JP6708365B2 - Black photosensitive resin composition for light-shielding film, cured product using the same, and color filter and touch panel using the cured product as a light-shielding film - Google Patents

Description

The present invention relates to a black photosensitive resin composition for a light-shielding film, a cured product using the same, and a color filter for a display such as an LCD and a touch panel for a display device having the cured film as a light-shielding film. 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. The 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 to each other with a sealing material, and liquid crystal is filled between both substrates. Among these, as a method for manufacturing a color filter, usually, a black matrix is formed on the surface of a transparent substrate such as glass or a plastic sheet, which plays a role of improving contrast by suppressing color mixture between red, green and blue. A method of sequentially forming different hues of red, green, and blue, which play a role of expressing all natural colors, in a color pattern such as a stripe shape or a mosaic shape is used.

Carbon black having a high light-shielding property is mainly used as a light-shielding agent for the black matrix. However, the transmitted light/reflected light of carbon black is not usually uncolored black, that is, achromatic black, and in many cases, it is colored slightly brownish color. There is a problem that a desired color cannot be displayed when black or a color with low brightness is displayed due to leakage of light, that is, light deviated from an achromatic color. Further, when the power is turned off, there is a problem that the color is deviated from that of the black bezel (the frame portion around the display screen of the liquid crystal display device or the touch panel) and the design is not good. In many cases, black light-shielding materials other than carbon black are not achromatic black, and therefore there is a demand for a technique for adjusting achromatic black. In recent years, in order to improve the visibility and the design of the liquid crystal panel, the black matrix is required to be "neutral black" (black not colored: achromatic). Also in the touch panel, it may be necessary to match the frame portion with the hue of the black bezel. In that case, the touch panel frame is required to be neutral black.

In order to realize neutral black, in Patent Document 1, the chromaticity coordinates in the XYZ color system of the transmitted light and/or the reflected light of the resin black matrix in the C light source or the F10 light source are made to coincide with the chromaticity coordinates of the light source. There is a statement that it is necessary. However, the technology specifically described is that, while carbon black and the carbon black have a brownish hue deviated from the achromatic color, a blue-based or purple-based hue that is a complementary color of the brownish hue. This is a technique for adjusting the chromaticity by dispersing an organic pigment composed of the above pigment, and it is necessary to add a large amount of complementary color pigments. However, especially when the content of carbon black is high in the resist in order to increase the light-shielding property, when a large amount of a complementary color pigment is further added, the mixing ratio of the binder resin and the acrylate component, etc., which contribute to the curability, is relatively high. Since the coating becomes harder to harden sufficiently, the adhesion between the coating and the glass substrate decreases, and peeling and other problems tend to occur. This will adversely affect the reliability characteristics of deterioration. Further, only the chromaticity adjustment of transmitted light is described, and the chromaticity adjustment of reflected light is not specifically shown.

WO95/35525 pamphlet

The present invention has been made in view of the drawbacks of the technique, and an object thereof is a black light-shielding film having high light-shielding property and having a color characteristic that reflected light is achromatic black. It is to provide a light-shielding film such as a black matrix for a liquid crystal color filter. Then, such an object of the present invention can be achieved by the following black photosensitive resin composition for a light shielding film. 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, chromaticity coordinates (a in the L*a*b* color system of reflected light of the light shielding film in the C light source *,b*) ≈ (0.0, 0.0) is the purpose, but practically, it is important to be able to adjust the chromaticity to match the chromaticity with the black bezel. , A*, b* are adjusted to the negative side (negative side) to obtain a light-shielding film that matches the hue of the black bezel.

The present inventors have conducted intensive studies to solve the above-mentioned problems of the prior art, and as a result, regarding carbon black, titanium black, a binder resin, and a pigment or dye compounded with a photopolymerization initiator, conventional carbon black Is a hue shifted from an achromatic color to a brownish hue, while the shifted hue and a complementary color (opposite color) of a blue pigment/dye or a purple pigment/dye are not blended, but rather By including a small amount of yellow pigment/dye or orange pigment/dye, which are organic pigments of the same color as the hue that is deviated from the achromatic color of carbon black, the light-shielding film can be removed without deteriorating the plate making characteristics and reliability characteristics. The present invention has been completed by finding that the chromaticity can be matched with that of a colored bezel or a black bezel. That is, the gist of the present invention is as follows.

(1) The present invention includes (A) a polymerizable unsaturated group-containing alkali-soluble resin, (B) a photopolymerizable monomer having at least one ethylenically unsaturated bond, (C) a photopolymerization initiator, and (D). A black photosensitive resin composition for a light-shielding film, which contains a light-shielding material, (E) an organic pigment or dye, and (H) a solvent, and excludes the (H) solvent, including a monomer component which becomes a solid content after photocuring. In the solid content, (A) is 10 to 60% by mass, (B) is 10 to 60 parts by mass, and (C) is (A) and (B) based on 100 parts by mass of (A). The total amount is 2 to 50 parts by mass, the solid content (D) is 30 to 60 mass%, and the solid content (E) is 1 to 15 mass%. And 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 bisphenol and an unsaturated group-containing monocarboxylic acid as the polymerizable unsaturated group-containing alkali-soluble resin. On the other hand, an alkali-soluble resin obtained by reacting (a) a dicarboxylic acid or a tricarboxylic acid or an acid anhydride thereof and (b) a tetracarboxylic acid or an acid dianhydride is used (1 The black photosensitive resin composition for light-shielding film as described in 1).
(3) In the present invention, the (E) organic pigment or dye is an organic pigment or dye having a chromaticity similar to that of the (D) light-shielding material, and the black for the light-shielding film according to (1) or (2). Photosensitive resin composition.
(4) A cured product obtained by patterning the black photosensitive resin composition for a light-shielding film according to any one of (1) to (3) by a photolithography method and then thermally curing it.

(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.

According to the present invention, it is possible to obtain a black photosensitive resin composition capable of obtaining a cured film in which a reflection color is an achromatic color, and to apply the cured film as a light-shielding film to a color filter or a touch panel for a display device. You can Therefore, it becomes possible to match the chromaticity of the color filter and the light-shielding film of the touch panel with the black bezel, which is almost achromatic in the chromaticity of the reflected color in a display device such as an LCD.

The present invention will be 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, some of the carboxyl groups of the resin obtained by radical copolymerization of (meth) acrylic acid and (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 one molecule. The unsaturated group-containing alkali-soluble resin preferable for obtaining the effect of the present invention is a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols and an unsaturated group-containing monocarboxylic acid. And an alkali-soluble resin obtained by reacting (a) a dicarboxylic acid or a tricarboxylic acid or an acid anhydride thereof, and (b) a tetracarboxylic acid or an acid dianhydride thereof. Here, the molar ratio of (a)/(b) is preferably 0.01 to 10.

Examples of the bisphenols as the raw material of (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, 9,9-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 and derivatives thereof. 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 are reacted with epichlorohydrin to obtain an epoxy compound having two glycidyl ether groups. During this reaction, since the diglycidyl ether compound is generally oligomerized, an epoxy compound represented by the following general formula (I) is obtained.

In 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 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 usually has a mixture of 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 value, when a black photosensitive resin composition using an alkali-soluble resin synthesized by using the epoxy compound is prepared, the viscosity of the composition becomes too large and the coating is successful. It may disappear or alkali solubility may not be sufficiently imparted, resulting in very poor alkali developability.

（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 the general formula (I) is reacted with acrylic acid or methacrylic acid as an unsaturated group-containing monocarboxylic acid, or both of them, and the resulting reaction product having a hydroxy group is treated with (a) dicarboxylic acid or A tricarboxylic acid or an acid anhydride thereof and (b) a tetracarboxylic acid or an acid dianhydride thereof are preferably reacted in a molar ratio of (a)/(b) of 0.01 to 10 to give the following: An alkali-soluble resin having a structure of an epoxy (meth)acrylate acid adduct represented by the general formula (II) is obtained.

(In the formula, 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 R ₅ is a hydrogen atom or a methyl group. the stands, 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 a direct bond, X represents a tetravalent carboxylic acid residue, Y ₁ and Y ₂ each independently represent a hydrogen atom or —OC-Z-(COOH) _m (however, , 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 provides photocurability, good developability, and patterning characteristics, and provides a good pattern shape.

Examples of the (a) dicarboxylic acid or tricarboxylic acid or its acid anhydride used in the epoxy (meth)acrylate acid adduct of the general formula (II) which is (A) of the present invention include a chain hydrocarbon dicarboxylic acid or tricarboxylic acid. Acids or acid anhydrides thereof, alicyclic dicarboxylic acids or tricarboxylic acids or acid anhydrides thereof, aromatic dicarboxylic acids or tricarboxylic acids or acid anhydrides thereof are used. Here, as the chain hydrocarbon dicarboxylic acid or tricarboxylic acid or acid anhydride thereof, for example, succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, There are compounds such as citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, and diglycolic acid, and further dicarboxylic acid or tricarboxylic acid having an optional substituent introduced therein or an acid anhydride thereof. Further, examples of the alicyclic dicarboxylic acid or tricarboxylic acid or an acid anhydride thereof include compounds such as cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid, and further optional. It may be a dicarboxylic acid or tricarboxylic acid having a substituent introduced therein or an acid anhydride thereof. Furthermore, examples of the aromatic dicarboxylic acid or tricarboxylic acid or acid anhydride thereof include compounds such as phthalic acid, isophthalic acid, and trimellitic acid, and further, a dicarboxylic acid or tricarboxylic acid into which any substituent is introduced or its An acid anhydride may be used.

The (b) tetracarboxylic acid or its dianhydride used in the epoxy (meth)acrylate acid adduct of the general formula (II) which is (A) of the present invention is a chain hydrocarbon tetracarboxylic acid. Alternatively, an acid dianhydride thereof, an alicyclic tetracarboxylic acid or an acid dianhydride thereof, or an aromatic polycarboxylic acid or an acid dianhydride thereof is used. Here, as the chain hydrocarbon tetracarboxylic acid or an acid dianhydride thereof, for example, butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, etc., further tetracarboxylic acid having a substituent introduced Alternatively, it may be an acid dianhydride. Examples of the alicyclic tetracarboxylic acid or its dianhydride include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid, and the like. Further, it may be a tetracarboxylic acid having a substituent introduced or its acid dianhydride. Furthermore, examples of the aromatic tetracarboxylic acid and its acid dianhydride include, for example, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid or its acid dianhydride, and further substitution It may be a tetracarboxylic acid having a group introduced or its acid dianhydride.

(A) a dicarboxylic acid or a tricarboxylic acid or an acid anhydride thereof and (b) a tetracarboxylic acid or an acid diacid thereof which are used in the epoxy (meth)acrylate acid adduct of the general formula (II) which is (A) of the present invention. The molar ratio (a)/(b) to the anhydride is preferably 0.01 to 10 and 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, and in the black photosensitive resin composition using (A), alkali developability, heat resistance, solvent resistance, pattern shape, etc. Is deteriorated, which is not preferable. The smaller the molar ratio (a)/(b), the higher the molecular weight, and the alkali solubility tends to deteriorate.

The epoxy (meth)acrylate acid adduct of the general formula (II), which is (A) of the present invention, preferably has a weight average molecular weight (Mw) of 2,000 to 10,000, more preferably 3,000 to 7,000. It is particularly preferable that If the weight average molecular weight (Mw) is less than 2000, the pattern adhesiveness cannot be maintained during development of the black photosensitive resin composition using (A), pattern peeling occurs, and the weight average molecular weight (Mw) When it exceeds 10,000, the development residue and the residual film in the unexposed area tend to remain. Furthermore, the acid value of (A) is preferably 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 be deteriorated, and thus special development conditions such as strong alkali are required. On the other hand, if it exceeds 200 mgKOH/g, the alkali developer penetrates into the black photosensitive resin composition containing (A) too quickly and peeling development occurs, which is not preferable.

The epoxy (meth)acrylate acid adduct of the general formula (II) used in the present invention is described in a known method, for example, in JP-A-8-278629 or JP-A-2008-9401 by the above-mentioned steps. It can be manufactured by the method of. First, as a method for reacting an epoxy compound of general formula (I) with an unsaturated group-containing monocarboxylic acid, 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 which is 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 chloride, triphenylphosphine, etc.), the reaction is carried out by heating and stirring at 90 to 130°C.

Examples of (B) the photopolymerizable monomer 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. , 2-ethylhexyl (meth)acrylate and other hydroxyl group-containing (meth)acrylic acid esters, 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, pentaerythritol tri(meth)acrylate, pentaerythritol Tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, glycerol(meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, or dipentaerythritol hexa(meth)acrylate, sorbitol hexa( Examples thereof include (meth)acrylates, alkylene oxide-modified hexa(meth)acrylates of phosphazene, and caprolactone-modified dipentaerythritol hexa(meth)acrylates. One or more of these are used. can do. As the photopolymerizable monomer having at least one ethylenically unsaturated bond, one having three or more photopolymerizable groups and capable of crosslinking the molecules of the unsaturated group-containing alkali-soluble resin is used. Preferably. The photopolymerizable monomer (B) 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, 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-diphenylbiimidazole, 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole, biimidazole compounds such as 2,4,5-triarylbiimidazole, 2-trichloromethyl-5 -Styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-methoxystyryl) -1,3,4-oxadiazole and other halomethylthiazole compounds, 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl) )-1,3,5-Triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)- 1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis( Trichloro-R-methyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-triazine Methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, etc. Halomethyl-S-triazine compounds, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(o-benzoylo Oxime), 1-(4-phenylsulfanylphenyl)butane-1,2-dione-2-oxime-o-benzoate, 1-(4-methylsulfanylphenyl)butane-1,2-dione-2-oxime- o-Acetate, o-acyl oxime compounds such as 1-(4-methylsulfanylphenyl)butan-1-one oxime-o-acetate, benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethyl Sulfur compounds such as thioxanthone, 2-methylthioxanthone and 2-isopropylthioxanthone, anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone and 2,3-diphenylanthraquinone, azobis Organic peroxides such as isobutyl nitrile, benzoyl peroxide, cumene peroxide, thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole, and tertiary amines such as triethanolamine and triethylamine And so on. Among these, o-acyl oxime compounds are preferably used from the viewpoint of easily obtaining a highly sensitive black photosensitive resin composition. Also, two or more kinds of these photopolymerization initiators can be used. The photopolymerization initiator as used in the present invention is meant to include a sensitizer.

As the light-shielding material (D) 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 the mixed color organic pigment include those obtained by mixing at least two kinds of pigments selected from red, blue, green, violet, yellow, cyanine, magenta and the like to be pseudo-blackened. Examples of the inorganic pigment include carbon black, chromium oxide, iron oxide, titanium black, titanium oxynitride, titanium nitride and the like. These light-shielding materials may be used alone or in combination of two or more, and carbon black is particularly preferable because it has good light-shielding properties, surface smoothness, dispersion stability, and affinity 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 (Colour Index: CI). Specific examples of the organic pigments and dyes include, but are not limited to, compounds having the following Color Index (C.I.) 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.
When carbon black is used as a light-shielding material, carbon black usually has a brownish reflection color, and thus Y139 and Y150, which are pigments of similar colors, are preferable.

The (E) organic pigment or dye preferably has a chromaticity similar to that of the (D) light-shielding material. Here, (D) the same color as the light-shielding material means that when the light-shielding material has a hue/chromaticity deviated from the achromatic color, the hue/chromaticity deviated is similar to the hue. For example, if the light-shielding material has a hue/chromaticity deviated to brown, the hues/chromaticities of orange and yellow at the same position on the hue circle are similar colors. By the way, the color opposite to that of the light-shielding material means that when the light-shielding material has a hue/chromaticity deviated from the achromatic color, it has a color opposite to the deviated hue/chromaticity. For example, if the light-shielding material has a hue and chromaticity that are deviated to brown, the hues and chromaticities of blue and violet that are located near the diagonal line on the hue circle are opposite colors. That is, while carbon black, which is one of the light-shielding materials, has a hue shifted from an achromatic color to a brownish color, conventionally, a “blue pigment” that is a pigment/dye of a complementary color (opposite color) to the shifted hue It has been considered to incorporate "/dye" or "purple pigment/dye".

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

Further, the (H) solvent in the black photosensitive resin composition of the present invention may contain one kind or a plurality of kinds of solvents and is not particularly limited. For example, alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol and propylene glycol, terpenes such as α- or β-terpineol, ketones such as acetone, methyl ethyl ketone, cyclohexanone and N-methyl-2-pyrrolidone. , Toluene, xylene, aromatic hydrocarbons such as 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 monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, glycol ethers such as diethylene glycol diethyl ether, ethyl acetate, butyl acetate, Acetic acid esters such as cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. are mentioned. A uniform composition that is stably dispersed can be obtained.

The amount of the solvent (H) used varies depending on the target viscosity, but it is preferable that the amount of the solvent (H) be contained in the black photosensitive resin composition in the range of 20 to 90% by mass. When using carbon black or an organic pigment as a light shielding material, the range of 60 to 90 mass% is preferable, and when using a light shielding material containing a metal such as titanium or a filler of a metal oxide as an inorganic pigment, 20 to 80 mass%. % Range is preferred.

Further, to the black photosensitive resin composition of the present invention, if necessary, a curing accelerator, a thermal polymerization inhibitor, a plasticizer, a filler, a leveling agent, an antifoaming agent, a coupling agent, a surfactant, etc. are added. Agents can be added. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, and the like. Examples of the plasticizer include dibutylphthalate, dioctylphthalate, tricresyl phosphate, and the like. Examples of the material include glass fiber, silica, mica, alumina and the like, and examples of the defoaming agent and the leveling agent include silicone-based, fluorine-based and acryl-based compounds. Further, examples of the surfactant include a fluorine-based surfactant and a silicone-based surfactant.

The black photosensitive resin composition of the present invention contains the above components (A) to (H) as main components. In the black photosensitive resin composition, preferably, (A) is 10 to 60 mass% in the solid content (including the monomer component that becomes the solid content after photocuring) excluding the solvent (H), ( A) is 10 to 60 parts by mass with respect to 100 parts by mass, and (C) is 2 to 50 parts by mass with respect to 100 parts by mass of the total amount of (A) and (B). More preferably, with respect to 100 parts by mass of (A), (B) is 15 to 35 parts by mass, 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. The content of the (D) light-shielding material is preferably in the range of 30 to 60% by mass, more preferably 40 to 50% by mass, based on the solid content. Further, (E) is preferably 1 to 15 mass% in the solid content, and more preferably 2 to 7 mass %.

Examples of the method for forming a cured film using the black photosensitive resin composition of the present invention include a method using a photolithography method. As a method for forming the same, first, a black photosensitive resin composition is applied to the surface of a substrate, then the solvent is dried (prebaking), and then the obtained coating film is irradiated with ultraviolet rays through a photomask to expose a portion. And a pattern is formed by performing development to elute the unexposed portion with an alkaline aqueous solution, and then heat curing (post-baking) is performed. Here, as the substrate to which the black photosensitive resin composition is applied, glass, a transparent film (eg, polycarbonate, polyethylene terephthalate, polyether sulfone, etc.) or the like is used.

As a method of applying the black photosensitive resin composition to the substrate, in addition to known solution dipping method, spraying method, any method such as a roller coater machine, a land coater machine, a slit coater machine or a spinner machine may be used. Can be adopted. A coating film is formed by applying a desired thickness by these methods and then removing the solvent (prebaking). After prebaking, the solvent is removed by vacuum drying (VCD) at 20 to 100 Pa for 15 to 60 seconds, and then heating is performed by an oven, a hot plate or the like. The heating temperature and heating time in this prebaking are appropriately selected according to the solvent used, and for example, the heating is performed 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 device, and the photosensitive resin and the photosensitive monomer in the portion corresponding to the pattern are exposed by exposing through the photomask. The exposure device and its exposure irradiation conditions are appropriately selected, and the exposure is performed using a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a deep ultraviolet ray lamp.

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

After developing in this way, a heat treatment (post-baking) is performed at a temperature of 200 to 240° C. for 20 to 60 minutes. This post-baking is performed for the purpose of increasing the adhesion between the patterned black film and the substrate. This is performed by heating with an oven, a hot plate or the like.

The hue and chromaticity of the obtained black cured product are preferably -1.0<b*<0.2, and more preferably -1.0<b*<0.2 for the purpose of adjusting the black color of the present invention to an achromatic color or a bluish black color. It is necessary to be able to adjust to 1.0<b*<0.0. This value of b* is the D65 light source (JIS Z8720 daylight standard illuminant (light for color measurement)) or C light source (JIS Z8720 daylight used when displaying an object color illuminated by daylight. The auxiliary illuminant of No. 1) was used and the value was measured at a viewing angle of 2° or 10°.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

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

[Solid content concentration]
A glass filter [weight: W ₀ (g)] was impregnated with 1 g of the resin solution obtained in the synthesis example, weighed [W ₁ (g)], and the weight [W ₂ ( g)] from the following equation.
Solids concentration _{(wt%) = 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 pieces) + TSKgelSuperH-3000 (1 piece) + TSKgelSuperH-4000 (1 piece) + TSKgelSuper- H5000 (1 piece) [manufactured by Tosoh Corporation, temperature: 40° C., speed: 0.6 ml/min], and measured by standard polystyrene [PS-Oligomer Kit manufactured by Tosoh Corporation] weight average molecular weight (Mw) ) Was asked.

[Average secondary particle size]
Prepare a dispersion liquid for particle size measurement (a concentration of the light shielding material or the 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, and then use the particle size of a dynamic light scattering method. Using an analyzer (particle size analyzer FPAR-1000, manufactured by Otsuka Electronics Co., Ltd.), the average particle size of the cumulant method when the light-shielding material or the organic pigment was dispersed in the solvent was measured and defined as the average secondary particle size.

The abbreviations used in Synthesis Examples and the like are as follows.
BPFE: A reaction product of 9,9-bis(4-hydroxyphenyl)fluorene and chloromethyloxirane. A compound of the formula (I), wherein A is 9,9-fluorenyl and R _{1 to} R ₄ are hydrogen.
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 equipped with a reflux condenser, BPFE 78.63g (0.17mol), acrylic acid 24.50g (0.34mol), TPP 0.45g, and PGMEA 114g were charged and stirred for 12 hours under heating at 100 to 105°C. And a reaction product was obtained.

Next, 25.01 g (0.085 mol) of BPDA and 12.93 g (0.085 mol) of THPA were charged to the obtained reaction product, and the mixture was stirred for 6 hours under heating at 120 to 125° C. to obtain a polymerizable unsaturated group-containing alkali-soluble resin solution ( A)-1 was obtained. The solid content concentration of the obtained resin solution was 55.8 wt%, the acid value (solid content conversion) was 103 mgKOH/g, and the Mw by GPC analysis was 2,600.

[Preparation of black photosensitive resin composition]
Compositions shown in Table 1 were added to prepare black photosensitive resin compositions of Examples 1 to 2, Reference Example 3, and Comparative Examples 1 and 2. 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 (trade name, manufactured by Nippon Kayaku Co., Ltd.) DPHA)
(C) Photopolymerization initiator: 1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethanone=O-acetyloxime (BASF Corporation, trade name Irgacure OXE02)
(D) Light-shielding material: 25% by mass of carbon black (average secondary particle size 109 nm), 6% by mass of polymer dispersant, carbon black dispersion of PGMEA solvent (E) Organic pigment, dye:
(E)-1: YELLOW pigment dispersion (E)-2:Y139 (average secondary particle diameter 123 nm) of PGMEA solvent in which 15% by mass of Y139 (average secondary particle size 108 nm) and 9% by mass of polymer dispersant are used. ) Is 15% by mass, the polymer dispersant is 9% by mass, and the PGMEA solvent YELLOW pigment dispersion (E)-3:Y139 (average secondary particle diameter 158 nm) is 15% by mass, and the polymer dispersant is 9% by mass. PGMEA solvent YELLOW pigment dispersion (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]
After spin coating the black photosensitive resin compositions of Examples 1 and 2, Reference Example 3 and Comparative Examples 1 and 2 on a glass plate (5 inch square), and drying on a hot plate at 90° C. for 1 minute. Post-baked at 230°C for 30 minutes. Thus, a black cured product having a thickness of 1.45 μm was obtained.
Using the solid substrate of this black cured product, the reflection color was measured by 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 reflection color of only the light-shielding material is shown, but it is necessary to bring a* and b* close to 0 in order to obtain an achromatic color. Particularly, the reflection color is slightly deviated from the achromatic color. In this case, it is necessary to set b* to a numerical value of-in the situation where a blue hue is required rather than a brown hue. On the other hand, in Examples 1 and 2 and Reference Example 3, by adding a yellow organic pigment having a chromaticity similar to that of the light-shielding material, b* was changed to − without significantly changing the reflected color a*. You can see that you could move it to the side (minus side).
On the other hand, when the blue dye having the chromaticity of the opposite color of the light-shielding material is added as in Comparative Example 2, the value of b* is increased and the reflection color is moved in the direction opposite to the achromatic color direction to obtain a desired value. It can be seen that it is not possible to obtain an achromatic or slightly blue hue.
Therefore, as in the present invention, the reflection color of the black cured product can be made achromatic or adjusted to a desired hue only by selecting an organic pigment (or dye) of the same color as the light-shielding material and adding a small amount of it. It became clear.

Claims (6)

(A) Polymerizable unsaturated group-containing alkali-soluble resin, (B) Photopolymerizable monomer having at least one ethylenically unsaturated bond, (C) Photopolymerization initiator, (D) Light-shielding material, (E) Organic A black photosensitive resin composition for a light-shielding film, which contains a pigment and (H) a solvent,
The (D) light-shielding material has an average secondary particle diameter of 60 to 150 nm,
Wherein (E) an organic pigment, wherein (D) the light blocking member and the similar color organic pigments der Rutotomoni with chromaticity, Ri the average secondary particle diameter of 40~150nm der,
(A) is 10 to 60 mass% in the solid content excluding the solvent (H), which includes a monomer component that becomes a solid content after photo-curing, and (B) with respect to 100 mass parts of (A). Is 10 to 60 parts by mass, (C) is 2 to 50 parts by mass with respect to 100 parts by mass of the total amount of (A) and (B), and further, (D) in the solid content is 30 to 60% by mass. , (E) is 1 to 15 mass% in the solid content, and the black photosensitive resin composition for a light-shielding film. The black photosensitive resin composition for a light-shielding film according to claim 1, wherein the (D) light-shielding material is carbon black. As a polymerizable unsaturated group-containing alkali-soluble resin (A), a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols and an unsaturated group-containing monocarboxylic acid is used. The light-shielding film according to claim 1 or 2 , 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 is used. Black photosensitive resin composition for use. A cured product obtained by patterning the black photosensitive resin composition for a light-shielding film according to any one of claims 1 to 3 by a photolithography method and then thermally curing the same. 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.