JP7227939B2 - Light-shielding film photosensitive resin composition, light-shielding film and color filter obtained by curing the same - Google Patents

Description

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

A color liquid crystal display device is composed of a liquid crystal portion that controls the amount of light transmission or reflection and a color filter. A method is used in which a black matrix is formed, and then different hues of red, green, and blue are sequentially formed in a color pattern such as stripes or mosaics.

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. Color filters are one of the important components that affect the visibility of color liquid crystal display devices. It is necessary to improve the color purity of pixels such as G) and blue (B) to a higher degree than ever before, and to achieve a high degree of light shielding in the black matrix. A large amount must be added.

In addition, in liquid crystal display devices, improvements are actively being made to improve characteristics such as viewing angle, contrast, and response speed. The required properties such as adhesion and insulation are becoming stricter.

Incidentally, carbon black is generally known as a light-shielding material (black color material) for a resin black matrix. However, since carbon black has low electric resistance, it may cause malfunction of the display device. In an in-plane switching (IPS) liquid crystal display device, which provides a particularly wide viewing angle, an electric field is applied in the in-plane direction of the liquid crystal layer. 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 (see Patent Document 1) has been applied. is increased, there is a limit to the degree of light shielding that can be achieved while maintaining sufficient photopatternability, and it has become difficult to achieve the required level of high light shielding and high resistance. Therefore, a technique using titanium black as a light-shielding material, which can achieve relatively high resistance and high light-shielding properties (see Patent Document 2), has been developed, but there is concern that photo-patternability and storage stability will be insufficient.

Black matrices currently in use are generally said to have a volume resistivity (applied voltage ^of 1 to 10 V) of 1×10 ¹⁰ Ω·cm or more. · cm volume resistivity is described. However, it is a numerical value measured by applying an alternating current of about several volts, and since the volume resistivity value generally decreases as the applied voltage increases, the volume resistivity value decreases further at an applied voltage of 10 V. It is feared that

Japanese Patent Application Laid-Open No. 2001-207079 JP 2008-260927 A

The present invention has been made in view of the above problems, and its object is to apply a voltage of 10 V to a photosensitive resin composition having an optical density OD of 3.5/μm or more and less than OD 4.0/μm. It maintains a volume resistivity of 1×10 ¹² Ω·cm or more at times, and maintains 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, it has excellent development adhesion even when forming fine lines of, for example, 10 μm or less. An object of the present invention 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 photolithography using the photosensitive resin composition, and further provides a color filter and a touch panel containing 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 By blending a polymerizable unsaturated group-containing alkali-soluble resin having a specific structure and acid value as the polymerizable unsaturated group-containing alkali-soluble resin, a photosensitive resin composition having excellent photopatterning properties can be obtained. , found that it is possible to obtain a light-shielding cured film having excellent properties of high light-shielding and high resistance, and 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、フルオレン-9,9-ジイル基を示し、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 reacting a compound represented by the following general formula (I) with (meth)acrylic acid and further reacting it with a polyvalent carboxylic acid or its anhydride. ,
(B) a photopolymerizable monomer having at least one ethylenically unsaturated bond;
(C) a photoinitiator,
(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 photosensitive resin composition for a light-shielding film, wherein the component (A) is a polymerizable unsaturated group-containing alkali-soluble resin having a weight average molecular weight of 4,000 to 7,000 and an acid value of 80 to 120 mgKOH/g.

However, in 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, X represents a fluorene-9,9-diyl group, n indicates an average value of 0-10.

(2) The present invention also provides that the component (A) comprises (a) a dicarboxylic acid or tricarboxylic acid or an acid anhydride thereof, and (b) a tetracarboxylic acid or an acid dicarboxylic acid thereof as the polycarboxylic acid or its anhydride. The photosensitive resin composition according to (1), which is obtained by reacting an anhydride at a molar ratio of (a)/(b) in the range of 0.1 to 0.5. It is a thing.

(3) In the present invention, the mass ratio (A)/(B) of component (A) and component (B) is 60/40 to 80/20, and the total of component (A) and component (B) 2 to 30 parts by mass of the component (C) per 100 parts by mass, and the solid content including the component where the component (D) becomes a solid content by photocuring of the photosensitive resin composition for a light shielding film 40 to 70% by mass of the photosensitive resin composition for a light-shielding film according to (1).
(4) The present invention also provides the photosensitive resin composition for a light-shielding film according to (1) or (2), wherein (D) the light-shielding component is carbon black.
(5) The present invention also forms 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. The photosensitive resin composition for a light-shielding film according to any one of (1) to (3), which is used for forming a light-shielding film.
(6) The present invention is also 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 ( A photosensitive resin composition for a light shielding film according to any one of 1) to (3).
(7) The present invention also provides a light-shielding film formed by curing the photosensitive resin composition for a light-shielding film according to any one of (1) to (6).
(8) The present invention also provides a method in which the photosensitive resin composition for a light-shielding film according to any one of (1) to (6) is coated on a transparent substrate, pre-baked, exposed with an ultraviolet exposure device, and subjected to an alkaline aqueous solution. A color filter characterized by comprising a light-shielding film produced by development and post-baking.

(9) The present invention also provides 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 photoinitiator,
(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 containing (E) a solvent and (F) a dispersant as essential components,
The component (A) contains (a) a dicarboxylic acid or tricarboxylic acid or an acid anhydride thereof and (b) a tetracarboxylic acid or an acid anhydride thereof as the polyvalent carboxylic acid or anhydride thereof, and (a)/ A polymerizable unsaturated group-containing alkali-soluble resin obtained by reacting (b) at a molar ratio of 0.1 to 0.5 and having an acid value of 80 to 120 mgKOH/g can be,
After previously dispersing the component (D) in part of the component (E) together with a portion of the component (A) and a dispersant (F), the remaining components (A), (B), and (C) A method for producing a photosensitive resin composition for a light-shielding film, characterized by mixing the component and the remaining component (E).

The photosensitive resin composition for a light-shielding film of the present invention is a highly light-shielding film with an OD of about 3.5/μm, and maintains a high resistance such as a volume resistivity of 1×10 ¹² Ω·cm or more even when a voltage of 10 V is applied. is possible, and even when thin lines with a line width of 10 μm, 8 μm, and 6 μm are formed, the development adhesion is excellent, and the adhesion to 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。 The present invention will be described in detail below.
The polymerizable unsaturated group-containing alkali-soluble resin of the component (A) is an epoxy compound represented by the general formula (I), (meth)acrylic acid (which means "acrylic acid and / or methacrylic acid" ), and the obtained compound having a hydroxy group is reacted with (a) a dicarboxylic acid or tricarboxylic acid or its acid anhydride, and (b) a tetracarboxylic acid or its acid dianhydride to obtain an epoxy (meta ) is an acrylate acid adduct. The epoxy compound represented by formula (I) means an epoxy compound obtained by reacting a bisphenol with epihalohydrin or an equivalent thereof. Since component (A) has both a polymerizable unsaturated double bond and a carboxyl group, it imparts excellent photocurability, good developability, and patterning properties to the photosensitive resin composition, and improves the physical properties of the light-shielding film.

However, in 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 -, -C ( _CF3 ) _2- , -Si( _CH3 ) _2- , _-CH2- , -C( _CH3 ) _2- , -O-, or fluorene-9,9-diyl group or absent; n is an average value of 0-10.

Bisphenols that give the epoxy compound of 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 general formula (I) is a fluorene-9,9-diyl group can be particularly preferably used.

The compound of general formula (I) for deriving the alkali-soluble resin (A) is an epoxy compound having two glycidyl ether groups obtained by reacting the above bisphenols with epichlorohydrin. This reaction generally involves oligomerization of a diglycidyl ether compound, and n usually has a plurality of values, so the average value of 0 to 10 (not necessarily an integer) is preferred, but the preferred average value of n is 0-3. If the average value of n exceeds the upper limit, when the composition is made into a photosensitive resin composition using the alkali-soluble resin synthesized using the epoxy compound, the viscosity of the composition becomes too large, and the coating becomes difficult. In other words, sufficient alkali solubility cannot be imparted, and the alkali developability is very poor.

Next, the compound of general formula (I) is reacted with, for example, 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 , (a) a dicarboxylic or tricarboxylic acid or anhydride thereof, and (b) a tetracarboxylic acid or anhydride thereof. At that time, the reaction is carried out in a range where the molar ratio of (a)/(b) is 0.01 to 0.5. This reaction yields a polymerizable unsaturated group-containing alkali-soluble resin having the structure of an epoxy (meth)acrylate acid adduct.

As the (a) dicarboxylic acid or tricarboxylic acid or its acid anhydride used for the epoxy (meth)acrylate acid adduct, a chain hydrocarbon dicarboxylic acid or tricarboxylic acid or its acid anhydride or an alicyclic dicarboxylic acid or tricarboxylic acid Acids or their anhydrides, aromatic dicarboxylic or tricarboxylic acids or their anhydrides are used. Examples of chain hydrocarbon dicarboxylic acids or tricarboxylic acids or acid anhydrides thereof include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citralalic acid, malonic acid, glutaric acid, There are compounds such as citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, and dicarboxylic or tricarboxylic acids or acid anhydrides thereof into which optional substituents are introduced. Examples of alicyclic dicarboxylic acids or tricarboxylic acids or acid anhydrides thereof include compounds such as cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and norbornanedicarboxylic acid. It may be a dicarboxylic acid or tricarboxylic acid or an acid anhydride thereof into which a substituent of is introduced. Furthermore, aromatic dicarboxylic acids or tricarboxylic acids or acid anhydrides thereof include compounds such as phthalic acid, isophthalic acid, and trimellitic acid, and dicarboxylic acids or tricarboxylic acids into which optional substituents have been introduced, or their It may be an acid anhydride.

In addition, as the (b) tetracarboxylic acid or its acid dianhydride used for the epoxy (meth)acrylate acid adduct, a chain hydrocarbon tetracarboxylic acid or its acid dianhydride, an alicyclic tetracarboxylic acid or Its dianhydride, or an aromatic polycarboxylic acid or its dianhydride is used. Examples of chain hydrocarbon tetracarboxylic acids or acid dianhydrides thereof include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid and the like. It may be a carboxylic acid or its dianhydride. Examples of alicyclic tetracarboxylic acids or acid dianhydrides thereof include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, and norbornanetetracarboxylic acid. Further, it may be a tetracarboxylic acid or an acid dianhydride thereof into which an arbitrary substituent has been introduced. Furthermore, aromatic tetracarboxylic acids and acid dianhydrides thereof include, for example, pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, biphenylethertetracarboxylic acid and acid dianhydrides thereof. It may be a tetracarboxylic acid or an acid dianhydride thereof into which a substituent of is introduced.

The molar ratio (a)/(b) of (a) dicarboxylic acid or tricarboxylic acid or anhydride thereof and (b) tetracarboxylic acid or dianhydride thereof used in the epoxy (meth)acrylate acid adduct is , is 0.01 to 0.5 as described above, preferably 0.02 or more and less than 0.1. If the molar ratio (a)/(b) deviates from the above range, it is not possible to obtain the optimum molecular weight for obtaining the photosensitive resin composition of the present invention having high light blocking and high resistance and good photopatternability. Therefore, it is not preferable. There is a tendency that 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 through the above-described steps by known methods such as those described in JP-A-8-278629 and JP-A-2008-9401. First, as a method of reacting (meth)acrylic acid with the epoxy compound of general formula (I), for example, (meth)acrylic acid is added to a solvent in an amount equimolar with the epoxy group of the epoxy compound, and a catalyst (triethylbenzyl ammonium chloride, 2,6-diisobutylphenol, etc.), heating to 90 to 120.degree. Next, as a method for reacting the acid anhydride with the hydroxyl group of the epoxy acrylate compound that is the reaction product, a predetermined amount of the epoxy acrylate compound and the acid dianhydride and the acid dianhydride are added to a solvent, and a catalyst (odor tetraethylammonium chloride, triphenylphosphine, etc.), heating and stirring at 90 to 130° C. for reaction.

The weight average molecular weight (Mw) of the polymerizable unsaturated group-containing alkali-soluble resin (A) is preferably in the range of 4,000 to 20,000, more preferably in the range of 4,500 to 7,000. 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. ) exceeds 20,000, development residues and residual films in unexposed areas tend to remain when a highly light-shielding photosensitive resin composition is formed. Furthermore, (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 alkali development of the photosensitive resin composition using (A), and if it exceeds 120 mgKOH/g, a highly light-shielding photosensitive resin composition using (A). Both are undesirable because the penetration of the alkaline developer into the film becomes too fast and peeling development occurs. The polymerizable unsaturated group-containing alkali-soluble resin (A) may be used alone or as a mixture of two or more thereof.

(B) Photopolymerizable monomers having at least one ethylenically unsaturated bond include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxyhexyl (meth) ) (Meth) acrylic 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, 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 (Meth)acrylic acid esters such as alkylene oxide-modified hexa(meth)acrylate and caprolactone-modified dipentaerythritol hexa(meth)acrylate can be mentioned, and one or more of these can be used. In addition, (B) the photopolymerizable monomer having at least one ethylenically unsaturated bond does not have a free carboxyl group.

The blending ratio of these components (A) and (B) is preferably 50/50 to 90/10, preferably 60/40 to 80/20 in mass ratio (A)/(B). is good. If the blending ratio of component (A) is less than 50/50 (A)/(B), the cured product after photocuring becomes brittle, and the acid value of the coating film is low in the unexposed areas, resulting in alkali development. Solubility in liquids is lowered, and pattern edges become rough and unsharp. In addition, the acid value of the resin component is too high, and the solubility in the alkaline developer in the exposed area increases, so that the formed pattern becomes narrower than the target line width. There is a risk that problems such as pattern dropouts or easy pattern dropouts may occur.

Examples of photopolymerization initiators for component (C) include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and p-tert-butyl. Acetophenones such as acetophenone, benzophenones such as benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone, benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2- (o-Chlorophenyl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-4,5-diphenyl Biimidazole compounds such as biimidazole, 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole, 2-trichloromethyl-5-styryl-1,3 ,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4 -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-triazines 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 O-acyloxime compounds such as -methylsulfanylphenyl)butan-1-one oxime-O-acetate, benzyldimethylketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxane Sulfur compounds such as sodium chloride, 2-isopropylthioxanthone, anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutylnitrile, benzoyl peroxide, cumene Examples include organic peroxides such as peroxides, thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole. Among these, O-acyloxime compounds are preferably used from the viewpoint of easily obtaining a highly sensitive photosensitive resin composition for a light shielding film. Two or more kinds of these photopolymerization initiators can also be used. In addition, the photoinitiator as used in the field of this invention is used in the meaning containing a sensitizer.

These photopolymerization initiators and sensitizers can be used alone or in combination of two or more. Also, a compound that does not act as a photopolymerization initiator or sensitizer by itself but can be used in combination to increase the ability of the photopolymerization initiator or 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 used as component (C) is preferably 2 to 30 parts by mass, preferably 5 to 25 parts by mass based on 100 parts by mass of components (A) and (B) combined. It is good to have When the blending ratio of component (C) is less than 2 parts by mass, the speed of photopolymerization slows down, resulting in a decrease in sensitivity. The width becomes thicker than the pattern mask, which may cause problems such as the line width being unable to be faithfully reproduced with respect to the mask, or the pattern edge being jagged and not sharp.

Component (D) is a light-shielding component selected from black organic pigments, mixed-color organic pigments, and light-shielding materials, and preferably has excellent heat resistance, light resistance, and solvent resistance. Examples of black organic pigments include perylene black, aniline black, and cyanine black. Examples of mixed-color organic pigments include pseudo-black pigments obtained by mixing two or more pigments selected from red, blue, green, purple, yellow, cyanine, magenta, and the like. Examples of the light shielding material include carbon black, chromium oxide, iron oxide, and titanium black. Although two or more kinds of light-shielding components can be appropriately selected and used, carbon black is particularly preferred because of its light-shielding properties, surface smoothness, dispersion stability, and compatibility with resins. Furthermore, when carbon black is used to increase the resistance of the light-shielding film, surface-coated carbon black obtained by coating the surface of the carbon black with a dye, pigment, resin, or the like may be used.

Examples of solvents for 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. , N-methyl-2-pyrrolidone and other ketones, toluene, xylene, tetramethylbenzene and other aromatic hydrocarbons, 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, ethyl acetate, butyl acetate, cellosolve Acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and other acetic acid esters, etc., and dissolution using these , can be mixed to form a uniform solution-like composition.

These light-shielding components are preferably dispersed in advance in a solvent together with the (F) dispersant to obtain a light-shielding dispersion liquid, and then blended as a photosensitive resin composition for a light-shielding film. Here, since the solvent to be dispersed is part of the component (E), it can be used as long as it is listed as the component (E) above. Examples include propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate. etc. are preferably used. The mixing ratio of the light-shielding component (D) that forms 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 weight is particularly preferred. If it is less than 40% by mass, the light-shielding properties are not sufficient for high light-shielding applications. If the amount exceeds 70% by mass, the content of the photosensitive resin, which is the original binder, is reduced, resulting in unfavorable problems such as impairing the developing properties and impairing the film-forming ability.

In the light-shielding dispersion, (F) a dispersant is used in order to stably disperse the light-shielding component. For this purpose, known dispersants such as various polymer dispersants can be used. . Examples of the dispersant include known compounds conventionally used for dispersing pigments (compounds commercially available under the names of dispersants, dispersion wetting agents, dispersion accelerators, etc.) can be used without particular limitation. , for example, cationic polymeric dispersants, anionic polymeric dispersants, nonionic polymeric dispersants, pigment derivative dispersants (dispersion aids), and the like. In particular, it has a cationic functional group such as an imidazolyl group, pyrrolyl group, pyridyl group, primary, secondary or tertiary amino group as an adsorption point to the pigment, and has an amine value of 1 to 100 mgKOH/g and a number average molecular weight. A cationic polymeric dispersant having a is in the range of 1,000 to 100,000 is preferred. The content of the dispersant is 1 to 30% by weight, preferably 2 to 25% by weight, based on the light-shielding component.

Furthermore, when preparing the light-shielding dispersion, a part of the polymerizable unsaturated group-containing alkali-soluble resin of the component (A) is co-dispersed in addition to the dispersant, thereby obtaining a photosensitive resin composition for light-shielding films. , the exposure sensitivity can be easily maintained at a high level, and a photosensitive resin composition can be obtained which has good adhesion during development and is less likely to cause the problem of residue. The blending amount of component (A) is preferably 2 to 20% by mass, more preferably 5 to 15% by mass in the light-shielding dispersion. If the amount of component (A) is less than 2% by mass, the effects of co-dispersion such as improved sensitivity, improved adhesion, and reduced residue cannot be obtained. On the other hand, when the content is 20% by mass or more, the viscosity of the light-shielding dispersion liquid is high, especially when the content of the light-shielding material is large, and it is difficult or takes an extremely long time to uniformly disperse the liquid, resulting in high resistance. It becomes difficult to obtain a photosensitive resin composition for obtaining a coating film. Then, the obtained light-shielding dispersion is mixed with the remaining components (A), (B), (C), and the remaining (E) to form a light-shielding film photosensitive resin composition. can do.

In addition, the photosensitive resin composition of the present invention may optionally contain curing accelerators, thermal polymerization inhibitors, plasticizers, fillers, solvents, leveling agents, antifoaming agents, coupling agents, surfactants, and the like. Additives can be added. Examples of thermal polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, and phenothiazine. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like. Examples of the material include glass fiber, silica, mica, and alumina. Examples of the antifoaming agent and leveling agent include silicone-, fluorine-, and acrylic-based compounds. Examples of surfactants include fluorine-based surfactants and silicone-based surfactants. Examples of coupling agents include 3-(glycidyloxy)propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, Silane coupling agents such as 3-ureidopropyltriethoxysilane can be mentioned.

The photosensitive resin composition of the present invention contains the above components (A) to (E) as main components. It is desired that the total amount of components (A) to (D) is 80% by mass, preferably 90% by mass or more, in the solid content excluding the solvent (the solid content includes monomers that become solid content after curing). (E) The amount of the solvent varies depending on the target viscosity, but it is preferable that the amount is in the range of 70 to 90% by weight in the photosensitive resin composition.

The photosensitive resin composition for a light-shielding film in the present invention is excellent as, for example, a photosensitive resin composition for forming a color filter light-shielding film, and the method for forming the light-shielding film includes the following photolithography methods. First, a photosensitive resin composition is applied onto a transparent substrate, then the solvent is dried (pre-baking), a photomask is placed on the film thus obtained, and ultraviolet rays are irradiated to expose the exposed area. A method of curing, further performing development using an alkaline aqueous solution to elute the unexposed portions to form a pattern, and further performing post-baking (thermal baking) as post-drying can be used.

Examples of the transparent substrate to which the photosensitive resin composition is applied include glass substrates, transparent films (for example, polycarbonate, polyethylene terephthalate, polyethersulfone, etc.) on which transparent electrodes such as ITO and gold are vapor-deposited or patterned. can be exemplified. As a method for applying the solution of the photosensitive resin composition onto the transparent substrate, any method such as a method using a roller coater, a land coater, a slit coater or a spinner, in addition to a known solution dipping method, a spray method, etc. can be used. methods can also be employed. By these methods, a film is formed by applying a desired thickness and then removing the solvent (pre-baking). Pre-baking is performed by heating with an oven, hot plate, or the like. The heating temperature and heating time in prebaking are appropriately selected according to the solvent used, and the prebaking is performed at a temperature of 60 to 110° C. for 1 to 3 minutes, for example.

The exposure performed after prebaking is performed by an ultraviolet exposure device, and by exposing through a photomask, only the portions of the resist corresponding to the pattern are exposed. The exposure apparatus and its exposure irradiation conditions are appropriately selected, and exposure is performed using a light source such as an ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and a deep ultraviolet lamp to photocure the photosensitive resin composition in the coating film.

Alkaline development after exposure is performed for the purpose of removing the resist from the unexposed portions, and a desired pattern is formed by this development. Examples of the developer suitable for this alkaline development include aqueous solutions of carbonates of alkali metals and alkaline earth metals, and aqueous solutions of hydroxides of alkali metals, particularly sodium carbonate, potassium carbonate and lithium carbonate. It is preferable to develop at a temperature of 23 to 28° C. using a weakly alkaline aqueous solution containing 0.05 to 3% by mass of carbonate such as, and fine images are formed using a commercially available developing machine, an ultrasonic cleaner, or the like. It can be formed precisely.

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

As described above, the photosensitive resin composition of the present invention is suitable for forming fine patterns by operations such as exposure and alkali development. In addition, 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 color filters used in liquid crystal display devices or imaging devices. 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 touch panels, and the like.

The high light shielding and high resistance light shielding film obtained by the present invention has a volume resistivity of 1×10 ¹² Ω·cm or more at an applied voltage of 10 V when the OD is 3.5/μm or more and less than OD4.0/μm. It will be. Also, 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·cm at an applied voltage of 10 V. cm or more can be secured. Furthermore, the pattern formed using the photosensitive resin composition of the present invention is resistant to heat sagging during post-baking, maintains a rectangular cross-sectional shape of the pattern, and has a light-shielding shape in which the side surface of the pattern is perpendicular to the substrate. Suitable for forming film patterns.

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

First, a synthesis example of the (A) polymerizable unsaturated group-containing alkali-soluble resin of the present invention is shown. Evaluation of resins in Synthesis Examples 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)], heated at 160° C. for 2 hours, and weighed [W ₂ ( g)] from the following formula.
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 [manufactured by Hiranuma Sangyo Co., Ltd., trade name COM-1600].

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

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. A compound of 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]
244.3 g (0.50 mol) of BPFE, 72.1 g (1.0 mol) of acrylic acid, 0.45 g of TPP, and 334 g of PGMEA were placed in a 1 L four-necked flask equipped with a reflux condenser, and heated at 100-105°C for 12 hours. Stirred to obtain a reaction product.

Next, 94.15 g (0.32 mol) of BPDA and 22.82 g (0.15 mol) of THPA were added to the resulting reaction product, stirred for 6 hours under heating at 115 to 120 ° C., and the polymerizable unsaturated group-containing alkali-soluble resin solution ( A)-1 was obtained. The resulting resin solution had a solid content concentration of 56.5 wt %, an acid value (in terms of solid content) of 102 mgKOH/g, and an Mw of 5,200 by GPC analysis.

[Synthesis Example 2]
244.3 g (0.50 mol) of BPFE, 72.1 g (1.0 mol) of acrylic acid, 0.45 g of TPP, and 318 g of PGMEA were placed in a 1 L four-necked flask equipped with a reflux condenser, and heated at 100-105°C for 12 hours. Stirred to obtain a reaction product.

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

[Synthesis Example 3]
219.9 g (0.45 mol) of BPFE, 64.9 g (0.9 mol) of acrylic acid, 0.45 g of TPP, and 294 g of PGMEA were placed in a 1 L four-neck flask equipped with a reflux condenser, and heated at 100-105°C for 12 hours. Stirred to obtain a reaction product.

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

[Comparative Synthesis Example 1]
244.3 g (0.50 mol) of BPFE, 72.1 g (1.0 mol) of acrylic acid, 0.45 g of TPP, and 329 g of PGMEA were placed in a 1 L four-necked flask equipped with a reflux condenser, and heated at 100-105°C for 12 hours. Stirred to obtain a reaction product.

Next, 73.56 g (0.25 mol) of BPDA and 38.03 g (0.25 mol) of THPA were added to the resulting reaction product, stirred for 6 hours under heating at 115 to 120 ° C., and the polymerizable unsaturated group-containing alkali-soluble resin solution ( A)-4 was obtained. The resulting resin solution had a solid content concentration of 56.5 wt %, an acid value (in terms of solid content) of 70 mgKOH/g, and an Mw of 3600 by GPC analysis.

[Preparation Example 1] Preparation of dye-coated carbon black 10 L of slurry was prepared by mixing 1000 g of carbon black with water, stirred at 95°C for 1 hour, allowed to cool, and then washed with water. This was again mixed with water 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. After standing to cool and washing with water, the slurry was mixed with water again to prepare 10 L of slurry, 769.2 g of 13% sodium hypochlorite aqueous solution was added, and the mixture was stirred at 40° C. for 6 hours. After allowing to cool and washing with water, 10 L of slurry is prepared by mixing with water again, 38.1 g of a dye (Direct Deep BLACK) with a purity of 38.4% is added and stirred at 40 ° C. for 1 hour, and then further 10.1 g of aluminum sulfate was added and stirred at 40° C. for 1 hour. This was allowed to cool, washed with water, filtered and dried to obtain 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 a photosensitive resin composition for light shielding films and cured products thereof, but the present invention is not limited to these. Here, the raw materials and abbreviations used in the production of the photosensitive resin compositions for light-shielding films and their cured products in the following Examples and Comparative Examples are as follows.

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

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

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

(Light-shielding dispersion pigment)
(D)-1: Propylene glycol monomethyl ether acetate dispersion with 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 the urethane-based dispersant, 146.0 g of the alkali-soluble resin solution obtained in Synthesis Example 2, and propylene glycol monomethyl ether 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 BYK-Chemie)

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

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

<Evaluation of development characteristics (pattern line width/pattern linearity)>
Each of the photosensitive resin compositions obtained above was applied to a 125 mm × 125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking was 1.1 µm, and the coating was performed at 90°C. Pre-baked for 1 minute. After that, the exposure gap was adjusted to 100 μm, a 10 μm or 6 μm negative photomask was placed on the dried coating film, and 80 mJ/cm ² ultraviolet rays were irradiated from an ultra-high pressure mercury lamp with an i-line illuminance of 30 mW/cm ² , A photo-curing reaction of the photosensitive area was performed.

Next, the exposed coated plate was placed in an aqueous 0.05% potassium hydroxide solution at 25° C. under a shower development pressure of 1 kgf/cm ² . After developing for 2 seconds, the film was washed with water spray at a pressure of 5 kgf/cm ² to remove the unexposed areas of the coating film to form a pixel pattern on the glass substrate. 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. If the pattern image did not appear even after the development time of 80 seconds, it was determined that the development was not possible. In addition, each evaluation method is as follows.

Pattern line width: Pattern line widths with mask widths of 10 µm and 6 µm were measured using a length measuring microscope ("XD-20" manufactured by Nikon Corporation).
Pattern linearity: A 10 μm or 6 μm mask pattern after post-baking is observed under a microscope, and when peeling from the substrate or burrs at the pattern edge portion is not observed, ◯ is observed, Δ is observed partially, and is observed over the entire surface. A thing was evaluated as x.

<Evaluation of OD/μm>
Each of the photosensitive resin compositions obtained above was applied to a 125 mm × 125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking was 1.1 µm, and the coating was performed at 90°C. Pre-baked for 1 minute. Thereafter, without covering with a negative type photomask, ultraviolet rays of 80 mJ/cm ² were irradiated from an ultra-high pressure mercury lamp with an i-line illuminance of 30 mW/cm ² to carry out a photo-curing reaction of the exposed portion.

Next, the exposed coated plate was developed in a 0.05% potassium hydroxide aqueous solution at 25° C. under a shower development pressure of 1 kgf/cm ² for 60 seconds, then spray washed with water at a pressure of 5 kgf/cm ² . After heat post-baking at 230° C. for 30 minutes using a hot air dryer, the OD of the light-irradiated portion was evaluated using a Macbeth transmission densitometer. Furthermore, the film thickness of the light-irradiated 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 coated on a 125 mm × 125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking was 1.1 µm. Prebaked for 1 minute. Then, without using a photomask, the film was solidly exposed at 80 mJ/cm ² with an ultra-high pressure mercury lamp with an i-line illuminance of 30 mW/cm ² , and thermal post-baked at 230° C. for 30 minutes using a hot air dryer. Then, the post-baked substrate obtained above was evaluated for adhesion strength to the glass substrate by an evaluation method according to the three-point bending adhesion test method of JIS K6856-1994 as follows. The post-baked substrate with coating film and the glass substrate (Corning 1737) not coated with the resin composition (substrate without coating film) were each cut into strips of 20 mm x 63 mm to prepare test pieces. A post-baked substrate with a coating film and a substrate without a coating film were pasted together with a certain amount of sealant epoxy adhesive so that the overlap width was 8 mm. The shape of the sealant epoxy adhesive when superimposed is circular and the diameter is about 5 mm. Thereafter, the superimposed test piece was prebaked at 90° C. for 20 minutes and then post-baked at 150° C. for 2 hours to prepare a three-point bending test piece. Furthermore, a sample for comparison test was also prepared by bonding 20 mm x 63 mm non-coated substrate test pieces together in the same manner as above.

In the test piece obtained above, a substrate with a coating film and a substrate without a coating film, or a sample for comparison test is supported by two supports so that the overlapping part is in the center (two supports The gap was 3 cm), and a weight was applied from directly above the overlapped portion to directly below using UCT-100 (trade name, manufactured by ORIENTEC) at a rate of 1 mm/min to separate the laminated portion. Here, the load at the time of peeling was read, divided by the applied area of the sealant epoxy adhesive, and the load per unit area was defined as the adhesion strength. Also, after a PCT (pressure cooker) test was conducted under the conditions of 121° C., 100% RH, 2 atm, and 5 hours, a similar adhesion strength test was conducted to determine 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 sample for comparison test before and after PCT is set to 100, respectively. A score of 70 or more before and after PCT was evaluated as ◯.

<Evaluation of Volume Resistivity>
Each of the photosensitive resin compositions obtained above was coated on a 125 mm × 125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking was 3.0 µm, and the coating was carried out at 90°C. Pre-baked for 1 minute. Then, after thermal post-baking at 230° C. for 180 minutes using a hot air dryer, the volume resistivity was measured at an applied voltage of 1 V to 10 V using an electrometer (manufactured by Keithley, Model 6517A). Table 2 shows the volume resistivity when 1 V was applied and when 10 V was applied.

When the photosensitive resin compositions for light-shielding films of Examples 1 to 4 were used, the line width tended to be slightly thicker at BT+20 seconds, and the development time needed to be slightly longer, but sufficient photopatternability was 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. I know it can be done. Especially in Example 4, the volume resistance is maintained at 1×10 ¹³ Ω·cm even at an OD of 4.0/μm where the light shielding degree is increased, and high light shielding and high resistance is possible, and adhesion strength with the glass substrate is also possible. (seal adhesion) is also high. These effects are obtained by co-dispersing the unsaturated group-containing alkali-soluble resin in the carbon black dispersion, which has the effect of improving development adhesion, etc., and dye-coated carbon black suitable for high resistance and high sealing adhesion. It was found that the characteristics of can be sufficiently expressed.

On the other hand, in Comparative Example 1, a volume resistivity of 1×10 ¹² Ω·cm or more can be secured when 1 V is applied, but the volume resistivity drops below 1×10 ¹² Ω·cm when 10 V is applied. , it can be seen that the required characteristics of high light shielding and high resistance for color filters of current liquid crystal displays cannot be satisfied.

Claims (6)

the following (A) ~ (E) components,
(A) A polymerizable unsaturated group-containing alkali-soluble resin obtained by reacting a compound represented by the following general formula (I) with (meth)acrylic acid and further reacting it with a polyvalent carboxylic acid or its anhydride. ,
(B) a photopolymerizable monomer having at least one ethylenically unsaturated bond;
(C) a photoinitiator,
(D) one or more light-shielding components selected from the group consisting of black organic pigments, mixed-color organic pigments, and light-shielding materials;
The component (A) contains (a) a dicarboxylic acid or tricarboxylic acid or an acid anhydride thereof, and (b) a tetracarboxylic acid or an acid anhydride thereof as a polyvalent carboxylic acid or anhydride thereof, and (a)/( b) obtained by reacting at a molar ratio of 0.01 to 0.5, having a weight average molecular weight of 4000 to 7000 and an acid value of 80 to 120 mgKOH/g. A group-containing alkali-soluble resin,
The mass ratio (A)/(B) of the component (A) and the component (B) is 60/40 to 80/20, and the total of the component (A) and the component (B) is 100 parts by mass. Containing 2 to 30 parts by mass of the component (C),
The component (D) is contained in an amount of 40 to 70% by mass in the solid content including the component that becomes a solid content by photocuring of the photosensitive resin composition for a light shielding film,
It is characterized by being used to form a coating film having an optical density OD of 3.5/μm or more and less than 4.0/μm and a volume resistivity of 1×10 ¹² Ω·cm or more when a voltage of 10 V is applied. A photosensitive resin composition for a light-shielding film.

However, in 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, X represents a fluorene-9,9-diyl group, n indicates an average value of 0-10. the following (A) ~ (E) components,
(A) A polymerizable unsaturated group-containing alkali-soluble resin obtained by reacting a compound represented by the following general formula (I) with (meth)acrylic acid and further reacting it with a polyvalent carboxylic acid or its anhydride. ,
(B) a photopolymerizable monomer having at least one ethylenically unsaturated bond;
(C) a photoinitiator,
(D) one or more light-shielding components selected from the group consisting of black organic pigments, mixed-color organic pigments, and light-shielding materials;
The component (A) contains (a) a dicarboxylic acid or tricarboxylic acid or an acid anhydride thereof, and (b) a tetracarboxylic acid or an acid anhydride thereof as a polyvalent carboxylic acid or anhydride thereof, and (a)/( b) obtained by reacting at a molar ratio of 0.01 to 0.5, having a weight average molecular weight of 4000 to 7000 and an acid value of 80 to 120 mgKOH/g. A group-containing alkali-soluble resin,
The mass ratio (A)/(B) of the component (A) and the component (B) is 60/40 to 80/20, and the total of the component (A) and the component (B) is 100 parts by mass. Containing 2 to 30 parts by mass of the component (C),
The component (D) is contained in an amount of 40 to 70% by mass in the solid content including the component that becomes a solid content by photocuring of the photosensitive resin composition for a light shielding film,
A photosensitive material for a light-shielding film, 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. elastic resin composition.

However, in 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, X represents a fluorene-9,9-diyl group, n indicates an average value of 0-10. 3. The photosensitive resin composition for a light-shielding film according to claim 1 , wherein the weight average molecular weight of component (A) is 4,600 to 5,500 . (D) The photosensitive resin composition for a light-shielding film according to any one of claims 1 to 3, wherein the light-shielding component is carbon black. A light-shielding film formed by curing the photosensitive resin composition for a light-shielding film according to any one of claims 1 to 4. The photosensitive resin composition for a light-shielding film according to any one of claims 1 to 5 is coated on a transparent substrate, pre-baked, exposed with an ultraviolet exposure device, developed with an alkaline aqueous solution, and post-baked. A color filter comprising a light shielding film.