JP2015180932A - Black photosensitive resin composition for light-shielding film, cured material using the same, and color filter and touch panel using the cured material as light-shielding film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a black photosensitive resin composition that can provide a black light-shielding film with a high light-shielding property, and has color characteristics that reflected light is in achromatic black.SOLUTION: There is provided a black photosensitive resin composition for a light-shielding film that contains (A) a polymerizable unsaturated group-containing alkali-soluble resin, (B) a photopolymerizable monomer having at least one ethylenically unsaturated bond, (C) a photopolymerization initiator, (D) a light-shielding material, (E) an organic pigment or dye, and (H) a solvent, where provided that the composition contains a monomer component becoming solid after photo-curing, the solid excluding (H) the solvent contains 10 to 60 mass% of (A), 10 to 60 parts by mass of (B) relative to 100 parts by mass of (A), 2 to 50 parts by mass of (C) relative to 100 parts by mass of the total amount of (A) and (B), and the solid further contains 30 to 60 mass% of (D) and 1 to 15 mass% of (E).

Description

  The present invention relates to a black photosensitive resin composition for a light shielding film, a cured product using the same, a color filter for a display such as an LCD having the cured film as a light shielding film, and a touch panel for a display device. More specifically, the present invention relates to an alkaline aqueous solution development type black photosensitive resin composition suitable for forming a fine light-shielding film on a transparent substrate, and a light-shielding film for a color filter or a touch panel formed using the same. .

  Color liquid crystal panels are used in various fields such as liquid crystal televisions, liquid crystal monitors, and color liquid crystal mobile phones. A color liquid crystal panel has a structure in which a substrate on which a color filter is formed and a counter substrate (TFT substrate) are bonded together with a sealing material, and liquid crystal is filled between both substrates. Among these, as a method for producing a color filter, a black matrix is usually formed on the surface of a transparent substrate such as glass or plastic sheet, which plays a role in improving contrast by suppressing color mixing between red, green, and blue colors. A method is used in which different hues of red, green, and blue, which play a role in expressing all natural colors, are sequentially formed in a color pattern such as a stripe shape or a mosaic shape.

  As a black matrix light-shielding agent, carbon black having a high light-shielding property is mainly used. However, the transmitted / reflected light of carbon black is usually not colored black, that is, it is not an achromatic black, and in many cases it is colored slightly brownish, so that the colored There is a problem that a desired color cannot be displayed when black or a color with low luminance is displayed due to leakage of light, that is, light deviated from an achromatic color. There is also a problem that the design is not good because the color is shifted from the black bezel (the frame portion around the display screen of the liquid crystal display device or touch panel) when the power is turned off. Even in the black light shielding material other than carbon black, in many cases, it is not achromatic black, and therefore a technique for adjusting to achromatic black is desired. In recent years, the black matrix is required to be “neutral black” (black without coloring: achromatic color) in order to improve the visibility and design of the liquid crystal panel. In addition, in the touch panel, it may be necessary to match the frame portion with the hue of the black bezel. In this case, the touch panel frame is required to be neutral black.

  In order to realize neutral black, Patent Document 1 discloses that the chromaticity coordinates in the XYZ color system of the transmitted light and / or reflected light of the resin black matrix in the C light source or the F10 light source coincide with the chromaticity coordinates of the light source. There is a description that it is necessary. However, the technology specifically described is that the carbon black and the carbon black have a brown hue deviated from an achromatic color, whereas the blue or purple that is a complementary color of the brown hue This is a technique for adjusting the chromaticity by dispersing an organic pigment composed of the above-mentioned pigments, and it is necessary to add a lot of complementary color pigments. However, especially when the carbon black content is high in the resist in order to increase the light-shielding property, the blending ratio of the binder resin and acrylate component that contributes to curability when the pigment for complementary color is further added is relatively high. Therefore, the coating film is hard to be cured sufficiently, the adhesion between the coating film and the glass substrate is lowered, and the photo-patterning deterioration problem, the resistivity, and the adhesiveness are likely to occur. This will adversely affect the reliability characteristics of the degradation. Further, only the chromaticity adjustment of the transmitted light is described, and the chromaticity adjustment of the reflected light is not specifically shown.

WO95 / 35525 pamphlet

  The present invention has been invented in view of various drawbacks of such technology, and the object thereof is a black light-shielding film having high light-shielding properties, and the reflected light has a color characteristic of achromatic black. The object is to provide a light-shielding film such as a black matrix for liquid crystal color filters. And the objective of this invention can be achieved with the following black photosensitive resin compositions for light shielding films. That is, by using a black photosensitive resin composition for a light shielding film in which a light shielding material is dispersed in a resin, the chromaticity coordinates (a in the L * a * b * color system of reflected light of the light shielding film in a C light source *, b *) ≒ (0.0, 0.0), but for practical purposes, it is important to be able to adjust the chromaticity to match the chromaticity with the black bezel. The object is to obtain a light-shielding film in which the hue of the black bezel is adjusted by adjusting the chromaticity of a, a *, b * to the minus side (minus side).

  As a result of diligent research to solve the above-mentioned problems of the prior art, the present inventors have found that carbon black, titanium black, a binder resin, and a pigment or dye blended with a photopolymerization initiator are conventional carbon blacks. Is not a blend of a blue pigment / dye or a purple pigment / dye, which is a pigment / dye of a complementary color (opposite color) to the shifted hue. By adding a small amount of yellow pigment / dye or orange pigment / dye, which are organic pigments of the same color as the hue deviated from the achromatic color of carbon black, there is no need for a light-shielding film without deteriorating the plate making characteristics and reliability characteristics. It has been found that chromaticity can be matched with chromaticity or black bezel, and the present invention has been completed. That is, the gist of the present invention is as follows.

(1) The present invention comprises (A) a polymerizable unsaturated group-containing alkali-soluble resin, (B) a photopolymerizable monomer having at least one ethylenically unsaturated bond, (C) a photopolymerization initiator, (D) A black photosensitive resin composition for a light-shielding film containing a light-shielding material, (E) an organic pigment or dye, and (H) a solvent, including a monomer component that becomes a solid content after photocuring, except for (H) the solvent In the solid content, (A) is 10 to 60% by mass, (A) 100 parts by mass, (B) is 10 to 60 parts by mass, and (C) is (A) and (B). It is 2-50 mass parts with respect to 100 mass parts of total amount, Furthermore, (D) in solid content is 30-60 mass%, (E) is 1-15 mass% in solid content, It is characterized by the above-mentioned. A black photosensitive resin composition for a light shielding film.

(2) The present invention also provides (A) a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols and an unsaturated group-containing monocarboxylic acid as a polymerizable unsaturated group-containing alkali-soluble resin. In contrast, (a) an alkali-soluble resin obtained by reacting dicarboxylic acid or tricarboxylic acid or acid anhydride thereof and (b) tetracarboxylic acid or acid dianhydride is used (1) The black photosensitive resin composition for light-shielding films described in (1).
(3) The present invention also relates to (E) the organic pigment or dye is (D) an organic pigment or dye having a chromaticity similar to that of the light shielding material, and the black for a light shielding film according to (1) or (2) Photosensitive resin composition.
(4) A cured product obtained by patterning by a photolithography method using the black photosensitive resin composition for a light-shielding film according to any one of (1) to (3), and then thermally curing.

(5) The present invention is also a color filter having the black cured film according to (4) as a light shielding film.

(6) The present invention is also a touch panel having the black cured film according to (4) as a light shielding film.

  ADVANTAGE OF THE INVENTION According to this invention, the black photosensitive resin composition from which the cured film from which an achromatic color is reflected can be obtained can be obtained, and it applies to the color filter and touch panel for display apparatuses which use the said cured film as a light shielding film. Can do. For this reason, the chromaticity of the color filter and the light shielding film of the touch panel can be matched with the black bezel which is substantially achromatic in the display device such as an LCD.

  The present invention is described in detail below.

  The (A) polymerizable unsaturated group-containing alkali-soluble resin in the black photosensitive resin composition of the present invention can be used as long as it is a resin having a polymerizable unsaturated group and an acidic group such as a carboxyl group in the molecule. . For example, a part of the carboxyl group of a resin obtained by radical copolymerization of (meth) acrylic acid and a (meth) acrylic ester compound, a polymerizable unsaturated group such as glycidyl (meth) acrylate and an epoxy group A wide range of resins can be used, including unsaturated group-containing alkali-soluble resins obtained by reacting a compound having in a molecule. Preferred unsaturated group-containing alkali-soluble resins for obtaining the effects of the present invention include a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols and an unsaturated group-containing monocarboxylic acid. And (a) an alkali-soluble resin obtained by reacting dicarboxylic acid or tricarboxylic acid or acid anhydride thereof, and (b) tetracarboxylic acid or acid dianhydride thereof. Here, the molar ratio of (a) / (b) is preferably 0.01 to 10.

  Examples of bisphenols used as a raw material for (A) include bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, bis (4-hydroxy-3,5-dichlorophenyl) ketone, Bis (4-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, -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-3,5-dimethylphenyl) fluorene, 9,9- Bis (4-hydroxy-3,5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene, 4,4′-biphenol, 3,3′-biphenol and the like Derivatives. Among these, those having a 9,9-fluorenyl group are particularly preferably used.

一般式（Ｉ）の式中、Ｒ₁、Ｒ₂、Ｒ₃及びＲ₄は、それぞれ独立して水素原子、炭素数１〜５のアルキル基、ハロゲン原子又はフェニル基を表し、Ａは、−ＣＯ−、−ＳＯ₂−、−Ｃ（ＣＦ₃）₂−、−Ｓｉ（ＣＨ₃）₂−、−ＣＨ₂−、−Ｃ（ＣＨ₃）₂−、−Ｏ−、９，９−フルオレニル基又は直結合を表す。ｌは０〜１０の数である。好ましいＲ₁、Ｒ₂、Ｒ₃、及びＲ₄は水素原子であり、好ましいＡは９，９−フルオレニル基である。また、ｌは通常複数の値が混在するため平均値０〜１０（整数とは限らない）となるが、好ましいｌの平均値は０〜３である。ｌの値が上限値を超えると、当該エポキシ化合物を使用して合成したアルカリ可溶性樹脂を用いた黒色感光性樹脂組成物としたとき、該組成物の粘度が大きくなりすぎて塗工がうまく行かなくなったり、アルカリ可溶性を十分に付与できずアルカリ現像性が非常に悪くなったりする。 Next, the bisphenols and epichlorohydrin are reacted to obtain an epoxy compound having two glycidyl ether groups. Since this reaction generally involves oligomerization of a diglycidyl ether compound, an epoxy compound of the following general formula (I) is obtained.

In the general formula (I), R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and A is — _{CO -, - SO 2 -,} - C (CF 3) 2 -, - Si (CH 3) 2 -, - CH 2 -, - C (CH 3) 2 -, - O-, 9,9- fluorenyl group Or it represents a direct bond. l is a number from 0 to 10. Preferred R ₁ , R ₂ , R ₃ , and R ₄ are hydrogen atoms, and preferred A is a 9,9-fluorenyl group. In addition, since l generally has a plurality of values, the average value is 0 to 10 (not necessarily an integer), but the preferable average value of l is 0 to 3. When the value of l exceeds the upper limit, when the black photosensitive resin composition using the alkali-soluble resin synthesized using the epoxy compound is used, the viscosity of the composition becomes too high and the coating is performed successfully. In other words, the alkali solubility cannot be sufficiently imparted, and the alkali developability becomes very poor.

（式中、Ｒ₁、Ｒ₂、Ｒ₃及びＲ₄は、それぞれ独立して水素原子、炭素数１〜５のアルキル基、ハロゲン原子又はフェニル基を表し、Ｒ₅は、水素原子又はメチル基を表し、Ａは、−ＣＯ−、−ＳＯ₂−、−Ｃ（ＣＦ₃）₂−、−Ｓｉ（ＣＨ₃）₂−、−ＣＨ₂−、−Ｃ（ＣＨ₃）₂−、−Ｏ−、９，９−フルオレニル基又は直結合を表し、Ｘは４価のカルボン酸残基を表し、Ｙ₁及びＹ₂は、それぞれ独立して水素原子又は−ＯＣ−Ｚ−（ＣＯＯＨ）_m（但し、Ｚは２価又は３価カルボン酸残基を表し、ｍは１〜２の数を表す）を表し、ｎは１〜２０の数を表す。） Next, the compound of general formula (I) is reacted with acrylic acid or methacrylic acid as an unsaturated group-containing monocarboxylic acid, or both, and the resulting reaction product having a hydroxy group is subjected to (a) dicarboxylic acid or Tricarboxylic acid or its acid anhydride and (b) tetracarboxylic acid or its acid dianhydride are preferably reacted in a range where the molar ratio of (a) / (b) is 0.01 to 10, and An alkali-soluble resin having the structure of an epoxy (meth) acrylate acid adduct represented by the general formula (II) is obtained.

Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and R ₅ represents a hydrogen atom or a methyl group. A represents —CO—, —SO ₂ —, —C (CF ₃ ) ₂ —, —Si (CH ₃ ) ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, —O—. , 9,9-fluorenyl group or a direct bond, X represents a tetravalent carboxylic acid residue, Y ₁ and Y ₂ each independently represents a hydrogen atom or —OC—Z— (COOH) _m (wherein Z represents a divalent or trivalent carboxylic acid residue, m represents a number of 1 to 2, and n represents a number of 1 to 20.)

  Since this epoxy (meth) acrylate acid adduct (II) is an alkali-soluble resin having both an ethylenically unsaturated double bond and a carboxyl group, it is excellent as (A) of the black photosensitive resin composition of the present invention. It gives photocurability, good developability, and patterning characteristics, and provides a good pattern shape.

  (A) Dicarboxylic acid or tricarboxylic acid or acid anhydride thereof used in the epoxy (meth) acrylate acid adduct of general formula (II) which is (A) of the present invention includes a chain hydrocarbon dicarboxylic acid or tricarboxylic acid. An acid or an acid anhydride thereof, an alicyclic dicarboxylic acid or tricarboxylic acid or an acid anhydride thereof, an aromatic dicarboxylic acid or a tricarboxylic acid or an acid anhydride thereof is used. Here, as the chain hydrocarbon dicarboxylic acid or tricarboxylic acid or an acid anhydride thereof, for example, succinic acid, acetyl succinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citrate malic acid, malonic acid, glutaric acid, There are compounds such as citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid and the like, and further, dicarboxylic acid or tricarboxylic acid having an arbitrary substituent introduced therein or an acid anhydride thereof may be used. Examples of the alicyclic dicarboxylic acid or tricarboxylic acid or acid anhydrides thereof include compounds such as cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornane dicarboxylic acid, and more It may be a dicarboxylic acid or a tricarboxylic acid or an acid anhydride having a substituent introduced therein. Furthermore, examples of the aromatic dicarboxylic acid or tricarboxylic acid or acid anhydride thereof include compounds such as phthalic acid, isophthalic acid, trimellitic acid, and the like. An acid anhydride may be used.

  The (b) tetracarboxylic acid or acid dianhydride used in the epoxy (meth) acrylate acid adduct of the general formula (II) which is (A) of the present invention includes a chain hydrocarbon tetracarboxylic acid. Or its acid dianhydride, alicyclic tetracarboxylic acid or its acid dianhydride, or aromatic polyhydric carboxylic acid or its acid dianhydride is used. Here, examples of the chain hydrocarbon tetracarboxylic acid or its acid dianhydride include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, and the like, and further, a tetracarboxylic acid into which a substituent is introduced. Or its acid dianhydride may be sufficient. Examples of the alicyclic tetracarboxylic acid or its acid dianhydride include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid, Furthermore, a tetracarboxylic acid or an acid dianhydride having a substituent introduced therein may be used. Furthermore, examples of the aromatic tetracarboxylic acid and its acid dianhydride include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, and acid dianhydrides thereof, and further substitution It may be a tetracarboxylic acid having an introduced group or an acid dianhydride thereof.

  (A) dicarboxylic acid or tricarboxylic acid or acid anhydride and (b) tetracarboxylic acid or acid diacid used in the epoxy (meth) acrylate acid adduct of general formula (II) which is (A) of the present invention. The molar ratio (a) / (b) with the anhydride is preferably 0.01 to 10, more preferably 0.1 to 3.0. When the molar ratio (a) / (b) deviates from the above range, the optimum molecular weight cannot be obtained. In the black photosensitive resin composition using (A), alkali developability, heat resistance, solvent resistance, pattern shape, etc. Is not preferable because it deteriorates. In addition, as the molar ratio (a) / (b) is smaller, the molecular weight increases and the alkali solubility tends to deteriorate.

  Moreover, it is preferable that the weight average molecular weight (Mw) is between 2000-10000, and the epoxy (meth) acrylate acid adduct of general formula (II) which is (A) of this invention is between 3000-7000. It is particularly preferred. When the weight average molecular weight (Mw) is less than 2000, the black adhesive resin composition using (A) cannot maintain the pattern adhesion at the time of development, resulting in pattern peeling, and the weight average molecular weight (Mw). If it exceeds 10,000, a development residue and a residual film of an unexposed part are likely to remain. Further, (A) desirably has an acid value in the range of 30 to 200 mgKOH / g. If this value is less than 30 mgKOH / g, the alkali development of the black photosensitive resin composition using (A) tends to deteriorate, and thus special development conditions such as strong alkali are required. On the other hand, if it exceeds 200 mgKOH / g, the alkaline developer will permeate the black photosensitive resin composition using (A) too quickly, and peeling development occurs.

  The epoxy (meth) acrylate acid adduct of the general formula (II) used in the present invention is described in known methods, for example, JP-A-8-278629 and JP-A-2008-9401, by the above-described steps. It can manufacture by the method of. First, as a method for reacting an unsaturated group-containing monocarboxylic acid with an epoxy compound of the general formula (I), for example, an epoxy group of an epoxy compound and an equimolar amount of an unsaturated group-containing monocarboxylic acid are added to a solvent, In the presence of a catalyst (triethylbenzylammonium chloride, 2,6-diisobutylphenol, etc.), there is a method of reacting by heating and stirring at 90 to 120 ° C. while blowing air. Next, as a method of reacting an acid anhydride with a hydroxyl group of an epoxy acrylate compound as a reaction product, a predetermined amount of an epoxy acrylate compound, an acid dianhydride, and an acid monoanhydride is added to a solvent, and a catalyst (odor In the presence of tetraethylammonium bromide, triphenylphosphine, etc.), the reaction is carried out by heating and stirring at 90 to 130 ° C.

  Examples of the photopolymerizable monomer (B) having at least one ethylenically unsaturated bond in the black photosensitive resin composition of the present invention include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. , (Meth) acrylic acid esters having a hydroxyl group such as 2-ethylhexyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (Meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, penta Rithritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, glycerol (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, or dipenta Examples include (meth) acrylic acid esters such as erythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene alkylene oxide-modified hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, These 1 type (s) or 2 or more types can be used. The photopolymerizable monomer having at least one ethylenically unsaturated bond is one having three or more photopolymerizable groups and capable of cross-linking molecules of the unsaturated group-containing alkali-soluble resin. It is preferable. Note that (B) the photopolymerizable monomer having at least one ethylenically unsaturated bond does not have a free carboxy group.

  Examples of the (C) photopolymerization initiator in the black photosensitive resin composition of the present invention include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, and trichloroacetophenone. Acetophenones such as p-tert-butylacetophenone, benzophenone, 2-chlorobenzophenone, benzophenones such as p, p'-bisdimethylaminobenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. Benzoin ethers, 2- (o-chlorophenyl) -4,5-phenylbiimidazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) biimidazole, 2- (o-fluorophenyl) -4,5-diphenylbi Biazole compounds such as dazole, 2- (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- Halomethylthiazole compounds such as oxadiazole, 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-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloroRmethyl) -1, 3,5-tri Azine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4,5-trimethoxystyryl) -4,6-bis (trichloro Halomethyl-S-triazine compounds such as methyl) -1,3,5-triazine, 2- (4-methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (o-benzoyloxime), 1- (4-phenylsulfanylphenyl) butane-1,2-dione-2-oxime-o-benzo Art, o-acyloxy such as 1- (4-methylsulfanylphenyl) butane-1,2-dione-2-oxime-o-acetate, 1- (4-methylsulfanylphenyl) butan-1-oneoxime-o-acetate Compounds, benzyldimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthio Sulfur compounds such as xanthone, 2-isopropylthioxanthone, anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutylnitrile, benzoyl peroxide, cumene Examples thereof include organic peroxides such as peroxides, thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole, and tertiary amines such as triethanolamine and triethylamine. Of these, o-acyloxime compounds are preferably used from the viewpoint of easily obtaining a highly sensitive black photosensitive resin composition. Two or more of these photopolymerization initiators can also be used. In addition, the photoinitiator as used in the field of this invention is used by the meaning containing a sensitizer.

  As the (D) light shielding material in the black photosensitive resin composition of the present invention, a black organic pigment, a mixed color organic pigment, an inorganic pigment, or the like can be used without particular limitation. Examples of black organic pigments include perylene black, cyanine black, and aniline black. Examples of mixed color organic pigments include those obtained by mixing at least two pigments selected from red, blue, green, purple, yellow, cyanine, magenta and the like into a pseudo black color. Examples of inorganic pigments include carbon black, chromium oxide, iron oxide, titanium black, titanium oxynitride, and titanium nitride. These light-shielding materials can be used alone or in combination of two or more, but carbon black is particularly good in terms of light-shielding properties, surface smoothness, dispersion stability, and compatibility with resins. preferable.

Examples of the (E) organic pigment or dye in the black photosensitive resin composition of the present invention include compounds classified as pigments and dyes in the Color Index (CI). Specific examples of the organic pigments and dyes include, but are not limited to, compounds having the following color index (Color Index: CI) numbers.
C. I. Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166 and 173;
C. I. Pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71;
C. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, and 254;
C. I. Pigment violet 14, 19, 23, 29, 32, 33, 36, 37 and 38;
C. I. Solvent violet 2, 8, 9, 11, 13, 14 etc .;
C. I. Pigment blue 15 (15: 3, 15: 4, 15: 6 etc.), 21, 22, 28, 60 and 64;
C. I. Solvent Blue 25, 38, 45, 64, 67, 70, 129;
C. I. Pigment green 7, 10, 15, 25, 36, 47 and 58;
C. I. Solvent Green 3, 28, 32 and 33;
C. I. Pigment brown 28;
C. I. Pigment Black 1 and 7.
However, when carbon black is used as a light shielding material, since carbon black usually has a brown-based reflection color, Y139 and Y150, which are pigments of similar colors, are preferable.

  Further, (E) the organic pigment or dye preferably has a chromaticity of the same color as (D) the light shielding material. Here, (D) having the same color as the light-shielding material indicates that when the light-shielding material has a hue / chromaticity that deviates from an achromatic color, the color is similar to the shifted hue / chromaticity. For example, if the light-shielding material has a hue / chromaticity shifted to a brown color, the orange / yellow hue / chromaticity at the same position on the hue ring are similar colors. Incidentally, the color opposite to the light-shielding material indicates that the color of the light-shielding material is opposite to that of the shifted hue / chromaticity when the hue / chromaticity is shifted from an achromatic color. For example, if the light shielding material has a hue / chromaticity shifted to a brown color, the blue / purple hue / chromaticity located in the vicinity of the diagonal line on the hue ring have opposite colors. That is, carbon black, which is one of the light shielding materials, has a hue shifted from an achromatic color to a brown color, whereas conventionally, a “blue pigment” which is a pigment / dye complementary to the shifted hue (opposite color). / Dye "and" purple pigment / dye "have been considered.

  When an organic pigment is used as the component (E), an average secondary particle diameter measured by a dynamic light scattering method and determined by a cumulant method is preferably 40 to 150 nm, more preferably 60 to 140 nm. However, in order to make b * on the negative side, it is effective to be equal to or smaller than the average secondary particle diameter measured by the dynamic light scattering method of the light shielding material. When carbon black is used as the light shielding material, the average secondary particle size measured by the dynamic scattering method and determined by the cumulant method is preferably 60 to 150 nm, more preferably 80 to 120 nm.

  Moreover, the (H) solvent in the black photosensitive resin composition of this invention can contain 1 type or multiple types of solvent, and it is not specifically limited. For example, alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, terpenes such as α- or β-terpineol, etc., ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone , Aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol Cole monoethyl ether, glycol ethers such as diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Acetic acid esters and the like can be used, and by dissolving and mixing them using several types, a uniform composition in which a light-shielding material, a pigment and the like are stably dispersed can be obtained.

  (H) Although the usage-amount of a solvent changes with target viscosity, it is good to make it contain in the range of 20-90 mass% in a black photosensitive resin composition. When carbon black or an organic pigment is used as the light shielding material, the range is preferably 60 to 90% by mass. When the light shielding material containing metal such as titanium or a metal oxide filler is used as the inorganic pigment, 20 to 80 mass% is used. % Range is preferred.

  Further, the black photosensitive resin composition of the present invention may be added with a curing accelerator, a thermal polymerization inhibitor, a plasticizer, a filler, a leveling agent, an antifoaming agent, a coupling agent, a surfactant and the like as necessary. An agent can be blended. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine and the like, and examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate and the like. Examples of the material include glass fiber, silica, mica, and alumina, and examples of the antifoaming agent and leveling agent include silicone-based, fluorine-based, and acrylic compounds. Examples of the surfactant include a fluorine-based surfactant and a silicone-based surfactant.

  The black photosensitive resin composition of this invention contains the said (A)-(H) component as a main component. In the black photosensitive resin composition, (A) is preferably 10 to 60% by mass in a solid content (including a monomer component that becomes a solid content after photocuring) excluding the solvent (H), A) 10 to 60 parts by mass of (B) with respect to 100 parts by mass, and 2 to 50 parts by mass of (C) with respect to 100 parts by mass of the total amount of (A) and (B). More preferably, (B) is 15 to 35 parts by mass with respect to 100 parts by mass of (A), and (C) is 5 to 30 parts by mass with respect to 100 parts by mass of the total amount of (A) and (B). is there. Moreover, about (D) light-shielding material, it is good that content is the range of 30-60 mass% with respect to solid content, More preferably, it is the range of 40-50 mass%. Moreover, (E) is good in it being 1-15 mass% in solid content, More preferably, it is the range of 2-7 mass%.

  Examples of a method for forming a cured film using the black photosensitive resin composition of the present invention include a method using a photolithography method. As the formation method, first, a black photosensitive resin composition is applied to the substrate surface, and then the solvent is dried (prebaked), and then the exposed coating is irradiated with ultraviolet rays through a photomask. And a method of forming a pattern by carrying out development that elutes an unexposed portion using an aqueous alkali solution, followed by thermal curing (post-baking). Here, as the substrate to which the black photosensitive resin composition is applied, glass, a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether sulfone, etc.) is used.

  As a method of applying the black photosensitive resin composition to the substrate, in addition to a known solution dipping method and spray method, any method such as a roller coater machine, a land coater machine, a slit coater machine or a spinner machine is used. Can be adopted. After applying to a desired thickness by these methods, the coating film is formed by removing the solvent (prebaking). After pre-baking, the solvent is removed by vacuum drying (VCD) at 20 to 100 Pa for 15 to 60 seconds, followed by heating with an oven, a hot plate or the like. The heating temperature and heating time in this pre-baking are appropriately selected according to the solvent to be used, and are performed, for example, at a temperature of 60 to 110 ° C. for 1 to 3 minutes.

  The exposure performed after the pre-baking is performed by an exposure machine, and the photosensitive resin and the photosensitive monomer corresponding to the pattern are exposed by exposing through a photomask. The exposure machine and the exposure irradiation conditions are appropriately selected, and exposure is performed using a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, or a deep ultraviolet lamp.

  Alkali development after exposure is performed for the purpose of removing the unexposed portions of the coating film, and a desired pattern is formed by this development. Examples of the developer suitable for the alkali development include an aqueous solution of an alkali metal or alkaline earth metal carbonate, an aqueous solution of an alkali metal hydroxide, and the like. It is preferable to develop at a temperature of 23 to 27 ° C. using a weakly alkaline aqueous solution containing 0.03 to 1% by mass of carbonate, and a fine image is precisely obtained using a commercially available developing machine or ultrasonic cleaner. Can be formed.

  After the development as described above, a heat treatment (post-bake) is performed at a temperature of 200 to 240 ° C. for 20 to 60 minutes. This post-baking is performed for the purpose of improving the adhesion between the patterned black film and the substrate. This is done by heating with an oven, hot plate or the like.

  The hue and chromaticity of the obtained black cured product is preferably −1.0 <b * <0.2, more preferably −for the purpose of adjusting the black color of the present invention to an achromatic or bluish black color. It must be adjustable to 1.0 <b * <0.0. The value of b * is the D65 light source (JIS Z8720 daylight standard illuminant (colorimetric light)) or C light source (JIS Z8720 daylight) used when displaying object colors illuminated by daylight. Using a supplementary illuminant) at a viewing angle of 2 ° or 10 °.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

  First, Synthesis Example 1 of the (A) polymerizable unsaturated group-containing alkali-soluble resin of the present invention is shown. Evaluation of the resin in the synthesis example was performed as follows.

[Solid content]
1 g of the resin solution obtained in the synthesis example was impregnated into a glass filter [weight: W ₀ (g)], weighed [W ₁ (g)], and heated at 160 ° C. for 2 hours [W ₂ ( g)] from the following equation.
Solid content concentration (% by weight) = 100 × (W ₂ −W ₀ ) / (W ₁ −W ₀ )

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

[Molecular weight]
Gel permeation chromatography (GPC) [trade name HLC-8220GPC manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2) + TSKgelSuperH-3000 (1) + TSKgelSuperH-4000 (1) + TSKgelSuper- Measured with H5000 (1 bottle) [manufactured by Tosoh Corporation, temperature: 40 ° C., speed: 0.6 ml / min], and converted to standard polystyrene [PS-oligomer kit made by Tosoh Corporation] as a weight average molecular weight (Mw )

[Average secondary particle size]
A dispersion for particle size measurement (concentration of light shielding material or organic pigment of 0.1 to 0.5% by mass) in which a light shielding material or an organic pigment is dispersed in a solvent together with a dispersant is prepared, and the particle size of the dynamic light scattering method Using an analyzer (manufactured by Otsuka Electronics Co., Ltd., particle size analyzer FPAR-1000), the average particle size of the cumulant method during dispersion of the light-shielding material or the organic pigment in the solvent was measured to obtain the average secondary particle size.

Abbreviations used in synthesis examples and the like are as follows.
BPFE: Reaction product of 9,9-bis (4-hydroxyphenyl) fluorene and chloromethyloxirane. A compound in which A is 9,9-fluorenyl and R _{1 to} R ₄ are hydrogen in the compound of the general formula (I).
BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride
THPA: 1,2,3,6-tetrahydrophthalic anhydride
TPP: Triphenylphosphine
PGMEA: Propylene glycol monomethyl ether acetate

[Synthesis Example 1]
In a 500 ml four-necked flask with a reflux condenser, charge 78.63 g (0.17 mol) of BPFE, 24.50 g (0.34 mol) of acrylic acid, 0.45 g of TPP, and 114 g of PGMEA, and stir for 12 hours under heating at 100 to 105 ° C. As a result, a reaction product was obtained.

  Next, 25.01 g (0.085 mol) of BPDA and 12.93 g (0.085 mol) of THPA were added to the obtained reaction product, stirred for 6 hours under heating at 120 to 125 ° C., and an alkali-soluble resin solution containing a polymerizable unsaturated group ( A) -1 was obtained. The obtained resin solution had a solid content concentration of 55.8 wt%, an acid value (in terms of solid content) of 103 mg KOH / g, and an Mw of 2600 by GPC analysis.

[Preparation of black photosensitive resin composition]
The black photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 and 2 were prepared by blending according to the composition shown in Table 1. The components used for each composition are shown below.
(A) Alkali-soluble resin solution: Alkali-soluble resin solution prepared in Synthesis Example 1 (B) Photopolymerizable monomer: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd. DPHA)
(C) Photopolymerization initiator: 1- [9-ethyl-6- (2-methylbenzoyl) carbazol-3-yl] ethanone = O-acetyloxime (trade name Irgacure OXE02 manufactured by BASF)
(D) Shading material: carbon black (average secondary particle diameter 109 nm) 25% by mass, polymer dispersant 6% by mass PGMEA solvent carbon black dispersion (E) organic pigment, dye:
(E) -1: YELLOW pigment dispersion of PGMEA solvent in which Y139 (average secondary particle size 108 nm) is 15% by mass and the polymer dispersant is 9% by mass (E) -2: Y139 (average secondary particle size 123 nm) ) Is 15% by mass, the polymer dispersant is 9% by mass, the PGMEA solvent YELLOW pigment dispersion (E) -3: Y139 (average secondary particle size 158 nm) is 15% by mass, and the polymer dispersant is 9% by mass. YELLOW pigment dispersion of PGMEA solvent (E) -4: Solvent Blue 45 (blue dye: powder)
(F) Surfactant: 1% propylene glycol monomethyl ether acetate solution (G) Silane coupling agent (H) Solvent: Mixed solvent of propylene glycol monomethyl ether acetate and cyclohexanone

[Evaluation of reflection color]
The black photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 and 2 were spin-coated on a glass plate (5 inch square), dried on a hot plate at 90 ° C. for 1 minute, and then at 230 ° C. Post-baked for 30 minutes. In this way, a black cured product having a thickness of 1.45 μm was obtained.
Using this solid black substrate, the reflected color was measured with UH-4100 manufactured by Hitachi High-Technologies Corporation. The light source is a C light source (2 ° field of view) or a D65 light source (10 ° field of view).

In Comparative Example 1, the chromaticity of the reflected color of only the light shielding material is shown, but it is necessary to make a * and b * close to 0 in order to obtain an achromatic color, and in particular, the reflected color slightly deviates from the achromatic color. In some cases, it is necessary to set b * to a negative value in situations where a hue of a blue system rather than a brown system is required. On the other hand, in Examples 1 to 3, by adding a yellow organic pigment having a chromaticity similar to that of the light-shielding material, b * is changed to the − side (minus side) without largely moving the reflected color a *. ) You can move it.
On the other hand, when a blue dye having a chromaticity opposite to that of the light shielding material is added as in Comparative Example 2, the b * value is increased and the reflected color is moved in the direction opposite to the direction of the achromatic color. It can be seen that an achromatic or slightly blue hue cannot be obtained.
Therefore, only by adding an organic pigment (or dye) of the same color as the light-shielding material and adding a small amount as in the present invention, the reflected color of the black cured product can be achromatic or adjusted to the desired hue. It became clear that.

Claims (6)

  (A) polymerizable unsaturated group-containing alkali-soluble resin, (B) a photopolymerizable monomer having at least one ethylenically unsaturated bond, (C) a photopolymerization initiator, (D) a light-shielding material, (E) organic It is a black photosensitive resin composition for a light-shielding film containing a pigment or dye and (H) solvent, and includes a monomer component that becomes a solid content after photocuring. (H) In the solid content excluding the solvent, ( A) is 10 to 60% by mass, (A) is 100 parts by mass, (B) is 10 to 60 parts by mass, and (C) is (A) and (B) is 100 parts by mass in total. 2 to 50 parts by weight, and further, (D) in the solid content is 30 to 60% by weight, and (E) is 1 to 15% by weight in the solid content. Resin composition.   (A) As a polymerizable unsaturated group-containing alkali-soluble resin, for a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols and an unsaturated group-containing monocarboxylic acid, (a) dicarboxylic acid 2. The black for a light-shielding film according to claim 1, wherein an alkali-soluble resin obtained by reacting an acid or a tricarboxylic acid or an acid anhydride thereof and (b) a tetracarboxylic acid or an acid dianhydride thereof is used. Photosensitive resin composition.   The black photosensitive resin composition for a light-shielding film according to claim 1 or 2, wherein (E) the organic pigment or dye is an organic pigment or dye having a chromaticity similar to that of (D) the light-shielding material.   The hardened | cured material obtained by patterning by the photolithographic method using the black photosensitive resin composition for light shielding films in any one of Claims 1-3, and carrying out subsequent thermosetting.   A color filter having the black cured product according to claim 4 as a light-shielding film   A touch panel having the black cured product according to claim 4 as a light shielding film.