JP6708367B2 - Photosensitive resin composition for light-shielding film, light-shielding film and color filter obtained by curing the same - Google Patents

Description

The present invention relates to a photosensitive resin composition for a light-shielding film, and a light-shielding film obtained by curing the same. More specifically, it is suitable for forming a fine light-shielding film on a transparent substrate. Regarding a resin composition and a light-shielding film obtained by curing the resin composition, the light-shielding film obtained by curing is suitably used when forming a black matrix or the like of a color filter.

A color liquid crystal display device has a liquid crystal part for controlling the amount of light transmitted or reflected and a color filter as constituent elements, and the method for manufacturing the color filter is usually performed on the surface of a transparent substrate such as glass or a plastic sheet. A method is used in which a black matrix is formed, and subsequently, different hues of red, green, and blue are sequentially formed in a stripe-shaped or mosaic-shaped color pattern.

In recent years, color liquid crystal display devices have been used in various fields such as liquid crystal televisions, liquid crystal monitors, and color liquid crystal mobile phones. The color filter is one of the important members that affect the visibility of the color liquid crystal display device, and in order to improve the visibility, that is, to obtain a clear image, the red (R), green ( G), blue (B), and other pixels need to have higher color purity than ever, and a black matrix needs to achieve high light shielding. For that purpose, a colorant is added to the photosensitive resin composition more than ever before. Must be added in large amounts.

Further, in liquid crystal display devices, improvements are actively being made to improve characteristics such as viewing angle, contrast, response speed, etc., which complicates the structure of the panel to which the color filter is adhered, and reduces the resin black matrix pattern substrate. The required properties such as adhesion and insulation are becoming more severe.

By the way, although carbon black is generally known as a light-shielding material (black color material) for a resin black matrix, since carbon black has a low electric resistance, it may cause a malfunction of the display device. Particularly, in an in-plane switching (IPS) type liquid crystal display device that can obtain a wide viewing angle, an electric field is applied in the in-plane direction of the liquid crystal layer, so that if the resistance value of the black matrix is low, the electric field is not normally applied, and the liquid crystal orientation is Disturbance occurs and causes display unevenness.

Therefore, as a method of increasing the electrical resistance of the black matrix using carbon black, a technique of coating the surface of carbon black with a resin has been applied (see Patent Document 1). However, if the number is increased, there is a limit to the degree of light shielding that can be realized while sufficiently maintaining the light patterning property, and it has become difficult to achieve the required high light shielding and high resistance. Therefore, a technique (see Patent Document 2) using titanium black as a light-shielding material, which has relatively high resistance and can realize high light-shielding, has been developed, but there is a concern that the photo-patterning property and the storage stability will be insufficient.

The black matrix currently used is generally said to have a volume resistivity (applied voltage of 1 to 10 V) of 1×10 ¹⁰ Ω·cm or more, and in Patent Document 2, 1×10 ¹² Ω. -The volume resistivity in cm is described. However, it is a value measured by applying an alternating current of about several V, and generally, the volume resistivity value decreases as the applied voltage increases, so that the volume resistivity value further decreases at an applied voltage of 10 V. There is a concern that it will be done.

JP 2001-207079 A JP 2008-260927 A

The present invention has been made in view of the above problems, and an object thereof is to apply a voltage of 10 V at an optical density OD of 3.5/μm or more and less than OD 4.0/μm in a photosensitive resin composition. Sometimes, it holds a volume resistivity of 1×10 ¹² Ω·cm or more, and holds a volume resistivity of 1×10 ¹¹ Ω·cm or more when a voltage of 10 V is applied at an OD of 4.0/μm or more. While maintaining light shielding and high resistance, even when a thin line of, for example, 10 μm or less is formed, it has excellent development adhesion, and it is possible to form a thin line of 8 μm or 6 μm, and sufficient adhesion to a glass substrate can be secured. It is to provide a photosensitive resin composition for a light-shielding film. The present invention also provides a cured product such as a light-shielding film pattern formed by a photolithography method using the photosensitive resin composition, and further provides a color filter or a touch panel including the cured product.

As a result of studies conducted by the present inventors to solve the above problems, a photosensitive resin composition containing a polymerizable unsaturated group-containing alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, a light shielding component, and a solvent. As the polymerizable unsaturated group-containing alkali-soluble resin, by blending a polymerizable unsaturated group-containing alkali-soluble resin having a specific structure and acid value, a photosensitive resin composition having excellent photopatterning characteristics can be obtained. The inventors have found that it is possible to obtain a light-shielding cured film having excellent characteristics of high light shielding and high resistance, and have completed the present invention.
That is, the gist of the present invention is as follows.

但し、一般式（Ｉ）において、Ｒ₁及びＲ₂は、独立に水素原子、炭素数１〜５のアルキル基、又はハロゲン原子を示し、Ｘは、‐CO‐、−SO₂−、‐C(CF₃)₂−、-Si(CH₃)₂‐、-CH₂‐、-C(CH₃)₂‐、-O-、又は、フルオレン-9,9-ジイル基又は不存在（すなわち単結合を意味する。以下同様。）を示し、ｎは平均値０〜１０を示す。 (1) The present invention provides the following components (A) to (E):
(A) A polymerizable unsaturated group-containing alkali-soluble resin obtained by further reacting a reaction product of a compound represented by the following general formula (I) and (meth)acrylic acid with a polyvalent carboxylic acid or an anhydride thereof. ,
(B) a photopolymerizable monomer having at least one ethylenically unsaturated bond,
(C) a photopolymerization initiator,
In a photosensitive resin composition for a light-shielding film, which comprises (D) one or more light-shielding components selected from the group consisting of black organic pigments, mixed-color organic pigments and light-shielding materials, and (E) a solvent,
(A) component is a polycarboxylic acid or its anhydride (a) dicarboxylic acid or tricarboxylic acid or its acid anhydride, and (b) tetracarboxylic acid or its acid dianhydride, (a) / ( It is a polymerizable unsaturated group-containing alkali-soluble resin which is obtained by reacting b) in a molar ratio of 0.01 to 0.5 and has an acid value of 80 to 120 mgKOH/g. A photosensitive resin composition for a light-shielding film, characterized in that

However, in the general formula (I), R ₁ and R ₂ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and X represents —CO—, —SO ₂ —, or —C. _{(CF 3) 2 -, -} Si (CH 3) 2 -, - CH 2 -, - C (CH 3) 2 -, - O-, or, 9,9-diyl group or absence (i.e. single Means a bond. The same applies hereinafter), and n represents an average value of 0 to 10.

(2) In the present invention, the mass ratio (A)/(B) of the component (A) and the component (B) is 50/50 to 90/10, and the total of the component (A) and the component (B). In the solid content containing 2 to 30 parts by mass of the component (C) with respect to 100 parts by mass, and the component (D) becomes a solid content by photocuring the photosensitive resin composition for a light shielding film 40-70 mass% is contained, It is a photosensitive resin composition for light-shielding films as described in (1).

(3) The present invention is also the photosensitive resin composition for a light-shielding film according to (1) or (2), wherein the (D) light-shielding component is carbon black.
(4) The present invention also has a volume resistivity of 1×10 when a voltage of 10 V is applied when the optical density OD is 3.5/μm or more and less than 4.0/μm. ¹² The photosensitive resin composition for a light-shielding film according to any one of (1) to (3), which is used for forming a coating film having Ω·cm or more.
(5) The present invention also has a volume resistivity of 1×10 when a voltage of 10 V is applied when the optical density OD is 4.0/μm or more. ¹¹ The photosensitive resin composition for a light-shielding film according to any one of (1) to (3), which is used for forming a coating film having Ω·cm or more.
(6) The present invention is also a light-shielding film formed by curing the photosensitive resin composition for a light-shielding film according to any one of (1) to (5).
(7) The present invention also applies the photosensitive resin composition for a light-shielding film according to any one of (1) to (5) onto a transparent substrate, pre-bakes it, and then exposes it with an ultraviolet exposure device and uses an alkaline aqueous solution. It is a color filter comprising a light-shielding film produced by development and post-baking.

(8) The present invention also includes the following components (A) to (F),
(A) A polymerizable unsaturated group-containing alkali-soluble resin obtained by further reacting a reaction product of the compound represented by the general formula (I) and (meth)acrylic acid with a polyvalent carboxylic acid or an anhydride thereof. ,
(B) a photopolymerizable monomer having at least one ethylenically unsaturated bond,
(C) a photopolymerization initiator,
(D) one or more light-shielding components selected from the group consisting of black organic pigments, mixed-color organic pigments and light-shielding materials,
(E) solvent, and
(F) A method for producing a photosensitive resin composition for a light-shielding film, which comprises a dispersant as an essential component,
The component (A) contains (a) a dicarboxylic acid or a tricarboxylic acid or an acid anhydride thereof as the polyvalent carboxylic acid or an anhydride thereof, and (b) a tetracarboxylic acid or an acid dianhydride thereof (a)/ A polymerizable unsaturated group-containing alkali-soluble resin having an acid value of 80 to 120 mgKOH/g, which is obtained by reacting (b) in a molar ratio of 0.01 to 0.5. Yes,
The component (D) is previously dispersed in a part of the component (E) together with a part of the component (A) and a dispersant (F), and then the remaining components (A), (B), and (C). The method is a method for producing a photosensitive resin composition for a light-shielding film, which comprises mixing the component and the remaining component (E).

The photosensitive resin composition for a light-shielding film of the present invention is a high light-shielding light-shielding film having an OD of about 3.5/μm and capable of maintaining a high resistance such as a volume resistivity of 1×10 ¹² Ω·cm or more even at an applied voltage of 10V. The adhesiveness is excellent in developing adhesion even when a fine line having a line width of 10 μm, and further 8 μm or 6 μm is formed, and moreover, the adhesiveness with the glass substrate can be sufficiently secured.

但し、一般式（Ｉ）において、Ｒ₁及びＲ₂は、独立に水素原子、炭素数１〜５のアルキル基、又はハロゲン原子を示し、Ｘは、‐CO‐、−SO₂−、‐C(CF₃)₂−、-Si(CH₃)₂‐、-CH₂‐、-C(CH₃)₂‐、-O-、又は、フルオレン-9,9-ジイル基又は不存在を示し、ｎは０〜１０の平均値である。 Hereinafter, the present invention will be described in detail.
The polymerizable unsaturated group-containing alkali-soluble resin as the component (A) is obtained by adding (meth)acrylic acid (this means “acrylic acid and/or methacrylic acid”) to the epoxy compound represented by the general formula (I). ) Is reacted, and the resulting compound having a hydroxy group is reacted with (a) a dicarboxylic acid or a tricarboxylic acid or an acid anhydride thereof, and (b) a tetracarboxylic acid or an acid dianhydride thereof to obtain an epoxy (meth ) Acrylic acid adduct. The epoxy compound represented by the general formula (I) means an epoxy compound obtained by reacting a bisphenol with epihalohydrin or an equivalent thereof. Since the component (A) has both a polymerizable unsaturated double bond and a carboxyl group, it imparts excellent photocurability, good developability and patterning characteristics to the photosensitive resin composition, and improves the physical properties of the light-shielding film.

However, in the general formula (I), R ₁ and R ₂ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and X represents —CO—, —SO ₂ —, or —C. _{(CF 3) 2 -, -} Si (CH 3) 2 -, - CH 2 -, - C (CH 3) 2 -, - O-, or represents a 9,9-diyl group or absent, n is an average value of 0-10.

Examples of the bisphenols giving the epoxy compound of the general formula (I) 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)hexafluoro Propane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dichlorophenyl)hexafluoropropane, bis(4-hydroxyphenyl)dimethylsilane, bis(4-hydroxy) -3,5-Dimethylphenyl)dimethylsilane, bis(4-hydroxy-3,5-dichlorophenyl)dimethylsilane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, bis (4-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2- Bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4 -Hydroxyphenyl)ether, bis(4-hydroxy-3,5-dimethylphenyl)ether, bis(4-hydroxy-3,5-dichlorophenyl)ether, 9,9-bis(4-hydroxyphenyl)fluorene, 9, 9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene, 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9, 9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene , 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene, 4,4'-biphenol, 3,3'- Biphenol etc. are mentioned. Among these, bisphenols in which X in the general formula (I) is a fluorene-9,9-diyl group can be particularly preferably used.

The compound of the general formula (I) for deriving the alkali-soluble resin (A) is an epoxy compound having two glycidyl ether groups, which is obtained by reacting the bisphenols with epichlorohydrin. In this reaction, generally, a diglycidyl ether compound is oligomerized, and since n is usually a mixture of a plurality of values, an average value of 0 to 10 (not necessarily an integer) is obtained, but a preferable average value of n. Is 0 to 3. When the average value of n exceeds the upper limit value, the viscosity of the composition becomes too large when the composition is made into a photosensitive resin composition using an alkali-soluble resin synthesized by using the epoxy compound, and coating may not be successful. However, alkali solubility cannot be sufficiently imparted, and alkali developability becomes extremely poor.

Next, the compound of the general formula (I) is reacted with, for example, acrylic acid or methacrylic acid as the unsaturated group-containing monocarboxylic acid, or both of them, and the reaction product having a hydroxy group obtained thereby is reacted. , (A) dicarboxylic acid or tricarboxylic acid or its acid anhydride, and (b) tetracarboxylic acid or its acid dianhydride. At that time, the reaction is carried out in the range of (a)/(b) molar ratio of 0.01 to 0.5. By this reaction, a polymerizable unsaturated group-containing alkali-soluble resin having a structure of an epoxy (meth)acrylate acid adduct is obtained.

The (a) dicarboxylic acid or tricarboxylic acid or its acid anhydride used in the epoxy (meth)acrylate acid adduct is a chain hydrocarbon dicarboxylic acid or tricarboxylic acid or its acid anhydride or alicyclic dicarboxylic acid or tricarboxylic acid. 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 an 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, a dicarboxylic acid or tricarboxylic acid having an optional substituent introduced or an acid anhydride thereof may be used. Further, examples of the alicyclic dicarboxylic acid or tricarboxylic acid or 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 in which the substituent is introduced 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 having an arbitrary substituent introduced therein or its An acid anhydride may be used.

Further, as the (b) tetracarboxylic acid or its acid dianhydride used in the epoxy (meth)acrylate acid addition product, a chain hydrocarbon tetracarboxylic acid or its acid dianhydride or alicyclic tetracarboxylic acid or The acid dianhydride, the aromatic polycarboxylic acid or the acid dianhydride is used. Here, as the chain hydrocarbon tetracarboxylic acid or its acid dianhydride, for example, butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, and the like, further tetra substituted optional substituents It may be a carboxylic acid or its 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 an arbitrary substituent introduced or its dianhydride. Further, 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 optional. It may be a tetracarboxylic acid having a substituent introduced therein or its dianhydride.

The molar ratio (a)/(b) of (a) dicarboxylic acid or tricarboxylic acid or its acid anhydride and (b) tetracarboxylic acid or its dianhydride used in the epoxy (meth)acrylate acid adduct is As described above, it is 0.01 to 0.5, preferably 0.02 or more and less than 0.1. When the molar ratio (a)/(b) deviates from the above range, the optimum molecular weight for obtaining the photosensitive resin composition of the present invention having high light-shielding and high resistance and good photopatternability cannot be obtained. Therefore, it is not preferable. The smaller the molar ratio (a)/(b), the higher the alkali solubility and the higher the molecular weight.

The epoxy (meth)acrylate acid adduct can be produced by the above-mentioned process by a known method, for example, the method described in JP-A-8-278629 or JP-A-2008-9401. First, as a method of reacting (meth)acrylic acid with an epoxy compound of the general formula (I), for example, (meth)acrylic acid in an equimolar amount to the epoxy group of the epoxy compound is added to a solvent, and a catalyst (triethylbenzyl) is added. In the presence of ammonium 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.

The weight average molecular weight (Mw) of the polymerizable unsaturated group-containing alkali-soluble resin (A) is preferably in the range of 4000 to 20000, and more preferably in the range of 4500 to 7000. If the weight average molecular weight (Mw) is less than 4000, it tends to be difficult to maintain the high resistance of the photosensitive resin composition using (A) over 1V to 10V, and the weight average molecular weight (Mw). When) is more than 20000, a development residue or a residual film in an unexposed area is likely to remain when the photosensitive resin composition is highly light-shielded. Further, (A) has an acid value in the range of 80 to 120 mgKOH/g. If this value is less than 80 mgKOH/g, a residue tends to remain during alkaline development of the photosensitive resin composition using (A), and if it exceeds 120 mgKOH/g, a highly light-shielding photosensitive resin composition using (A). Any of these is not preferable because the permeation of the alkaline developer into the toner becomes too fast and peeling development occurs. Regarding the polymerizable unsaturated group-containing alkali-soluble resin (A), only one kind thereof may be used or a mixture of two or more kinds may be used.

Next, as the photopolymerizable monomer having (B) at least one ethylenically unsaturated bond, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxyhexyl (meth ) (Meth)acrylic acid esters having a hydroxyl group such as acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetra Methylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, Of dipentaerythritol tetra(meth)acrylate, glycerol(meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, or dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, phosphazene Examples thereof include (meth)acrylic acid esters such as alkylene oxide-modified hexa(meth)acrylate and caprolactone-modified dipentaerythritol hexa(meth)acrylate, and one or more of these can be used. The photopolymerizable monomer (B) having at least one ethylenically unsaturated bond does not have a free carboxy group.

The mixing ratio of these (A) component and (B) component is preferably 50/50 to 90/10 in terms of mass ratio (A)/(B), and preferably 60/40 to 80/20. Is good. If the blending ratio of the component (A) is less than 50/50 in (A)/(B), the cured product after photocuring becomes brittle, and the acid value of the coating film in the unexposed area is low, resulting in alkali development. There is a problem that the solubility in the liquid is lowered and the pattern edge is not sharp and sharp, and when (A)/(B) is more than 90/10, the proportion of the photoreactive functional group in the resin is large. Formation of the cross-linked structure is not sufficient, and the acid value of the resin component is too high, and the solubility in the alkali developing solution in the exposed area is high, so that the formed pattern is thinner than the target line width. There is a possibility that a problem such as the occurrence of a pattern or a missing pattern easily occurs.

Examples of the photopolymerization initiator as the component (C) include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and p-tert-butyl. Acetophenones such as acetophenone, benzophenone, 2-chlorobenzophenone, benzophenones such as p,p'-bisdimethylaminobenzophenone, benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2- (o-Chlorophenyl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-4,5-diphenyl Biimidazole, 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole and other biimidazole compounds, 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 -Halomethyldiazole 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(trichloromethyl)-1 ,3,5-Triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4, Halomethyl-s-triazine system such as 6-bis(trichloromethyl)-1,3,5-triazine and 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine Compounds, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime), 1-(4-phenyl Rusulfanylphenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylsulfanylphenyl)butane-1,2-dione-2-oxime-O-acetate, 1-(4 -Methylsulfanylphenyl)butan-1-one oxime-O-acetate and other O-acyl oxime compounds, benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxane , Sulfur compounds such as 2-isopropylthioxanthone, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, anthraquinones such as 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. Among these, O-acyl oxime compounds are preferably used from the viewpoint that a highly sensitive photosensitive resin composition for a light shielding film can be easily obtained. 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.

These photopolymerization initiators and sensitizers may be used alone or in combination of two or more. Further, a compound which does not act as a photopolymerization initiator or a sensitizer by itself but can be used in combination to increase the ability of the photopolymerization initiator or the sensitizer can be added. Examples of such compounds include tertiary amines such as triethanolamine and triethylamine, which are effective when used in combination with benzophenone.

The amount of the photopolymerization initiator as the component (C) used is preferably 2 to 30 parts by mass, and preferably 5 to 25 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). Good to have. When the blending ratio of the component (C) is less than 2 parts by mass, the photopolymerization rate becomes slow and the sensitivity decreases, while when it exceeds 30 parts by mass, the sensitivity is too strong and the pattern line There is a possibility that the width becomes thick with respect to the pattern mask, a line width faithful to the mask cannot be reproduced, or the pattern edge is not sharp and sharp.

The component (D) is a light-shielding component selected from black organic pigments, mixed-color organic pigments or light-shielding materials, and preferably has excellent heat resistance, light resistance and solvent resistance. Here, examples of black organic pigments include perylene black, aniline black, and cyanine black. Examples of the mixed color organic pigment include those obtained by mixing two or more kinds of pigments selected from red, blue, green, violet, yellow, cyanine, magenta and the like to give a pseudo black color. Examples of the light shielding material include carbon black, chromium oxide, iron oxide, titanium black and the like. Two or more kinds of light-shielding components can be appropriately selected and used, but carbon black is particularly preferable in terms of good light-shielding properties, surface smoothness, dispersion stability, and compatibility with resins. Further, when it is desired to further increase the resistance value of the light-shielding film by using carbon black, surface-coated carbon black obtained by coating the surface of carbon black with a dye, a pigment, a resin or the like may be used.

Examples of the solvent of the component (E) include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol and propylene glycol, terpenes such as α- or β-terpineol, acetone, methyl ethyl ketone and cyclohexanone. , Ketones such as N-methyl-2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol. Glycol ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve Acetates such as acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. can be mentioned and dissolved using these. By mixing, it is possible to obtain a composition in the form of a uniform solution.

Then, these light-shielding components are preferably dispersed in a solvent together with the (F) dispersant in advance to form a light-shielding dispersion liquid, and then blended as a light-shielding film photosensitive resin composition. Here, since the solvent to be dispersed becomes a part of the component (E), any solvent listed in the above component (E) can be used. For example, propylene glycol monomethyl ether acetate, 3 methoxybutyl acetate. Etc. are preferably used. The blending ratio of the light-shielding component (D) forming the light-shielding dispersion is preferably in the range of 40 to 70% by mass based on the total solid content of the photosensitive resin composition for a light-shielding film of the present invention. , 40 to 60% by mass is particularly preferable. If it is less than 40% by mass, the light-shielding property will not be sufficient for high light-shielding. If it exceeds 70% by mass, the content of the photosensitive resin serving as the original binder is reduced, so that the development characteristics are impaired and the film forming ability is impaired, which is an undesirable problem.

Further, the (F) dispersant is used in the light-shielding dispersion liquid in order to disperse the light-shielding component in a stable manner. For this purpose, known dispersants such as various polymer dispersants can be used. .. As examples of the dispersant, known compounds conventionally used for pigment dispersion (such as compounds commercially available under the names of dispersant, dispersion wetting agent, dispersion accelerator, etc.) can be used without particular limitation. Examples thereof include cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, pigment derivative type dispersants (dispersion aids), and the like. In particular, it has a cationic functional group such as an imidazolyl group, a pyrrolyl group, a pyridyl group, a primary, secondary or tertiary amino group as an adsorption point on the pigment, and has an amine value of 1 to 100 mgKOH/g and a number average molecular weight. A cationic polymer dispersant having a ratio of 1,000 to 100,000 is suitable. The compounding amount of this dispersant is 1 to 30% by mass, preferably 2 to 25% by mass, based on the light-shielding component.

Further, when preparing the light-shielding dispersion liquid, a part of the polymerizable unsaturated group-containing alkali-soluble resin as the component (A) is co-dispersed in addition to the above-mentioned dispersant, whereby the light-shielding film photosensitive resin composition is obtained. In such a case, the exposure sensitivity can be easily maintained at a high level, the adhesiveness at the time of development is good, and the problem of residue does not easily occur. The content of the component (A) in the light-shielding dispersion is preferably 2 to 20% by mass, more preferably 5 to 15% by mass. If the amount of the component (A) is less than 2% by mass, the effects of co-dispersion such as sensitivity improvement, adhesion improvement, and residue reduction cannot be obtained. Further, when the content is 20% by mass or more, particularly when the content of the light shielding material is large, the viscosity of the light shielding dispersion liquid is high, and it becomes difficult or extremely time-consuming to disperse the light shielding dispersion liquid, and thus the high resistance is high. It becomes difficult to obtain a photosensitive resin composition for obtaining a coating film. Then, the obtained light-shielding dispersion liquid is mixed with the remaining component (A), component (B), component (C), and remaining component (E) to form a photosensitive resin composition for light-shielding film. can do.

Further, the photosensitive resin composition of the present invention, if necessary, a curing accelerator, a thermal polymerization inhibitor, a plasticizer, a filler, a solvent, a leveling agent, a defoaming agent, a coupling agent, a surfactant, etc. Additives 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, and examples of the coupling agent include 3-(glycidyloxy)propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, A silane coupling agent such as 3-ureidopropyltriethoxysilane can be mentioned.

The photosensitive resin composition of the present invention contains the above-mentioned components (A) to (E) as main components. It is desirable that the components (A) to (D) are contained in a total amount of 80% by mass, preferably 90% by mass or more in the solid content excluding the solvent (the solid content includes a monomer which becomes the solid content after curing). The amount of the solvent (E) varies depending on the target viscosity, but it is preferable that the amount of the solvent (E) be contained in the photosensitive resin composition in the range of 70 to 90% by mass.

The photosensitive resin composition for a light-shielding film in the present invention is excellent as a photosensitive resin composition for forming a color filter light-shielding film, for example, and the following photolithography method is used as a method for forming the light-shielding film. First, the photosensitive resin composition is applied on a transparent substrate, then the solvent is dried (prebaking), a photomask is applied to the coating film thus obtained, and ultraviolet rays are applied to expose the exposed portion. Examples include a method of curing, further developing using an alkaline aqueous solution to elute unexposed portions to form a pattern, and post-baking (thermal baking) as post-drying.

As the transparent substrate for applying the photosensitive resin composition, in addition to a glass substrate, a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether sulfone, etc.) on which a transparent electrode such as ITO or gold is vapor-deposited or patterned, etc. Can be illustrated. The method of applying the solution of the photosensitive resin composition on the transparent substrate, in addition to known solution dipping method, spray method, any of roller coater machine, land coater machine, slit coater machine or a method using a spinner machine, etc. The method can also be adopted. By these methods, after coating to a desired thickness, the solvent is removed (prebaking) to form a film. Prebaking is performed by heating with an oven, a hot plate, or the like. The heating temperature and heating time in 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 ultraviolet exposure device, and only the resist corresponding to the pattern is exposed by exposing through a photomask. The exposure apparatus and its exposure irradiation conditions are appropriately selected, and light exposure is performed using a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a far ultraviolet ray lamp, and the photosensitive resin composition in the coating film is photocured.

The alkali development after exposure is performed for the purpose of removing the resist in the unexposed portion, and a desired pattern is formed by this development. Examples of the developer suitable for the 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, and particularly sodium carbonate, potassium carbonate, lithium carbonate. It is preferable to develop at a temperature of 23 to 28° C. using a weak alkaline aqueous solution containing 0.05 to 3 mass% of a carbonate such as, and a fine image can be obtained by using a commercially available developing machine or an ultrasonic cleaner. It can be precisely formed.

After the development, a heat treatment (post-baking) is performed preferably at a temperature of 180 to 250° C. for 20 to 60 minutes. This post-baking is performed for the purpose of increasing the adhesion between the patterned light-shielding film and the substrate. This is performed by heating with an oven, a hot plate or the like as in the pre-baking. The patterned light-shielding film of the present invention is formed through the above-mentioned steps of the photolithography method.

As described above, the photosensitive resin composition of the present invention is suitable for forming a fine pattern by operations such as exposure and alkali development. Further, the photosensitive resin composition for a light-shielding film of the present invention can be suitably used as a coating material, and is particularly suitable as an ink for a color filter used in a liquid crystal display device or a photographing element, and formed by this. The light shielding film is useful as a color filter, a black matrix for liquid crystal projection, a light shielding film, a light shielding film for a touch panel, and the like.

The high light-shielding and high-resistance light-shielding film obtained in the present invention has a volume resistivity of 1×10 ¹² Ω·cm or more at an applied voltage of 10 V when OD 3.5/μm or more and less than OD 4.0/μm. It will be. Further, even at a light-shielding level of OD 4.0/μm or more, a volume resistivity of 1×10 ¹¹ Ω·cm or more can be secured at an applied voltage of 10 V, and more preferably 1×10 ¹² Ω·at an applied voltage of 10 V. The volume resistivity of cm or more can be secured. Further, the pattern formed by using the photosensitive resin composition of the present invention is less likely to undergo thermal sagging during post-baking, keeps the cross-sectional shape of the pattern rectangular, and shields the side surface of the pattern perpendicular to the substrate. Suitable for forming a film pattern.

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

First, a synthesis example 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.
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 pieces) + TSKgelSuperH-3000 (1 piece) + TSKgelSuperH-4000 (1 piece) + TSKgelSuper- H5000 (1 piece) (manufactured by Tosoh Corp.), temperature: 40° C., speed: 0.6 ml/min], and measured as standard polystyrene [PS-Oligomer Kit manufactured by Tosoh Corp.] weight average molecular weight ( Mw).

The abbreviations used in Synthesis Examples and Comparative Synthesis Examples are as follows.
BPFE: A reaction product of 9,9-bis(4-hydroxyphenyl)fluorene and chloromethyloxirane. The compound of the general formula (I), wherein X is fluorene-9,9-diyl, and R ₁ and R ₂ 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]
BPFE 244.3g (0.50mol), acrylic acid 72.1g (1.0mol), TPP 0.45g, and PGMEA 334g were charged into a 1L four-necked flask equipped with a reflux condenser, and heated at 100 to 105°C for 12 hours. The reaction product was obtained by stirring.

Next, 94.15 g (0.32 mol) of BPDA and 22.82 g (0.15 mol) of THPA were added to the obtained reaction product, and the mixture was stirred for 6 hours under heating at 115 to 120° C. to give a polymerizable unsaturated group-containing alkali-soluble resin solution ( A)-1 was obtained. The solid content concentration of the obtained resin solution was 56.5 wt %, the acid value (solid content conversion) was 102 mgKOH/g, and the Mw by GPC analysis was 5200.

[Synthesis example 2]
BPFE 244.3g (0.50mol), acrylic acid 72.1g (1.0mol), TPP 0.45g, and PGMEA 318g were charged into a 1L four-necked flask equipped with a carbonization condenser, and heated at 100 to 105°C for 12 hours. The reaction product was obtained by stirring.

Next, 94.15 g (0.32 mol) of BPDA and 3.04 g (0.02 mol) of THPA were charged to the obtained reaction product, and the mixture was stirred under heating at 115 to 120°C for 6 hr to obtain a polymerizable unsaturated group-containing alkali-soluble resin solution ( A)-2 was obtained. The solid content concentration of the obtained resin solution was 56.5 wt%, the acid value (solid content conversion) was 90 mgKOH/g, and the Mw by GPC analysis was 4,600.

[Synthesis example 3]
BPFE 219.9g (0.45mol), acrylic acid 64.9g (0.9mol), TPP 0.45g, and PGMEA 294g were charged into a 1L four-necked flask equipped with a carbonization condenser, and heated under 100 to 105°C for 12 hours. The reaction product was obtained by stirring.

Next, 94.15 g (0.32 mol) of BPDA and 3.04 g (0.02 mol) of THPA were added to the obtained reaction product, and the mixture was stirred for 6 hours under heating at 115 to 120° C. to give a polymerizable unsaturated group-containing alkali-soluble resin solution ( A)-3 was obtained. The solid content concentration of the obtained resin solution was 56.5 wt%, the acid value (solid content conversion) was 97 mgKOH/g, and the Mw by GPC analysis was 5,500.

[Comparative Synthesis Example 1]
BPFE 244.3g (0.50mol), acrylic acid 72.1g (1.0mol), TPP 0.45g, and PGMEA 329g were charged into a 1L four-necked flask equipped with a carbonizing condenser, and heated at 100 to 105°C for 12 hours. The reaction product was obtained by stirring.

Next, 73.56 g (0.25 mol) of BPDA and 38.03 g (0.25 mol) of THPA were added to the obtained reaction product, and the mixture was stirred for 6 hours under heating at 115 to 120° C. to give a polymerizable unsaturated group-containing alkali-soluble resin solution ( A)-4 was obtained. The solid content concentration of the obtained resin solution was 56.5 wt%, the acid value (solid content conversion) was 70 mgKOH/g, and the Mw by GPC analysis was 3,600.

[Preparation Example 1] Preparation of dye-coated carbon black 1000 g of carbon black was mixed with water to prepare 10 L of a slurry, which was stirred at 95°C for 1 hour, allowed to cool, and then washed with water. This was mixed with water again to prepare 10 L of slurry, 42.9 g of 70% nitric acid was added, and the mixture was stirred at 40° C. for 4 hours. This was allowed to cool, washed with water, and then mixed with water again to prepare 10 L of a slurry, 769.2 g of a 13% sodium hypochlorite aqueous solution was added, and the mixture was stirred at 40° C. for 6 hours. This was allowed to cool, washed with water, then mixed again with water to prepare 10 L of a slurry, 38.1 g of a dye (Direct Deep BLACK) having a purity of 38.4% was added, and the mixture was stirred at 40° C. for 1 hour, and then further. 10.1 g of aluminum sulfate was added, and the mixture was stirred at 40° C. for 1 hour. This was allowed to cool, washed with water, filtered and dried to obtain a dye-coated carbon black.

(Examples 1 to 4, Comparative Example 1)
Next, the present invention will be specifically described based on Examples and Comparative Examples relating to the production of the photosensitive resin composition for a light-shielding film and the cured product thereof, but the present invention is not limited thereto. Here, the raw materials and abbreviations used in the production of the photosensitive resin compositions for light-shielding films and the cured products thereof in Examples and Comparative Examples below are as follows.

(Polymerizable unsaturated group-containing alkali-soluble resin)
(A)-1 component: Alkali-soluble resin solution obtained in Synthesis Example 1 above
(A)-2 component: Alkali-soluble resin solution obtained in Synthesis Example 2 above
(A)-3 component: alkali-soluble resin solution obtained in Synthesis Example 3 above
(A)-4 component: Alkali-soluble resin solution obtained in Comparative Synthesis Example 1 above

(Photopolymerizable monomer)
(B): Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name DPHA manufactured by Nippon Kayaku Co., Ltd.)

(Photopolymerization initiator)
(C): Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(0-acetyloxime) (BASF Japan, product name Irgacure OXE02 )

(Light-shielding dispersion pigment)
(D)-1: Propylene glycol monomethyl ether acetate dispersion liquid having a carbon black concentration of 25.0% by mass and a polymer dispersant concentration of 5.0% by mass (solid content: 30.0%)
(D)-2: 300.0 g of the dye-coated carbon black prepared in Preparation Example 1, 24.0 g of a urethane dispersant, 146.0 g of the alkali-soluble resin solution obtained in Synthesis Example 2, and propylene glycol monomethyl ether. A dispersion obtained by dispersing 729.6 g of acetate with a bead mill (solid content: 33.9%)

(solvent)
(E)-1: Propylene glycol monomethyl ether acetate
(E)-2: Cyclohexanone

(Silane coupling agent)
(F): 3-mercaptopropyltrimethoxysilane (trade name: KBM-803: manufactured by Shin-Etsu Chemical Co., Ltd.)

(Surfactant)
(G): BYK-330 (manufactured by Big Chemie)

The above-mentioned blending components were blended in the proportions shown in Table 1 to prepare the photosensitive resin compositions of Examples 1 to 4 and Comparative Example 1. In addition, all the numerical values in Table 1 represent parts by mass. Further, (E)-1 in the column of solvent is PGMEA (the same as (E)-1) in the unsaturated group-containing resin solution (polymerizable unsaturated group-containing alkali-soluble resin solution), and the light-shielding dispersion liquid. The amount does not include PGMEA (same as (E)-1).

[Evaluation]
Using the photosensitive resin compositions for light-shielding films of Examples 1 to 4 and Comparative Example 1, the following evaluations were performed. The results of these evaluations are shown in Table 2.

<Evaluation of development characteristics (pattern line width/pattern linearity)>
Each of the photosensitive resin compositions obtained above was applied onto a 125 mm×125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking would be 1.1 μm, and at 90° C. Prebaked for 1 minute. After that, the exposure gap was adjusted to 100 μm, a 10 μm or 6 μm negative photomask was covered on the dry coating film, and an ultraviolet ray of 80 mJ/cm ² was irradiated with an ultrahigh pressure mercury lamp having an i-line illuminance of 30 mW/cm ² . The photocuring reaction of the photosensitive portion was performed.

Next, this exposed coated plate was subjected to a shower development pressure of 1 kgf/cm ^{2 in} a 0.05% potassium hydroxide aqueous solution at 25° C., from the development time (break time=BT) at which a pattern started to appear, +20 seconds and +30. After developing for 2 seconds, spray-washing with 5 kgf/cm ² pressure is performed to remove the unexposed portion of the coating film to form a pixel pattern on the glass substrate, and then heat at 230° C. for 30 minutes using a hot air dryer. The line width and pattern linearity with respect to the mask width of 10 μm line and 6 μm line after post-baking were evaluated. When the pattern image did not appear even after the development time of 80 seconds, it was determined that development was not possible. The evaluation methods are as follows.

Pattern line width: The pattern line widths of the mask widths of 10 μm and 6 μm were measured using a length measuring microscope (“XD-20” manufactured by Nikon Corporation).
Pattern linearity: 10 μm or 6 μm mask pattern after post-baking is observed under a microscope. Peeling on the substrate and pattern edge part jaggedness are not observed, and some are observed, and all are observed. The thing was evaluated as x.

<Evaluation of OD/μm>
Each of the photosensitive resin compositions obtained above was applied onto a 125 mm×125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking would be 1.1 μm, and at 90° C. Prebaked for 1 minute. Then, without covering the negative type photomask, ultraviolet rays of 80 mJ/cm ² were irradiated with an ultrahigh pressure mercury lamp having an i-line illuminance of 30 mW/cm ² to perform a photocuring reaction on the exposed portion.

Next, the exposed coated plate was developed in a 0.05% potassium hydroxide aqueous solution at 25° C. at a shower development pressure of 1 kgf/cm ² for 60 seconds, and then washed with spray water at 5 kgf/cm ² pressure. After hot post-baking at 230° C. for 30 minutes using a hot air dryer, the OD of the light irradiation portion was evaluated using a Macbeth transmission densitometer. Further, the film thickness of the light irradiation portion was measured, and the value obtained by dividing the OD value by the film thickness was defined as OD/μm.

<Evaluation of adhesion strength with glass substrate>
Each of the photosensitive resin compositions obtained above was applied onto a 125 mm×125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking would be 1.1 μm, and the coating was performed at 90° C. for 1 hour. Prebaked for a minute. After that, solid exposure was performed at 80 mJ/cm ² with an ultrahigh pressure mercury lamp having an i-line illuminance of 30 mW/cm ² without using a photomask, and hot post-baking was performed at 230° C. for 30 minutes using a hot air dryer. Then, the post-baked substrate obtained above was evaluated for adhesion strength with a glass substrate as follows by an evaluation method according to the three-point bending adhesion test method of JIS K6856-1994. The post-baked coated substrate and the glass substrate not coated with the resin composition (Corning 1737) (non-coated substrate) were each cut into strips of 20 mm x 63 mm to prepare test pieces. Both substrates (test pieces) were attached so that the post-baked substrate with coating film and the substrate without coating film were overlapped with each other with a fixed amount of a sealant epoxy adhesive so that the overlapping width was 8 mm. The sealant epoxy adhesive has a circular shape and a diameter of about 5 mm when laminated. After that, the laminated test pieces were prebaked at 90° C. for 20 minutes, and then post-baked at 150° C. for 2 hours to form three-point bent test pieces. Further, 20 mm×63 mm uncoated substrate test pieces were also bonded together in the same manner as above to prepare a sample for a comparative test.

In the test piece obtained above, the coated substrate and the uncoated substrate or the sample for the comparative test are supported by two supports so that the overlapping portion is centered. The interval was 3 cm), and the bonded portion was peeled off by using ORIENTEC (trade name) UCT-100 (trade name) from directly above the laminated portion at a speed of 1 mm/min. Here, the weight at the time of peeling was read, divided by the application area of the sealant epoxy adhesive, and the weight per unit area was taken as the adhesion strength. Moreover, after performing a PCT (pressure cooker) test under the conditions of 121° C., 100% RH, 2 atm, and 5 hours, the same adhesion strength test was performed to obtain the adhesion strength before and after PCT. The adhesion strength of each composition is shown as a relative value when the adhesion strength of the comparative test sample before and after PCT is 100. Before and after PCT, 70 or more was evaluated as ◯.

<Evaluation of volume resistivity>
Each of the photosensitive resin compositions obtained above was applied onto a 125 mm×125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking would be 3.0 μm, and at 90° C. Prebaked for 1 minute. Then, after hot-post-baking at 230° C. for 180 minutes using a hot air drier, the volume resistivity at an applied voltage of 1 V to 10 V was measured using an electrometer (“6517A type” manufactured by Keithley). The measurement was performed under the condition that the voltage was held for 60 seconds at each applied voltage in 1 V steps, and Table 2 shows the volume resistivity when 1 V is applied and when 10 V is applied.

When the photosensitive resin compositions for light-shielding films of Examples 1 to 4 are used, the line width tends to be slightly thicker at BT+20 seconds and the development time needs to be slightly longer, but sufficient photopatterning property is obtained. And has a volume resistivity of 1×10 ¹³ Ω·cm at an applied voltage of 10 V at an OD of 3.8/μm, and has a required volume resistivity of 1×10 ¹² Ω·cm or more. You can see that it can be realized. Among them, particularly in Example 4, the volume resistance was maintained at 1×10 ¹³ Ω·cm even at an OD of 4.0/μm in which the light-shielding degree was increased, and high light-shielding and high resistance can be achieved, and the adhesion strength with the glass substrate was high. It can be seen that (seal adhesion) is also high. These effects are obtained by co-dispersing the unsaturated group-containing alkali-soluble resin in the carbon black dispersion, and the effect of improving development adhesion and the like was obtained, and the dye-coated carbon black suitable for high resistance and high seal adhesion was obtained. It was found that the characteristics of can be fully expressed.

On the other hand, in Comparative Example 1, the volume resistivity can be secured at 1×10 ¹² Ω·cm or more when 1 V is applied, but the volume resistivity decreases to less than 1×10 ¹² Ω·cm when 10 V is applied. It can be seen that the characteristics required for high light-shielding and high resistance such as color filter applications of current liquid crystal displays cannot be satisfied.

Claims (8)

The following (A) to (E) components,
(A) A polymerizable unsaturated group-containing alkali-soluble resin obtained by further reacting a reaction product of a compound represented by the following general formula (I) and (meth)acrylic acid with a polyvalent carboxylic acid or an anhydride thereof. ,
(B) a photopolymerizable monomer having at least one ethylenically unsaturated bond,
(C) a photopolymerization initiator,
In a photosensitive resin composition for a light-shielding film, which comprises (D) one or more light-shielding components selected from the group consisting of black organic pigments, mixed-color organic pigments and light-shielding materials, and (E) a solvent,
(A) component is a polycarboxylic acid or its anhydride (a) dicarboxylic acid or tricarboxylic acid or its acid anhydride, and (b) tetracarboxylic acid or its acid dianhydride, (a) / ( a polymerizable unsaturated group-containing alkali-soluble resin having an acid value of 80 to 120 mgKOH/g, which is obtained by reacting b) in a molar ratio of 0.02 to less than 0.1. A photosensitive resin composition for a light-shielding film, which is characterized by being present.

However, in the general formula (I), R ₁ and R ₂ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and X represents a fluorene-9,9-diyl group, n shows average value 0-10. The mass ratio (A)/(B) of the (A) component and the (B) component is 50/50 to 90/10, and (C) is (C) for 100 parts by mass of the total of the (A) component and the (B) component. ) Component in an amount of 2 to 30 parts by mass, and the component (D) is included in an amount of 40 to 70% by mass in a solid content including a component which becomes a solid content by photocuring of the photosensitive resin composition for a light shielding film. The photosensitive resin composition for a light-shielding film according to claim 1. The photosensitive resin composition for a light-shielding film according to claim 1 or 2, wherein the light-shielding component (D) is carbon black. The composition is used for forming a coating film having a volume resistivity of 1×10 ¹² Ω·cm or more when a voltage of 10 V is applied when the optical density OD is 3.5/μm or more and less than 4.0/μm. 4. The photosensitive resin composition for a light shielding film according to any one of 3 to 3. The method according to any one of claims 1 to 3, which is used to form a coating film having an optical density OD of 4.0/μm or more and a volume resistivity of 1×10 ¹¹ Ω·cm or more when a voltage of 10 V is applied. The photosensitive resin composition for a light-shielding film as described above. A light-shielding film, which is formed by curing the photosensitive resin composition for a light-shielding film according to claim 1. A photosensitive resin composition for a light-shielding film according to any one of claims 1 to 5 was applied onto a transparent substrate, prebaked, exposed by an ultraviolet exposure device, developed with an alkaline aqueous solution, and postbaked. A color filter having a light-shielding film. The following (A) to (F) components,
(A) A polymerizable unsaturated group-containing alkali-soluble resin obtained by further reacting a reaction product of a compound represented by the following general formula (I) and (meth)acrylic acid with a polyvalent carboxylic acid or an anhydride thereof. ,
(B) a photopolymerizable monomer having at least one ethylenically unsaturated bond,
(C) a photopolymerization initiator,
(D) one or more light-shielding components selected from the group consisting of black organic pigments, mixed-color organic pigments and light-shielding materials,
A method for producing a photosensitive resin composition for a light-shielding film, which comprises (E) a solvent and (F) a dispersant as essential components,
The component (A) contains (a) a dicarboxylic acid or a tricarboxylic acid or an acid anhydride thereof as the polyvalent carboxylic acid or an anhydride thereof, and (b) a tetracarboxylic acid or an acid dianhydride thereof (a)/ A polymerizable unsaturated group-containing alkali-soluble resin obtained by reacting (b) in a molar ratio of 0.02 or more and less than 0.1 and having an acid value of 80 to 120 mgKOH/g. And
The component (D) is previously dispersed in a part of the component (E) together with a part of the component (A) and a dispersant (F), and then the remaining components (A), (B), and (C). A method for producing a photosensitive resin composition for a light-shielding film, which comprises mixing the component and the remaining component (E).

However, in the general formula (I), R ₁ and R ₂ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and X represents a fluorene-9,9-diyl group, n shows average value 0-10.