TW202124499A - Photosensitive resin composition for black resist, light-shielding film cured the same, color filter and touch panel having the light-shielding film, display device having the color filter and the touch panel - Google Patents

Abstract

An object of the present invention is to provide a photosensitive resin composition for black resist, which has high light-shielding property and low reflectance and can suppress the generation of agglomerates.

The photosensitive resin composition for black resist of the present invention comprises: (A) an unsaturated group-containing photosensitive resin, (B) a photopolymerizable monomer having at least two or more unsaturated bonds, (C) a photopolymerization initiator, (D) at least one light-shielding component selected from black pigments, mixed color pigments and light-shielding materials, (E) silica particles, and (F) a solvent.

Description

Photosensitive resin composition for black resist, light-shielding film, color filter, touch panel and display device

The present invention relates to a photosensitive resin composition for a black resist, a light-shielding film formed by hardening the photosensitive resin composition, a color filter and a touch panel having the light-shielding film, and a color filter and a touch panel. Panel display device.

In recent years, due to the vigorous development of mobile terminals, display devices such as touch panels and liquid crystal panels used outdoors or in vehicles have increased. In the above-mentioned display device, a light shielding film is provided on the outer frame of the touch panel in order to shield the light leakage of the peripheral portion of the back liquid crystal panel, and in order to suppress the leakage of light from the screen when displaying black, and to suppress the adjacent color resist ( The color resists are mixed with each other, and a black matrix is provided on the above-mentioned liquid crystal panel.

In display devices and the like, in order to suppress light leakage and the like to improve the screen visibility of the above-mentioned display devices and the like, there are cases in which the concentration of black pigment in the light-shielding film is increased to increase the light-shielding property of the light-shielding film (decrease the light transmittance of the light-shielding film). Compared with the refractive index of transparent substrates or curable resins, black pigments have a higher refractive index. Therefore, when the black pigment concentration in the light-shielding film is increased, the reflectance may increase when viewed from the side opposite to the surface on which the light-shielding film of the transparent substrate is formed. Therefore, the reflection at the interface between the light-shielding film formed on the transparent substrate and the transparent substrate increases, and the reflection on the light-shielding film and the black matrix boundary due to the difference in reflectivity with the colored part of the color filter are obvious. And other bad conditions.

Therefore, a photosensitive resin composition for a black resist having both high light-shielding properties and low reflectance, a light-shielding film formed by curing the photosensitive resin composition, and a color filter are desired.

For example, Patent Document 1 discloses a black photosensitive resin composition containing hydrophobic silica particles and a specific dispersant (urethane-based dispersant). According to Patent Document 1, by using hydrophobic silica particles and a specific dispersant, a black matrix having both high light-shielding properties and low reflectance can be formed.

[Prior Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Application Publication No. 2015-161815

However, when the inventors of the present application conducted an examination, it was found that the black photosensitive resin composition described in Patent Document 1 could not provide a light-shielding film having both desired light-shielding properties and reflectance. In addition, in the black photosensitive resin composition described in Patent Document 1, aggregates derived from silicon oxide particles are generated, which may cause light leakage at the thick line portion, the outer frame portion, and foreign matter in the opening portion.

Therefore, the inventors of the present application have conducted careful examinations to solve the problems in the previous photosensitive resin composition, and found that the silica particles have silanol groups that are easily permeated on the surface of the particles. The characteristic of agglomeration, generally speaking, can be dispersed in an organic solvent by being coated with a silane coupling agent. However, it is not easy to coat all the silanol groups present on the surface with a silane coupling agent, and when mixed with a resin composition having a different polarity, the dispersion state becomes unstable and tends to aggregate. It was found that by mixing a polar solvent with a high relative permittivity as a resist solvent in an appropriate range, the silanol group on the surface of the silica particles can be stabilized by solvation, and the aggregation of the silica particles can be inhibited. .

The present invention was completed in view of this point to provide a photosensitive resin composition for a black resist that has high light-shielding properties and low reflectance and can inhibit the generation of aggregates, and hardened the photosensitive resin composition The light-shielding film, the color filter and touch panel with the light-shielding film, and the display device with the color filter and the touch panel are the purpose.

The photosensitive resin composition for black resists of the present invention contains the following components as essential components: (A) a photosensitive resin containing an unsaturated group, (B) a photopolymerizable monomer having at least two unsaturated bonds , (C) photopolymerization initiator, (D) at least one light-shielding component selected from black pigments, color-mixing pigments and light-shielding materials, (E) silica particles, (F) solvent; wherein, the aforementioned (F) solvent Contains: the first solvent that is propylene glycol monomethyl ether acetate, and the second solvent that has a relative permittivity of 10 to 30 at 23°C; the aforementioned (F) solvent as a whole has a relative permittivity of 8.5 or more at 23°C .

The light-shielding film of this invention hardens the said photosensitive resin composition for black resists.

The color filter of the present invention has the above-mentioned light-shielding film as a black matrix.

The touch panel of the present invention has the above-mentioned light-shielding film as a black matrix.

The display device of the present invention has the above-mentioned color filter or the above-mentioned touch panel.

According to the present invention, it is possible to provide a photosensitive resin composition for a black resist that has high light-shielding properties and low reflectance and can suppress the generation of aggregates, and a photosensitive resin composition obtained by curing the photosensitive resin composition A light-shielding film, a color filter and a touch panel having the light-shielding film, and a display device having the color filter and the touch panel.

The present invention will be described in detail below. The photosensitive resin composition for black resists of the present invention (hereinafter referred to as the photosensitive resin composition) contains the following components as essential components: (A) a photosensitive resin containing an unsaturated group, (B) having at least two Photopolymerizable monomer with saturated bond, (C) photopolymerization initiator, (D) at least one light-shielding component selected from black pigments, color-mixing pigments, and light-shielding materials, (E) silica particles, (F) solvent . Hereinafter, the components (A) to (F) will be explained.

1. (A) Ingredient

The unsaturated group-containing photosensitive resin belonging to the component (A) of this embodiment preferably has a polymerizable unsaturated group and an acidic group for expressing alkali solubility in one molecule, and more preferably contains a polymerizable unsaturated group. Both saturated and carboxyl groups. As long as it is the above-mentioned resin, it will not specifically limit, It can use widely.

Examples of the above-mentioned unsaturated group-containing photosensitive resin include epoxy (meth)acrylate acid adducts obtained in the following manner: epoxy resin having two glycidyl ether groups derived from bisphenols (Hereinafter, also referred to as "bisphenol-type epoxide represented by the general formula (1)"), react with (meth)acrylic acid, and then react the obtained compound having a hydroxyl group with a polycarboxylic acid or its anhydride. Winner. Epoxides derived from bisphenols refer to epoxides or equivalents obtained by reacting bisphenols with epihalohydrin. In addition, "(meth)acrylic acid" is a general term for acrylic acid and methacrylic acid, and it refers to one or both of these.

The unsaturated group-containing photosensitive resin belonging to the component (A) is preferably an epoxide having two glycidyl ether groups derived from bisphenols represented by the general formula (1) and (meth)acrylic acid The reactant of is further reacted with a polybasic carboxylic acid or its anhydride to obtain an unsaturated group-containing photosensitive resin.

(In formula (1), R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and X is -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, 茀-9,9 represented by general formula (2) -Dibase or single bond, l is an integer from 0 to 10).

The bisphenol type epoxide represented by the general formula (1) is an epoxide having two glycidyl ether groups obtained by reacting bisphenols with epichlorohydrin. In this reaction, oligomerization of the diglycidyl ether compound is generally accompanied, and therefore epoxides having two or more bisphenol skeletons are also included.

Examples of bisphenols used in this reaction include: bis(4-hydroxyphenyl) ketone, bis(4-hydroxy-3,5-dimethylphenyl) ketone, bis(4-hydroxy-3,5 -Dichlorophenyl) ketone, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxy-3,5-dimethylphenyl) sulfide, bis(4-hydroxy-3,5-dichlorophenyl) ), 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-dichloro) Phenyl) 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 Alkane, 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-dichloro) Phenyl) ether, 9,9-bis(4-hydroxyphenyl) pyrene, 9,9-bis(4-hydroxy-3-methylphenyl) pyrene, 9,9-bis(4-hydroxy-3- Chlorophenyl) quince, 9,9-bis(4-hydroxy-3-bromophenyl) quince, 9,9-bis(4-hydroxy-3-fluorophenyl) quince, 9,9-bis(4- Hydroxy-3-methoxyphenyl) pyrene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl) pyrene, 9,9-bis(4-hydroxy-3,5-dichloro Phenyl) pyrene, 9,9-bis(4-hydroxy-3,5-dibromophenyl) pyrene, 4,4'-bisphenol, 3,3'-bisphenol, etc. Among them, preferred are bisphenols having a -9,9-diyl group.

Furthermore, the epoxy (meth)acrylate molecule is obtained by reacting such an epoxide with (meth)acrylic acid, and (a) dicarboxylic acid which reacts with the hydroxyl group in the epoxy (meth)acrylate molecule Examples of acid or tricarboxylic acid monoanhydrides include: chain hydrocarbon dicarboxylic acid or tricarboxylic acid monoanhydride, alicyclic dicarboxylic acid or tricarboxylic acid monoanhydride, aromatic dicarboxylic acid or tricarboxylic acid monoanhydride Acid anhydrides of carboxylic acids, etc. Here, examples of chain hydrocarbon dicarboxylic acid or tricarboxylic acid monoanhydrides include: succinic acid, acetosuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid ( citramalic acid), malonic acid, glutaric acid, citric acid, tartaric acid, pendant oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, 3-oxoglutaric acid (diglycollic acid) and other acid monoanhydrides . Furthermore, it contains the acid monoanhydride etc. of the dicarboxylic acid or tricarboxylic acid which introduce|transduced arbitrary substituents. Furthermore, examples of alicyclic dicarboxylic acid or tricarboxylic acid monoanhydrides include: cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornane Acid mono anhydrides such as dicarboxylic acid. Further, it also includes acid monoanhydrides of dicarboxylic acid or tricarboxylic acid introduced with optional substituents, and the like. Furthermore, examples of the acid monoanhydrides of aromatic dicarboxylic acids or tricarboxylic acids include acid monohydrides such as phthalic acid, isophthalic acid, and trimellitic acid. Furthermore, it contains the acid monoanhydride of the dicarboxylic acid or tricarboxylic acid which introduce|transduced arbitrary substituents.

Furthermore, (b) the acid dianhydride of tetracarboxylic acid which reacts with epoxy (meth)acrylate is the acid dianhydride of chain hydrocarbon tetracarboxylic acid, the acid dianhydride of alicyclic tetracarboxylic acid or aromatic The dianhydride of a tetracarboxylic acid. Here, examples of the acid dianhydrides of chain hydrocarbon tetracarboxylic acid include acid dianhydrides such as butane tetracarboxylic acid, pentane tetracarboxylic acid, and hexane tetracarboxylic acid. Furthermore, it includes acid dianhydride of tetracarboxylic acid introduced with optional substituents and the like. Furthermore, alicyclic tetracarboxylic acid Examples of acid dianhydrides include acid dianhydrides such as cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, norbornane tetracarboxylic acid. Furthermore, it includes acid dianhydride of tetracarboxylic acid introduced with optional substituents and the like. Furthermore, examples of the acid dianhydrides of aromatic tetracarboxylic acids include acid dianhydrides such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, and diphenyl ether tetracarboxylic acid. Furthermore, it includes acid dianhydride of tetracarboxylic acid introduced with optional substituents and the like.

The molar ratio (a)/(b) of (a) dicarboxylic acid or tricarboxylic acid anhydride and (b) tetracarboxylic acid dianhydride reacted with epoxy (meth)acrylate is preferably 0.01 to 10.0, more preferably 0.02 or more and less than 3.0. When the molar ratio (a)/(b) is out of the above range, the optimal molecular weight for forming a photosensitive resin composition with good patterning performance cannot be obtained, which is unfavorable. In addition, the smaller the molar ratio (a)/(b), the larger the molecular weight, and the alkali solubility tends to decrease.

In addition, the reaction of the epoxide and (meth)acrylic acid and the reaction of the epoxy (meth)acrylate obtained by the reaction with the polycarboxylic acid or its anhydride are not particularly limited, and a conventional method can be used. Furthermore, the weight average molecular weight (Mw) of the unsaturated group-containing photosensitive resin synthesized in the above reaction is preferably from 2000 to 10,000, and the acid value is preferably from 30 to 200 mgKOH/g.

Other examples of preferable resins as the unsaturated group-containing photosensitive resin of the component (A) include copolymers of (meth)acrylic acid, (meth)acrylate, etc., which have a (meth)acryloyl group And carboxyl resin. Examples of the above-mentioned resins include polymerizable unsaturated group-containing alkali-soluble resins obtained by copolymerizing (meth)acrylates containing glycidyl (meth)acrylate in a solvent to obtain copolymers, and The copolymer is obtained by reacting with (meth)acrylic acid and finally reacting the anhydride of dicarboxylic acid or tricarboxylic acid. The above-mentioned copolymer can refer to the copolymer shown in JP 2014-111722 A. The copolymer is a di-ester glycerol esterified with (meth)acrylic acid at 20 to 90 mol% of hydroxyl groups derived from both ends. (diester gylcerol) repeating unit and 10 to 80 mol% of repeating units derived from one or more polymerizable unsaturated compounds that can be copolymerized with the repeating unit, the number average molecular weight (Mn) is 2000 to 20000, And the acid value is 35 to 120mgKOH/g; and Japanese Patent Application Publication No. 2018-141968 The polymerizable unsaturated group-containing alkali-soluble resin shown, the polymerizable unsaturated group-containing alkali-soluble resin contains a unit derived from a (meth)acrylate compound, and has a (meth)acrylic group and The polymer of units of di- or tricarboxylic acid residues has a weight average molecular weight (Mw) of 3000 to 50000, and an acid value of 30 to 200 mgKOH/g.

(A) As for the unsaturated group containing photosensitive resin of a component, only 1 type may be used individually, and 2 or more types may be used together.

2. (B) Ingredient

Examples of the photopolymerizable monomer having at least two or more unsaturated bonds in the component (B) of this embodiment include: ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate , Triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, glycerol di(meth)acrylate, trimethylol Propane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl erythritol di(meth)acrylate, neopentyl erythritol tri(meth)acrylate, neopentyl erythritol Alcohol tetra(meth)acrylate, dineopentaerythritol tetra(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate, dineopentaerythritol penta(meth)acrylate Base) acrylate, dineopentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, phosphazene (phosphazene) alkylene oxide modified hexa(meth)acrylate, hexamethylene Lactones modify (meth)acrylates such as dineopentaerythritol hexa(meth)acrylate, and dendrimers having (meth)acrylic groups as compounds having vinyl double bonds, and the like. These monomers may be used individually by 1 type, and may use 2 or more types together. Furthermore, the photopolymerizable monomer having at least two ethylenically unsaturated bonds is preferably one that can cross-link the molecules containing the alkali-soluble resin with each other. In order to achieve this function, it is preferable to use a Those with more than one unsaturated bond. Furthermore, the acrylic acid 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 acid equivalent is more preferably 80 to 200 g/eq. In addition, the component (B) does not have a free carboxyl group.

The dendrimer having a (meth)acrylic acid group is a compound having an unsaturated bond that can be contained in the composition as component (B), and the dendrimer having a (meth)acrylic acid group is Examples can be exemplified: dendrimers obtained by adding polyvalent mercapto compounds to part of the carbon-carbon double bonds in the (meth)acrylic groups of the polyfunctional (meth)acrylate. Specifically, it includes a dendrimer obtained by reacting the (meth)acrylic group of the polyfunctional (meth)acrylate represented by the general formula (3) with the polyvalent mercapto compound represented by the general formula (4), and the like.

n) (In the formula (3), R ₅ is a hydrogen atom or a methyl group, and R ₆ is the remainder after n hydroxyl groups in the k hydroxyl groups of _{R 7} (OH) _{k are supplied to the ester bond in the formula. R 7} is The residue after removing the hydroxyl group from the polyol, the polyol ether or the ester of the polyol ether and the hydroxy acid. The preferred R ₇ (OH)k is a non-aromatic linear or branched chain with 2 to 8 carbon atoms. Hydrocarbon skeleton-based polyhydric alcohols, or polyhydric alcohol ethers formed by dehydration and condensation of alcohols with multiple molecules of the polyhydric alcohols connected by ether bonds, or esters of these polyhydric alcohols or polyhydric alcohol ethers and hydroxy acids. k and n independently represents an integer from 2 to 20, but k

n)

(In formula (4), R ₈ is a single bond or a 2 to 6 valent hydrocarbon group with carbon numbers of 1 to 6, and m _{is 2 when R 8} is a single bond, and when R ₈ is a 2 to 6 valent group, it is the same as R8 Same price)

Examples of the polyfunctional (meth)acrylate represented by the general formula (3) include: ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate Base) acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, neopentaerythritol di(meth)acrylate, neopentaerythritol tri(meth)acrylate, dixin Pentaerythritol penta(meth)acrylate, dineopentaerythritol hexa(meth)acrylic acid Ester and caprolactone are used to modify (meth)acrylates such as neopentylerythritol tri(meth)acrylate. These compounds may be used individually by 1 type, and may use 2 or more types together.

Examples of the polyvalent mercapto compound represented by the general formula (4) include: trimethylolpropane tris (thioglycolate), trimethylolpropane tris (mercaptopropionate), neopentyl erythritol tetrakis (mercaptoacetate) ), neopentaerythritol three (mercaptoacetate), neopenteritol tetra (mercaptopropionate), dineopentylene erythritol hexa (mercaptoacetate), dineopentyl erythritol hexa (mercaptopropionate) )Wait. These compounds may be used individually by 1 type, and may use 2 or more types together.

The blending ratio of (A) component and (B) component is based on the weight ratio (A)/(B), preferably 30/70 to 90/10, more preferably 60/40 to 80/20. (A) When the blending ratio of component (A) is 30/70 or more, the cured product after photocuring is less likely to become brittle, and the acid value of the coating film in the unexposed area is less likely to become low, so dissolution in the alkaline developer can be suppressed Sexual decrease. Accordingly, it is unlikely that the pattern edges are jagged and cannot be sharpened. Furthermore, when the blending ratio of the component (A) is 90/10 or less, the ratio of the photoreactive functional group in the resin is sufficient, and therefore the desired crosslinked structure can be formed. Furthermore, since the acid value in the resin component is not too high, the solubility of the exposed portion in the alkali developer is not easily increased, and therefore, it is possible to prevent the formed pattern from becoming thinner than the target line width or pattern defect.

3. (C) Ingredients

二唑、2-三氯甲基-5-(對氰基苯乙烯基)-1,3,4-

二唑、2-三氯甲基-5-(對甲氧基苯乙烯基)-1,3,4-

二唑 等鹵甲基噻唑化合物類；2,4,6-參(三氯甲基)-1,3,5-三

、2-甲基-4,6-雙(三氯甲基)-1,3,5-三

、2-苯基-4,6-雙(三氯甲基)-1,3,5-三

、2-(4-氯苯基)-4,6-雙(三氯甲基-1,3,5-三

、2-(4-甲氧基苯基)-4,6-雙(三氯甲基)-1,3,5-三

、2-(4-甲氧基萘基)-4,6-雙(三氯甲基)-1,3,5-三

、2-(4-甲氧基苯乙烯基)-4,6-雙(三氯甲基)-1,3,5-三

、2-(3,4,5-三甲氧基苯乙烯基)-4,6-雙(三氯甲基)-1,3,5-三

、2-(4-甲基硫基苯乙烯基)-4,6-雙(三氯甲基)-1,3,5-三

等鹵甲基-S-三

系化合物類；乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯基肟)、1,2-辛二酮、1-[4-(苯基硫基)苯基]-,2-(O-苯甲醯基肟)、1-(4-苯基氫硫基苯基)丁-1,2-二酮-2-肟-O-苯甲酸酯、1-(4-甲基氫硫基苯基)丁-1,2-二酮-2-肟-O-乙酸酯、1-(4-甲基氫硫基苯基)丁-1-酮肟-O-乙酸酯、4-乙氧基-2-甲基苯基-9-乙基-6-硝基-9H-咔唑(carbazolo)-3-基-O-乙醯基肟等O-醯基肟系化合物類；苄基二甲基縮酮、噻噸酮、2-氯噻噸酮、2,4-二乙基噻噸酮、2-甲基噻噸酮、2-異丙基噻噸酮等的硫化合物；2-乙基蒽醌、八甲基蒽醌、1,2-苯并蒽醌、2,3-二苯基蒽醌等蒽醌類；偶氮雙異丁腈、過氧化苯甲醯、過氧化異丙苯等有機過氧化物；2-巰基苯并咪唑、2-巰基苯并

唑、2-巰基苯并噻唑等硫醇化合物、三乙醇胺、三乙胺等3級胺等。此等的光聚合起始劑可僅單獨使用1種，亦可併用2種以上。 Examples of the (C) photopolymerization initiator of this embodiment include: acetophenone, 2,2-diethoxyacetophenone, p-dimethyl acetophenone, and p-dimethylaminopropyl benzene , Dichloroacetophenone, trichloroacetophenone, p-tertiary butyl acetophenone and other acetophenones; diphenyl ketone, 2-chlorodiphenyl ketone, p,p'-bisdimethylamino group Diphenyl ketones such as diphenyl ketone; benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether; 2-(o-chlorobenzene Yl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-bis(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-4,5- Biimidazole compounds such as diphenylbiimidazole, 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole; 2-trichloromethyl -5-styryl-1,3,4-

Diazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-

Diazole, 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-

Diazole and other halomethylthiazole compounds; 2,4,6-ginseng (trichloromethyl)-1,3,5-tri

, 2-Methyl-4,6-bis(trichloromethyl)-1,3,5-tri

, 2-Phenyl-4,6-bis(trichloromethyl)-1,3,5-tri

, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl-1,3,5-tri

, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-tri

, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-tri

, 2-(4-Methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-tri

, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-tri

, 2-(4-Methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-tri

Isohalomethyl-S-tri

Series compounds; ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime), 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzyloxime), 1-(4-phenylhydrothiophenyl)butyl -1,2-Dione-2-oxime-O-benzoate, 1-(4-methylsulfanylphenyl)butan-1,2-dione-2-oxime-O-acetate , 1-(4-Methylthiophenyl)butan-1-one oxime-O-acetate, 4-ethoxy-2-methylphenyl-9-ethyl-6-nitro- 9H-carbazolo-3-yl-O-acetyloxime and other O-acetoxy oxime compounds; benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4 -Diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone and other sulfur compounds; 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone , 2,3-Diphenylanthraquinone and other anthraquinones; azobisisobutyronitrile, benzyl peroxide, cumene peroxide and other organic peroxides; 2-mercaptobenzimidazole, 2-mercaptobenzene and

Thiol compounds such as azoles and 2-mercaptobenzothiazole, tertiary amines such as triethanolamine and triethylamine, etc. These photoinitiators may be used individually by 1 type, and may use 2 or more types together.

Examples of O-acyl oxime-based compounds that can be preferably used include O-acyl oxime-based photopolymerization initiators represented by general formula (5) and general formula (6). Among these compounds, when the light-shielding component is used at a high concentration, it is preferable to use an O-acetoxime-based photopolymerization initiator having a molar absorption coefficient at 365 nm of 10000 or more. In addition, the "photopolymerization initiator" referred to in the present invention means a sensitizer.

(In formula (5), R ₉ and R ₁₀ each independently represent an alkyl group having 1 to 15 carbons, an aryl group having 6 to 18 carbons, an aryl alkyl group having 7 to 20 carbons, or a carbon number of 4 to 12 R ₁₁ represents an alkyl group with 1 to 15 carbons, an aryl group with 6 to 18 carbons, or an arylalkyl group with 7 to 20 carbons. Here, the alkyl group and the aryl group may also have 1 carbon atoms. Alkyl groups up to 10, alkoxy groups having 1 to 10 carbons, and alkanoyl groups having 1 to 10 carbons, and may be substituted with halogen. The alkylene moiety may also contain unsaturated bonds, ether bonds, and thioethers. Bond, ester bond. In addition, the alkyl group may be any of linear, branched, or cyclic).

(In formula (6), R ₁₂ and R ₁₃ are each independently a linear or branched alkyl group having 1 to 10 carbons, or a cycloalkyl or cycloalkyl-alkyl group having 4 to 10 carbons ( cycloalkyl-alkyl) or alkyl-cycloalkyl (alkyl-cycloalkyl), or a phenyl group which may be substituted with an alkyl group having 1 to 6 carbons. R _{14 is} each independently a linear or linear chain having 2 to 10 carbons. A branched alkyl or alkenyl group, part of the -CH ₂ -group in the alkyl or alkenyl group may be substituted with an -O- group. Furthermore, part of the hydrogen atoms in _{these R 12} to R _{14 groups} It can also be substituted by halogen atoms).

The use amount of the photopolymerization initiator of the component (C) is preferably 3 to 30 parts by weight, more preferably 5 to 20 parts by weight based on 100 parts by weight of the total of each component of (A) and (B). (C) When the blending ratio of the component is 3 parts by weight or more, the sensitivity is good, and a sufficient photopolymerization rate can be obtained. (C) Blending ratio of components For example, when the amount is less than 30 parts by weight, it can have appropriate sensitivity, and can obtain the desired pattern line width and the desired pattern edge.

4. (D) Ingredients

The light-shielding components such as black pigments, color-mixing pigments, and light-shielding materials of the component (D) of this embodiment have an average particle diameter of 1 to 1000 nm (laser diffraction/scattering particle size distribution meter or dynamic light scattering particle size The average particle size measured by the distribution meter) is not particularly limited, and a conventional light-shielding component can be used.

(D) Examples of the black pigment of the component include perylene black, cyanine black, aniline black, internal amide black, carbon black, titanium black, and the like.

顏料、還原(threne)顏料、苝顏料、紫環酮(perinone)顏料、喹酞酮(quinophthalone)顏料、吡咯并吡咯二酮(diketopyrrolopyrrole)顏料、硫靛顏料等有機顏料中的至少2色混合而成的顏料。 (D) Examples of color mixing pigments of component include: selected from azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline Pigment, two

At least 2 colors of organic pigments such as pigments, threne pigments, perylene pigments, perinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, and thioindigo pigments are mixed and mixed Into the pigment.

The above-mentioned (D) component may be used alone or in combination of two or more according to the function of the target photosensitive resin composition.

In addition, examples of organic pigments that can be used in the case of using a color-mixed pigment as the component (D) include those whose color index names have the following numbers, but are not limited thereto.

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, 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 blending ratio of the light-shielding component of the component (D) can be arbitrarily determined according to the desired degree of light-shielding, but it is preferably 20 to 80% by mass relative to the solid content in the photosensitive resin composition, more preferably 40 To 70% by mass. When using organic pigments such as aniline black, cyanine black, and internal amide black, or carbon-based light-shielding components such as carbon black as the light-shielding component of component (D), it is particularly preferable that the solid content of the photosensitive resin composition is 40 to 60% by mass. When the light-shielding component is 20% by mass or more with respect to the solid content in the photosensitive resin composition, sufficient light-shielding properties can be obtained. When the light-shielding component is 80% by mass or less relative to the solid content in the photosensitive resin composition, the content of the photosensitive resin originally used as the binder does not decrease, and therefore, the desired development characteristics and film-forming ability can be obtained.

The above-mentioned component (D) is usually mixed with other blending ingredients as a light-shielding component dispersion dispersed in a solvent, and a dispersant may be added in this case. The dispersant is not particularly limited, and conventional compounds for dispersing pigments (light-shielding components) (commercially available compounds such as dispersing agents, dispersion wetting agents, dispersion accelerators, etc.) can be used.

Examples of dispersants include cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, and pigment derivative type dispersants (dispersion aids). The dispersant is particularly preferably a cationic polymer dispersant which has cationic functional groups such as imidazole groups, pyrrolyl groups, pyridyl groups, primary, secondary or tertiary amine groups as the coloring The adsorption point of the agent, the amine value is 1 to 100 mgKOH/g, and the number average molecular weight (Mn) is in the range of 1,000 to 100,000. The blending amount of this dispersant is preferably 1 to 35% by mass, more preferably 2 to 25% by mass relative to the light-shielding component. In addition, 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 regarded as dispersants. However, the purpose of its use is not limited to stabilizing the dispersion.

5.(E) Ingredient

The silicon oxide particles of the component (E) are not particularly limited, such as the production method and shape (spherical, non-spherical) of gas phase reaction or liquid phase reaction.

The type of the silicon oxide particles of the component (E) used in the present invention is not particularly limited. Solid silica or hollow silica particles can be used. In addition, "hollow silica particles" refer to silica particles with voids in the particles.

By using the above-mentioned silicon oxide particles, the refractive index of the light-shielding film containing the silicon oxide particles can be reduced.

The average particle diameter of the silicon oxide particles is preferably 1 to 100 nm, more preferably 10 to 90 nm. Compared with the case where the average particle diameter is as small as several nm, it is considered that the agglomeration of silica particles with each other is unlikely to occur in the size within the above-mentioned range. Thereby, in the range of the above-mentioned particle diameter, the silica particles are excellent in dispersion stability, and therefore can be uniformly present in the light-shielding film. Therefore, uneven reflectance on the light-shielding film is unlikely to occur.

The average particle diameter of the above-mentioned silica particles can be measured by the accumulation method using a particle size distribution meter "particle size analyzer FPAR-1000" (manufactured by Otsuka Electronics Co., Ltd.) of the dynamic light scattering method.

Furthermore, the content of the silicon oxide particles is preferably 0.1 to 5 parts by mass, and more preferably 0.1 to 2 parts by mass relative to the total mass of the photosensitive resin composition. When the content of silicon oxide particles is within the above range, low reflectivity can be achieved and good patterning performance can be ensured.

Furthermore, the above-mentioned silicon oxide particles can be those with a refractive index of 1.10 to 1.47. In addition to using ordinary silica particles with a refractive index of 1.45 to 1.47, compared to only containing ordinary silica particles The refractive index of the light-shielding film can be further reduced by using hollow silica particles with a low refractive index.

In addition, the refractive index of the silicon oxide particles can be obtained from a transparent mixed liquid obtained by mixing the above-mentioned silicon oxide particles into a powder form and a standard refracting liquid with a known refractive index. At this time, the refractive index of the standard refracting liquid of the above-mentioned mixed liquid is set to the refractive index of the silica particles. In addition, the refractive index of the aforementioned silica particles can be measured using an Abbe refractometer.

Furthermore, since the reflection caused by the difference in refractive index between the transparent substrate and the formed light-shielding film can be suppressed, the reflection can be suppressed even if an anti-reflection film or the like is not separately provided on the substrate.

The shape of the silicon oxide particles may be true spherical or elliptical. The shape of the silicon oxide particles used in the present invention is preferably a true spherical shape.

The above-mentioned silicon oxide particles preferably have a sphericity of 1.0 to 1.5. As long as the sphericity of the silicon oxide particles is within this range, the particle shape is close to a true sphere. Therefore, it is possible to uniformly fill the light-shielding film with a thin film thickness, maintain the smoothness of the film surface, and form a light-shielding film in which the silicon oxide particles are not exposed to the outside from the surface of the film. Therefore, a light-shielding film having a low refractive index and sufficient strength can be obtained.

The sphericity of the aforementioned silica particles can be obtained from the ratio of the longest diameter to the shortest diameter of the particles (the average value of any 100 silica particles). Here, the longest and shortest diameters of the silicon oxide particles are obtained by photographing the silicon oxide particles with a transmission electron microscope and measuring the longest and shortest diameters of the silicon oxide particles from the obtained microscope image.

6.(F) Ingredient

The solvent of the component (F) includes a first solvent that is propylene glycol monomethyl ether acetate, and a second solvent that has a relative permittivity of 10 to 30 at 23°C.

(F) Among the solvents, the first solvent is propylene glycol monomethyl ether acetate. The content of the first solvent is preferably 10 to 90% by mass relative to the total mass of component (F), more preferably 20 to 80% by mass, and still more Preferably, it is 20 to 74% by mass. By containing 10 to 90% by mass of propylene glycol monomethyl ether acetate as the first solvent, the solubility of the binder resin and the dispersibility of the black pigment can be improved.

Furthermore, the relative permittivity of the second solvent at 23° C. is 10-30, more preferably 13-20, and still more preferably 13-18. By using a solvent with a relative permittivity of 10 to 30 at 23°C as the second solvent, the silanol group on the surface of the silica particles can be stabilized by solvent cooperation, and the silica in the resist composition can be suppressed Particle aggregation.

The above-mentioned second solvent preferably contains saturated or unsaturated ketones having a chain, branched or cyclic structure with 3 to 12 carbons, or saturated or unsaturated ketones having a chain, branched or cyclic structure with 3 to 12 carbons Alcohols.

Examples of the aforementioned second solvent include: ketones such as acetone, methyl ethyl ketone, cyclopentanone, and cyclohexanone; alcohols such as ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, and ethyl lactate; Serousl, methyl Serousl, Ethyl Serousl, Carbitol, Methyl Carbitol, Ethyl Carbitol, Butyl Carbitol, Propylene Glycol Monomethyl Ether, Propylene Glycol Monoethyl Ether, 3-Methyl Carbitol Glycol ethers such as oxy-3-methylbutanol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether. Among the above-mentioned second solvents, preferred are: cyclohexanone, ethyl lactate, 3-methoxy-3-methylbutanol, propylene glycol monoethyl ether, more preferably: cyclohexanone, ethyl lactate, 3-methyl Oxy-3-methylbutanol.

The content of the second solvent is preferably 10 to 50% by mass relative to the total mass of the solvent (F), more preferably 20 to 50% by mass, and still more preferably 25 to 50% by mass. By making the content of the solvent within the above-mentioned range, agglomeration of silicon oxide particles can be suppressed, and good coating properties can be imparted.

In addition, the relative permittivity of the solvent (F) can be measured using a relative permittivity meter "Model 871" (manufactured by Nihon Rufuto Co., Ltd.).

In addition, in the solvent (F), in addition to the above-mentioned first solvent and the above-mentioned second solvent, a third solvent having a boiling point of 150°C to 350°C under normal pressure may be included. The boiling point of the third solvent under normal pressure is preferably 150 to 350°C, more preferably 160 to 300°C.

In addition to the propylene glycol monomethyl ether acetate as the first solvent and the above-mentioned second solvent with a relative permittivity of 10 to 30 at 23°C, a mixture with a boiling point of 150°C to 350°C under normal pressure can also be used in combination. The third solvent.

Examples of the third solvent include: butyl cyrus acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monoethyl ether acetate, 3- Acetate esters such as ethyl ethoxypropionate; ethers such as diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether; α-or Terpenes such as β-terpineol. Among the above-mentioned third solvents, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether are preferable.

The content of the third solvent is preferably 1 to 30% by mass, and more preferably 1 to 20% by mass relative to the total mass of the solvent (F). By containing the above-mentioned third solvent in the above-mentioned range of 1 to 30% by mass, agglomeration of silicon oxide particles can be suppressed. Furthermore, by controlling the drying properties of the resist, it is possible to suppress bumping during vacuum drying and the generation of dry foreign matter in the coating nozzle.

Furthermore, (F) the relative permittivity of the entire solvent at 23° C. is preferably 8.5 or more and 15.0 or less, more preferably 8.8 or more and 15.0 or less, and still more preferably 9.3 or more and 15.0 or less. By setting the relative permittivity of the above-mentioned (F) solvent as a whole at 23° C. to 8.5 or more, the silanol group remaining on the surface of the silica particles can be stabilized by solvent cooperation, and the agglomeration of the silica particles can be suppressed. Furthermore, by setting the relative permittivity at 23°C to 15.0 or less, it is possible to ensure the drying properties and good coating properties in the VCD step of drying the solvent under reduced pressure. Here, "the whole solvent" refers to a mixed solvent of the first solvent and the second solvent, or a mixed solvent of the first solvent, the second solvent, and the third solvent.

Furthermore, the photosensitive resin composition of the present invention may be blended with resins other than (A) components such as epoxy resins, hardeners, hardening accelerators, thermal polymerization inhibitors, antioxidants, plasticizers, and oxidizers. Additives such as fillers, leveling agents, defoamers, surfactants, and coupling agents other than silicon.

、受阻酚系化合物等。塑化劑的例子 包含：鄰苯二甲酸二丁酯、磷苯二甲酸二辛酯、磷酸三甲苯酯等。填充材的例子包含：玻璃纖維、氧化矽、雲母、氧化鋁等。消泡劑或均染劑的例子包含：聚矽氧系、氟系、丙烯酸系的化合物。界面活性劑的例子包含：氟系界面活性劑、聚矽氧系界面活性劑等。偶合劑的例子包含：3-(縮水甘油氧基)丙基三甲氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、3-異氰酸基丙基三乙氧基矽烷、3-脲基丙基三乙氧基矽烷等。 Examples of thermal polymerization inhibitors and antioxidants include: hydroquinone, hydroquinone monomethyl ether, pyrogallol, tertiary butylcatechol, phenothiol

, Hindered phenolic compounds, etc. Examples of plasticizers include dibutyl phthalate, dioctyl phosphate, tricresyl phosphate, and the like. Examples of fillers include: glass fiber, silica, mica, alumina, etc. Examples of defoaming agents or leveling agents include silicone-based, fluorine-based, and acrylic-based compounds. Examples of surfactants include fluorine-based surfactants, silicone-based surfactants, and the like. Examples of coupling agents include: 3-(glycidoxy)propyltrimethoxysilane, 3-propenyloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3- Ureayl propyl triethoxy silane and so on.

The photosensitive resin composition of the present invention is preferably an unsaturated group-containing photosensitive resin containing component (A), ( B) a photopolymerizable monomer having at least two unsaturated bonds of the component, a photopolymerization initiator of the component (C), and at least one light-shielding selected from black pigments, color-mixing pigments, and light-shielding materials for the component (D) Ingredients, (E) Silica particles. The amount of the solvent varies according to the target viscosity, but it is preferably 40 to 90% by mass relative to the total amount.

Furthermore, the light-shielding film formed by curing the photosensitive resin composition of the present invention can be prepared by applying a solution of the photosensitive resin composition to a substrate or the like, drying the solvent and irradiating light (including ultraviolet rays, radiation, etc.). ) To harden it. Use a photomask or the like to set the illuminated part and the non-illuminated part, only harden the illuminated part, and dissolve the other parts with an alkaline solution, so that the desired pattern can be obtained.

Furthermore, a color filter or touch panel having the light-shielding film of the present invention as a black matrix, for example, can be produced by the following method: forming a light-shielding film with a thickness of 1.0 to 2.0 μm on a transparent substrate, and then forming a light-shielding film Then, the red, blue, and green pixels are formed by photolithography, and the red, blue, and green inks are sprayed onto the light-shielding film by an inkjet process.

In addition, the light-shielding film formed by curing the photosensitive resin composition of the present invention can also be used as a black column spacer (Black Column Spacer) of a liquid crystal display device. For example, a single black resist may be used to produce a plurality of portions with different film thicknesses, and one of them may function as a spacer and the other may function as a black matrix.

Specifically, each step in the method of forming a light-shielding film by coating and drying the photosensitive resin composition is exemplified.

The method of applying the photosensitive resin composition to the substrate may also be a conventional solution dipping method, spray method, method using a roll coater, land coater, slit coater, or spin coater. And so on any method. After coating to a desired thickness by such methods, the solvent is removed (pre-baking), thereby forming a film. The pre-baking can be carried out by heating with an oven, a hot plate, etc., vacuum drying, or a combination of these. The heating temperature and heating time in the pre-baking can be appropriately selected according to the solvent used, but it is preferably carried out at 80 to 120°C for 1 to 10 minutes, for example.

The radiation used in the exposure can be, for example, visible light, ultraviolet, extreme ultraviolet, electron beam, X-ray, etc., but the wavelength range of the radiation is preferably 250 to 450 nm. Furthermore, a developer suitable for this alkaline development can use, for example, aqueous solutions such as sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, and tetramethylammonium hydroxide. These developers can be appropriately selected according to the characteristics of the resin layer, but it is also effective to add a surfactant according to the needs. The developing temperature is preferably 20 to 35°C, and a commercially available developing machine or ultrasonic cleaner can be used to precisely form a fine image. In addition, water washing is usually performed after alkali development. The development treatment method may use: shower development method, spray development method, immersion (dipping) development method, paddle development method, and the like.

After developing in this way, heat treatment (post-baking) is performed at 180 to 250° C. for 20 to 100 minutes. The purpose of the subsequent baking is to improve the adhesion between the patterned cured film (light-shielding film) and the substrate. This can be performed by heating by an oven, a hot plate, etc. similarly to the pre-baking. The patterned cured film (light-shielding film) of the present invention can be formed through various steps in the photolithography method. Then, polymerization and curing are completed by heat (the two are sometimes referred to as curing together), and a light-shielding film having a desired pattern can be obtained.

The photosensitive resin composition for black resists of the present invention, as mentioned above, is not only suitable for the formation of fine patterns by exposure, alkali development, etc., but also excellent light-shielding properties can be obtained even if the patterns are formed by conventional screen printing. , Adhesion, electrical insulation, heat resistance, and chemical resistance of light-shielding film.

The photosensitive resin composition for black resists of this invention is suitable for use as a coating material. The ink for color filters used in liquid crystal display devices or imaging elements, and the light-shielding film formed thereby are particularly useful as color filters, black matrices for liquid crystal projection, and the like. Furthermore, the photosensitive resin composition for a black resist of the present invention can also be used as an organic electroluminescent device represented by an organic EL element, a color liquid crystal display device, in addition to the color filter ink of a color liquid crystal display. Color faxes, image sensors, and other multi-color displays are used to distinguish various colors or shading ink materials. According to the color filter of the present invention, it is possible to reduce the reflection of external light at the interface between the colored layer (including the black resist layer) and the substrate, and the reflection of light emitted from the device when used in, for example, an organic EL device. That is, the reflection of external light can be reduced to improve the contrast of bright parts, and the efficiency of extracting light from the light-emitting side can be improved to increase the luminous efficiency.

[Example]

Hereinafter, embodiments of the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited to these embodiments.

First, the synthesis example of the polymerizable unsaturated group-containing alkali-soluble resin of (A) component is demonstrated, unless otherwise stated, the evaluation of the resin in these synthesis examples is performed as follows.

[Solid content concentration]

1 g of the resin solution obtained in the synthesis example was impregnated in a glass filter [weight: W0(g)] and weighed [W1(g)]. From the weight [W2(g)] after heating at 160°C for 2 hours, borrow It can be obtained from the following formula.

Solid content concentration (weight%)=100×(W2-W0)/(W1-W0)

[Acid value]

烷，使用電位差滴定裝置「COM-1600」(平沼產業股份有限公司製)，以1/10N-KOH水溶液進行滴定而求得。 Dissolve the resin solution in two

The alkane was obtained by titration with a 1/10 N-KOH aqueous solution using a potentiometric titration device "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[Molecular Weight]

Gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by TOSOH Co., Ltd., solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2) + TSKgelSuperH-3000 (1) + TSKgelSuperH-4000 (1) )+TSKgelSuperH-5000 (1 piece) (manufactured by TOSOH Co., Ltd.), temperature: 40°C, speed: 0.6 ml/min), measured as standard polystyrene (manufactured by TOSOH Co., Ltd., PS-Oligomer Kit) conversion value , Calculate the weight average molecular weight (Mw).

[The average particle size]

The average particle size of the silica particles was determined by the accumulation method using a particle size distribution meter "particle size analyzer FPAR-1000" (manufactured by Otsuka Electronics Co., Ltd.) using a dynamic light scattering method.

The abbreviations used in the synthesis example and the comparative synthesis example are as follows.

BPFE: 9,9-bis(4-hydroxyphenyl) pyridium and 1-chloro-2,3-1 propylene oxide (chloromethyloxirane) reactant. Among the compounds of the general formula (1), X is a compound in which X is a -9,9-diyl group, and R ₁ to R ₄ are hydrogen.

AA: Acrylic

BPDA: 3,3’,4,4’-biphenyltetracarboxylic dianhydride

THPA: Tetrahydrophthalic anhydride

TEAB: Tetraethylammonium bromide

PGMEA: Propylene Glycol Monomethyl Ether Acetate

[Synthesis example]

Charge BPFE (114.4g, 0.23 mol), AA (33.2g, 0.46 mol), PGMEA (157g) and TEAB (0.48g) into a 500ml four-necked flask with reflux cooler, and stir at 100 to 105°C 20 hours to make it react. Next, BPDA (35.3g, 0.12 mol), THPA (18.3g, 0.12 mol) and stirring at 120 to 125°C for 6 hours to obtain an alkali-soluble resin (A) containing polymerizable unsaturated groups. The solid content concentration of the obtained resin solution was 56.1% by mass, the acid value (in terms of solid content) was 103 mgKOH/g, and the Mw obtained by GPC analysis was 3600.

The photosensitive resin compositions of Examples 1 to 14 and Comparative Examples 1 to 8 were prepared in the blending amount (unit: mass %) described in Table 1. The blending components used in the table are as follows.

(Alkali-soluble resin containing polymerizable unsaturated groups)

(A): Alkali-soluble resin solution obtained in the above synthesis example (solid content concentration 56.1% by mass)

(Photopolymerizable monomer)

(B): A mixture of dineopentaerythritol hexaacrylate and dineopentaerythritol pentaacrylate (ARONIX M-405, manufactured by Toagosei Co., Ltd., "ARONIX" is the company's registered trademark)

(Photopolymerization initiator)

(C): Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime)( Irgacure OXE-02, manufactured by BASF Japan, "Irgacure" is the company's registered trademark)

(Carbon black dispersion)

(D): PGMEA dispersion (solid content 35.0% by mass) of carbon black concentration 25.0% by mass, polymer dispersant concentration of 5.0% by mass, and dispersing resin (alkali-soluble resin (A) of the synthesis example (solid content: 5.0% by mass))

(E): Silica PGMEA dispersion liquid "YA050C" (made by Admatechs Co., Ltd., solid content concentration 40% by mass, average particle size 50nm)

(Solvent)

(The first solvent)

(F)-1: Propylene glycol monomethyl ether acetate (PGMEA)

(Second solvent)

(F)-2: Cyclohexanone (ANON)

(F)-3: Ethyl lactate (EL)

(F)-4: 3-Methoxy-3-methylbutanol (MMB)

(F)-5: Propylene glycol monomethyl ether (PGME)

(3rd solvent)

(F)-6: Diethylene glycol dimethyl ether (MDM)

(F)-7: Diethylene glycol ethyl methyl ether (EDM)

(F)-8: Diethylene glycol diethyl ether (EDE)

(F)-9: Diethylene glycol dibutyl ether (BDB)

[evaluate]

The cured film (light-shielding film) which hardened the photosensitive resin composition for black resists used for evaluation was produced as follows.

(Production of cured film (shading film) for evaluation of foreign matter, optical density, and reflectivity)

Heating to a thickness of 1.2μm after hardening manner, a low pressure mercury lamp in advance to a wavelength of 254nm UV illuminance 1000mJ / cm ² and the surface is cleaned 125mm × 125mm glass substrates "# 1737" (Corning The photosensitive resin composition shown in Table 1 was coated on the company) (hereinafter referred to as "glass substrate") using a spin coating method, and pre-baked at 90°C for 1 minute using a hot plate to produce a dry light-shielding film. ^{Next, ultraviolet rays of 50 mJ/cm 2} were irradiated with an ultra-high pressure mercury lamp with an i-line illuminance of 30 mW/cm ² to the entire surface of the dried light shielding film to perform a photocuring reaction of the light shielding film.

Subsequently, by 25 ℃, 0.04% potassium hydroxide solution, to shower pressure 1kgf / cm ^2, the above-mentioned cured film (light shielding film) for one minute after the exposure development processing performed 5kgf / cm ² of water spray The developed light-shielding film was cured (post-baked) at 230° C. for 30 minutes using a hot air dryer to obtain cured films (light-shielding films) of Examples 1 to 14 and Comparative Examples 1 to 8.

The following evaluation items were performed for the cured film (light-shielding film) obtained by curing the photosensitive resin composition for black resists of Examples 1 to 14 and Comparative Examples 1 to 8 obtained above.

[Foreign body assessment]

(assessment method)

Observe the cured film (light-shielding film) after the main curing (post-baking) with a microscope to confirm the presence or absence of foreign matter originating from aggregates. In addition, △ or more is regarded as a pass.

(Evaluation criteria for foreign body evaluation)

○: No foreign matter originating from aggregates is confirmed in the cured film (light-shielding film)

△: Part of the cured film (light-shielding film) is confirmed to be a foreign matter originating from agglomerates

×: Foreign matter originating from aggregates is confirmed on the entire surface of the cured film (light-shielding film)

[Optical Density Evaluation]

(assessment method)

A Macbeth penetrating densitometer was used to evaluate the optical density (OD) of the produced hardened film (shading film). Furthermore, the film thickness of the cured film (light-shielding 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 taken as OD/μm.

The optical density (OD) is calculated by the following formula (1).

Optical density (OD)=-log10T(1)

(T means penetration rate)

[Reflectivity evaluation]

(assessment method)

For a substrate with a hardened film (light-shielding film) manufactured by the same method as the hardened film (light-shielding film) for optical density (OD) evaluation, use the ultraviolet-visible-infrared spectrophotometer "UH4150" (hitachi hightech science Co., Ltd.) Manufacture), and the reflectance on the substrate (glass substrate) side was measured at an incident angle of 2°.

[Evaluation of uneven coating]

(assessment method)

(Production of cured film (shading film) for evaluation of uneven coating)

Heating to a thickness of 1.2μm after hardening manner, a low pressure mercury lamp in advance to the wavelength 254nm, illuminance 1000mJ / cm ² of ultraviolet rays through the surface of 125mm × 125mm glass substrate cleaned "# 1737" (Corning Company (made by the company) (hereinafter referred to as "glass substrate"), apply the photosensitive resin composition shown in Table 1 using the spin coating method, vacuum-dry at 200 Pa by VCD for 1 minute, and pre-baked at 90°C on a hot plate 1 minute to make a dry shading film. Next, the obtained dry light-shielding film was subjected to main curing (post-baking) at 230° C. for 30 minutes to obtain cured films (light-shielding films) of Examples 1 to 14 and Comparative Examples 1 to 8.

(assessment method)

The cured film (light-shielding film) after the main curing (post-baking) was visually observed to confirm the uniformity of the coating film. In addition, △ or more is regarded as a pass.

(Evaluation criteria for evaluation of uneven coating)

○: No unevenness is confirmed in the cured film (light-shielding film)

△: Unevenness is confirmed in part of the cured film (light-shielding film)

×: The cured film (light-shielding film) was not uniformly formed, and unevenness was confirmed on the entire surface

The above evaluation results are shown in Table 2.

As shown in Examples 1 to 14, it can be seen that by including a second solvent having a relative permittivity of 10 to 30 at 23°C and setting the relative permittivity of the entire solvent at 23°C to 8.5 or more, it is possible to obtain a high A light-shielding film with light-shielding and low reflectivity, and the generation of aggregates is suppressed. It is speculated that by setting the relative permittivity of the second solvent to 10 to 30 and setting the relative permittivity of the entire solvent to 8.5 or more at 23°C, the residual on the surface of the silicon oxide particles can be made by solvent cooperation. Silanol is stable.

In particular, including the second solvent having a relative permittivity of 13 or more at 23° C., the content of the second solvent is 20 to 50% by mass relative to the mass of all solvents in Examples 1 to 3, 7 to 11, 13, and In 14, the generation of aggregates observed in Comparative Examples 4 to 8 was significantly suppressed, and no decrease in optical density was observed. It is speculated that the above-mentioned second solvent with high relative permittivity can more effectively solvate the silanol groups on the surface of the silicon oxide particles.

In Examples 9 to 14 containing the third solvent, in addition to the effect of the second solvent for suppressing agglomerates derived from silica particles, the effect of the third solvent with a high boiling point also improves the drying properties, which can suppress Uneven coating.

[Industrial availability]

According to the photosensitive resin composition of the present invention, it is possible to provide a photosensitive resin composition for a black matrix having both high light-shielding properties and low reflectance, and a light-shielding film, color filter, and touch panel using the photosensitive resin composition. Furthermore, with the color filter and the touch panel, various display devices with excellent visibility can be provided.

Claims (9)

A photosensitive resin composition for black resists, which contains the following components as essential components: (A) photosensitive resin containing unsaturated groups, (B) A photopolymerizable monomer having at least 2 or more unsaturated bonds, (C) photopolymerization initiator, (D) At least one light-shielding component selected from black pigments, mixed color pigments and light-shielding materials, (E) Silica particles, and (F) Solvent; The aforementioned (F) solvent includes a first solvent that is propylene glycol monomethyl ether acetate, and a second solvent that has a relative permittivity of 10 to 30 at 23°C; The aforementioned (F) solvent as a whole has a relative permittivity of 8.5 or more at 23°C. The photosensitive resin composition for a black resist according to claim 1, wherein the aforementioned (A) unsaturated group-containing photosensitive resin is derived from bisphenols represented by the general formula (1) and has two The reaction product of glycidyl ether group epoxide and (meth)acrylic acid is further reacted with polybasic carboxylic acid or its anhydride to obtain unsaturated group-containing photosensitive resin;

In the general formula (1), R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and X is -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, Fu-9 represented by general formula (2), 9-diyl or single bond, l is an integer from 0 to 10;

The photosensitive resin composition for black resists according to claim 1 or 2, wherein the (F) solvent system includes a third solvent in addition to the first solvent or the second solvent, and the third solvent is The boiling point under normal pressure is 150°C to 350°C. The photosensitive resin composition for black resists according to any one of claims 1 to 3, wherein the second solvent contains saturated ketones having a chain, branch, or cyclic structure with 3 to 12 carbon atoms. The photosensitive resin composition for a black resist according to any one of claims 1 to 3, wherein the second solvent contains a saturated or unsaturated chain, branched, or cyclic structure having a carbon number of 3 to 12 Alcohols. A light-shielding film obtained by curing the photosensitive resin composition for a black resist according to any one of claims 1 to 5. A color filter having the light-shielding film described in claim 6 as a black matrix. A touch panel having the light-shielding film described in claim 6 as a black matrix. A display device having the color filter described in claim 7 or the touch panel described in claim 8.