-color organic pigments as an essential component. The polymerizable unsaturated group-containing alkali-soluble resin (i) has a weight average molecular weight of 2500 or more and 100,000 or less.
The (meth) acrylate resin (ii) has a weight average molecular weight of 6000 or more and 1,000,000 or less.
The photosensitive resin composition according to claim 1, wherein the mass of the (ii) is 1 to 60% by mass with respect to the total mass of the (i) and the (ii). The photosensitive resin composition according to claim 1 or 2, wherein the polymerizable unsaturated group-containing alkali-soluble resin (i) has a structure represented by the general formula (1).

(In the formula (1), R ₁ is an independent hydrocarbon group having 2 to 4 carbon atoms, R ₂ is an independent hydrocarbon group having 1 to 3 carbon atoms, and R ₃ is an independent hydrocarbon group. a hydrogen atom or a methyl group, X is a divalent organic radical independently carbon atoms which may contain a hetero element therein 1~20, -CO -, - SO 2 -, - C ( CF ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -Si (CH ₃ ) _2- , -O-, fluorene-9,9-diyl group represented by the general formula (2) Alternatively, it is a single bond, Y is a tetravalent carboxylic acid residue, and Z is an independently hydrogen atom or a substituent represented by the general formula (3), wherein at least one of Z is general. It is a substituent represented by the formula (3), G is a hydrocarbon atom independently or a substituent represented by the general formula (4), and a is a number of 0 to 10 independently. b is independently a number from 0 to 4, and n is an integer having an average value of 1 to 20.)

In formulas (3) and (4), R ₄ and R ₆ are hydrogen atoms or methyl groups, R ₅ and R ₇ are hydrocarbon groups having 2 to 4 carbon atoms, and L is divalent or trivalent. It is a carboxylic acid residue, where c and f are numbers 0 or 1, d and e are numbers 0, 1 or 2, and d + e is a number 1 or 2.) The (meth) acrylate resin (ii) is a carboxy group in a copolymer of a (meth) acrylate represented by the general formula (5) and a (meth) acrylic acid represented by the general formula (6). A (meth) acrylate resin having a carboxy group and a polymerizable unsaturated group in a side chain obtained by partially reacting with a (meth) acrylate having an epoxy group represented by the general formula (7). , The photosensitive resin composition according to any one of claims 1 to 3.

(In the formula (5), R ₈ is a hydrogen atom or a methyl group, R ₉ is a hydrocarbon group having 1 to 20 carbon atoms, and R ₉ contains an ether oxygen atom or a urethane bond inside. May be good.)

(In formula (6), R ₁₀ is a hydrogen atom or a methyl group.)

(In formula (7), R ₁₁ is a hydrogen atom or a methyl group, R ₁₂ is a divalent hydrocarbon group having 2 to 10 carbon atoms, and g is a number of 0 or 1.) In addition to the photosensitive resin composition according to any one of claims 1 to 4.
(Iv) With a photopolymerizable monomer having at least two polymerizable unsaturated groups,
(V) Photopolymerization initiator and
A photosensitive resin composition containing as an essential component. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 5. A color filter having the cured film according to claim 6 as a black matrix.