TWI686669B - Photosensitive resin composition for light shielding film, light shielding film using the same, and color filter including that film - Google Patents

Abstract

A photosensitive resin composition for obtaining a light shielding film is provided. The light shielding film maintains a high light shielding property and a high electric resistance, has an excellent developing adhesion property even when formed into a fine line and has an excellent adhesion property to a substrate. In addition, a light shielding film formed by photolithography using the photosensitive resin composition, and a color filter containing the light shielding film are provided. The photosensitive resin composition for a light shielding film including (A) a prescribed alkali soluble resin which contains a polymerizable unsaturated group and has an acid value of 80 mgKOH/g to 120 mgKOH/g, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, (D) a light shielding component and (E) a solvent as essential components is provided. The light shielding film obtained by curing the photosensitive resin composition and the color filter containing the light shielding film are also provided.

Description

Photosensitive resin composition for shading film, shading made by hardening Films and color filters

The present invention relates to a photosensitive resin composition for a light-shielding film and a light-shielding film made by curing it, and more particularly to a photosensitive solution for an alkaline aqueous solution-developable light-shielding film suitable for forming a fine light-shielding film on a transparent substrate The resin composition and the light-shielding film obtained by curing it, and the light-shielding film obtained by curing can be suitably used when forming a black matrix of a color filter or the like.

The color liquid crystal display device has a liquid crystal portion and a color filter that control the amount of light transmission or reflection as constituent elements. The method of manufacturing the color filter generally uses the following method: on the surface of a transparent substrate such as glass or plastic sheet A black matrix is formed, and successively different color hues of red, green, and blue are formed with color patterns 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 displays, and color liquid crystal mobile phones. Color filters affect color One of the important components of the visibility of the color liquid crystal display device, in order to improve the visibility, that is, to obtain a clear image, the red (R), green (G), blue (B), etc. constituting the color filter The pixels have higher color purity than before, and high blackout is achieved in the black matrix. Therefore, it is necessary to add a larger amount of coloring agent to the photosensitive resin composition than now.

In addition, the liquid crystal display device is actively improving the viewing angle, contrast, response speed and other characteristics, and the structure of the panel with the color filter is complicated, and the adhesion and insulation of the resin black matrix pattern substrate Requirements such as sex become stricter.

However, the resin black matrix light-shielding material (black color material) is generally known as carbon black, but carbon black has a low resistance, and thus may cause a malfunction of the display device. In particular, in an In Plane Switching (IPS) liquid crystal display device that obtains a wide viewing angle, an electric field is applied in the direction of the liquid crystal plane. Therefore, if the resistance value of the black matrix is low, the electric field cannot be normally applied. Upward chaos is the cause of uneven display.

Therefore, as a method of increasing the resistance of the black matrix using carbon black, a technique of coating resin on the surface of carbon black (refer to Patent Document 1), but if the amount of resin coating is increased in order to increase the resistance, it is sufficient The degree of shading that can be achieved while maintaining the light patternability is limited, making it difficult to achieve the required level of high shading and high resistance. Therefore, a technology using titanium black that can achieve high light shielding with a relatively high resistance as a light shielding material has been developed (refer to Patent Document 2), but there is a concern that the light patternability and storage stability are insufficient.

The black matrix used now generally refers to a volume resistivity (applied voltage of 1V~10V) of 1×10 ¹⁰ Ω. cm or more, described in Patent Document 2 1×10 ¹² Ω. Volume resistivity in cm. Among them, it is a value measured by applying an alternating current of about several V. In general, the larger the applied voltage, the smaller the volume resistivity value. Therefore, there is a concern that the volume resistivity value will be further lowered at an applied voltage of 10V.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2001-207079

[Patent Document 2] Japanese Patent Laid-Open No. 2008-260927

The present invention was made in view of the above problems, and its object is to provide a photosensitive resin composition for a light-shielding film having the following properties: maintaining high light-shielding and high resistance (in the photosensitive resin composition, the optical density OD is 3.5/ μm or more and less than 4.0/μm, maintain a volume resistivity of 1×101 ² Ω·cm or more when a voltage of 10V is applied, and maintain an OD of 4.0/μm or more and maintain a pressure of 1×10 ¹¹ Ω·cm or more when a voltage of 10V is applied Volume resistivity), even when forming fine lines of, for example, 10 μm or less, is excellent in developing adhesion, and can also form fine lines of 8 μm or 6 μm, and can sufficiently ensure the adhesion to the glass substrate. 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 or a touch panel including the cured product.

The inventors of the present invention conducted studies to solve the above-mentioned problems, and as a result, they found that by preparing a polymerizable unsaturated group-containing alkali-soluble resin having a specific structure and acid value as an alkali-soluble resin containing a polymerizable unsaturated group, The polymerizable unsaturated group-containing alkali-soluble resin of the photosensitive resin composition of the photopolymerizable monomer, photopolymerization initiator, light-shielding component, and solvent can be made into a photosensitive resin composition having excellent photopatterning characteristics. The invention can be completed by obtaining a light-shielding cured film excellent in characteristics of high light-shielding and high resistance.

That is, the gist of the present invention is as follows.

(1) The present invention is a photosensitive resin composition for a light-shielding film, which is a photosensitive resin composition for a light-shielding film containing the following components (A) to (E) as essential components: (A) Saturated base-soluble resin obtained by reacting a compound represented by the following general formula (I) with (meth)acrylic acid and a polycarboxylic acid or its anhydride, (B) having at least one ethylene Unsaturated monomer photopolymerizable monomer, (C) 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, and (E ) Solvent; characterized in that (A) component is the polycarboxylic acid or its anhydride (a) dicarboxylic acid or tricarboxylic acid or its anhydride, and (b) tetracarboxylic acid or its acid dianhydride (a)/(b) an alkali-soluble resin containing a polymerizable unsaturated group and having a molar ratio in the range of 0.01 to 0.5 and obtained by reacting, and having an acid value of 80 mgKOH/g to 120 mgKOH/g;

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 -, and -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, or 茀-9,9-diyl or single bond, n represents the average value of 0 ~10.

(2) The present invention is also the photosensitive resin composition for a light-shielding film according to (1), wherein the mass ratio of (A) component to (B) component (A)/(B) is 50/50 to 90/ 10, containing 2 parts by mass to 30 parts by mass of the (C) component relative to 100 parts by mass of the (A) component and (B) component in total, and the inclusion of the photosensitive resin composition for the light-shielding film due to light curing becomes Solid component The solid component contains 40 to 70% by mass of the component (D).

(3) The present invention is also a photosensitive resin composition for a light-shielding film according to (1) or (2), which further contains (F) a dispersant, and makes a part of (D) component and (A) component and ( F) After dispersing the dispersant in a part of the (E) component in advance, it is manufactured by mixing with the remaining (A) component, (B) component, (C) component, and the remaining (E) component.

(4) The present invention is also the photosensitive resin composition for a light-shielding film according to any one of (1) to (3), wherein (D) the light-shielding component is carbon black.

(5) The present invention is also a photosensitive resin composition for a light-shielding film according to any one of (1) to (4), which is used to form when the optical density OD is 3.5/μm or more and less than 4.0/μm , The volume resistivity when a voltage of 10V is applied becomes 1×10 ¹² Ω. Coating film above cm.

(6) The present invention is also a photosensitive resin composition for a light-shielding film according to any one of (1) to (4), which is used to form when a 10 V voltage is applied when the optical density OD is 4.0/μm or more The volume resistivity becomes 1×10 ¹¹ Ω. Coating film above cm.

(7) The present invention is also a light-shielding film characterized by being formed by hardening the photosensitive resin composition for a light-shielding film according to any one of (1) to (6).

(8) The present invention is also a color filter, characterized by comprising a light-shielding film coated with the photosensitive resin composition for a light-shielding film according to any one of (1) to (6) After being prebaked on the transparent substrate, it is exposed by an ultraviolet exposure device, developed by an alkaline aqueous solution, and post-baked.

The photosensitive resin composition for a light-shielding film of the present invention can maintain a volume resistivity of 1×10 ¹² Ω even in a high-light-shielding light-shielding film having an OD of about 3.5/μm even under an applied voltage of 10V. The high resistance of cm or more enables excellent adhesion in development even when thin lines with a line width of 10 μm, further 8 μm, and 6 μm are formed, and the adhesion to the glass substrate can be sufficiently ensured.

Hereinafter, the present invention will be described in detail.

(A) The alkali-soluble resin containing a polymerizable unsaturated group of the component is to react the epoxy compound represented by the general formula (I) with (meth)acrylic acid (which means "acrylic acid and/or methacrylic acid") to make An epoxy (meth)acrylate acid adduct obtained by reacting the obtained compound having a hydroxyl group with (a) a dicarboxylic acid or a tricarboxylic acid or its anhydride, and (b) a tetracarboxylic acid or its acid dianhydride. The epoxy compound represented by the general formula (I) means an epoxy compound obtained by reacting bisphenols and epihalohydrin or an equivalent thereof. (A) The component has both a polymerizable unsaturated double bond and a carboxyl group. Therefore, it can provide the photosensitive resin composition with excellent photocurability, good developability, and patterning characteristics, thereby improving the physical properties of the light-shielding film.

[Chem 2]

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 -, and -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, or, Fu-9,9-diyl or single bond, n is 0~ The average of 10.

Examples of the bisphenols that provide the epoxy compound of the general formula (I) include bis(4-hydroxyphenyl) ketone, bis(4-hydroxy-3,5-dimethylphenyl) ketone, and bis(4-hydroxy- 3,5-dichlorophenyl) ketone, bis(4-hydroxyphenyl) ash, bis(4-hydroxy-3,5-dimethylphenyl) ash, bis(4-hydroxy-3,5-di Chlorophenyl) ash, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dichloro Phenyl) hexafluoropropane, bis(4-hydroxyphenyl) dimethyl silane, bis(4-hydroxy-3,5-dimethylphenyl) dimethyl silane, bis(4-hydroxy-3,5 -Dichlorophenyl)dimethylsilane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy-3,5-dibromo Phenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxyl -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-dimethylbenzene Group) ether, bis(4-hydroxy-3,5-dichlorophenyl) ether, 9,9-bis(4-hydroxyphenyl) stilbene, 9,9-bis(4-hydroxy-3-methylbenzene Radicals) stilbene, 9,9-bis(4-hydroxy-3-chlorophenyl) stilbene, 9,9-bis(4-hydroxy-3-bromophenyl) stilbene, 9,9-bis(4-hydroxy- 3-fluorophenyl) stilbene, 9,9-bis(4-hydroxy-3-methoxyphenyl) stilbene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl) stilbene, 9,9-bis(4-hydroxy-3,5-dichlorophenyl) stilbene, 9,9-bis(4-hydroxy-3,5-dibromophenyl) stilbene, 4,4'-biphenol, 3,3'-biphenol, etc. Among them, bisphenols in which X in the general formula (I) is fluorene-9,9-diyl can be particularly preferably used.

The compound of the general formula (I) used to derive the alkali-soluble resin of (A) is an epoxy compound having two glycidyl ether groups obtained by reacting the bisphenols with epichlorohydrin. In this reaction, generally, as the oligomerization of the diglycidyl ether compound, n usually has a plurality of values mixed together, so the average value is 0 to 10 (not limited to an integer), and the preferred average value of n is 0 ~3. If the average value of n exceeds the upper limit, the viscosity of the composition becomes too large when a photosensitive resin composition using an alkali-soluble resin (the alkali-soluble resin is a resin synthesized using the epoxy compound) is prepared. On the other hand, the coating cannot be applied well, and the alkali solubility cannot be sufficiently imparted, and the alkali developability becomes very poor.

Next, for example, acrylic acid or methacrylic acid, which is an unsaturated group-containing monocarboxylic acid, or both, is reacted with the compound of the general formula (I), and (a) dicarboxylic acid or tricarboxylic acid or its anhydride, and ( b) The tetracarboxylic acid or its acid dianhydride reacts with the reactant having a hydroxyl group thus obtained. At this time, the reaction is performed in a range where the molar ratio of (a)/(b) becomes 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.

As the (a) dicarboxylic acid or tricarboxylic acid or its anhydride used in the epoxy (meth)acrylate acid adduct, chain hydrocarbon dicarboxylic acid or tricarboxylic acid or its anhydride or alicyclic dicarboxylic acid can be used Acid or tricarboxylic acid or its anhydride, aromatic dicarboxylic acid or tricarboxylic acid or its anhydride. Here, the chain hydrocarbon dicarboxylic acid or tricarboxylic acid or its anhydride is, for example, succinic acid, acetyl succinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citracallic acid, malonic acid Compounds such as acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, etc., or dicarboxylic acid or an optional substituent may be further introduced Tricarboxylic acid or its anhydride. Further, for example, alicyclic dicarboxylic acid or tricarboxylic acid or its anhydride includes, for example, cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornane dicarboxylic acid The compound such as carboxylic acid may be a dicarboxylic acid or tricarboxylic acid or an anhydride thereof to which an optional substituent is further introduced. Furthermore, aromatic dicarboxylic acid or tricarboxylic acid or its anhydride, for example, compounds such as phthalic acid, isophthalic acid, trimellitic acid, etc. may be present, or a dicarboxylic acid or an optional substituent may be further introduced Tricarboxylic acid or its anhydride.

Furthermore, as the (b) tetracarboxylic acid or its acid dianhydride used in the epoxy (meth)acrylate acid adduct, a chain hydrocarbon tetracarboxylic acid or its acid dianhydride or an alicyclic tetracarboxylic acid or Its acid dianhydride, or aromatic polycarboxylic acid or its acid dianhydride. Here, the chain hydrocarbon tetracarboxylic acid or its acid dianhydride exists, for example, butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, etc., and may also be a tetracarboxylic acid or a tetracarboxylic acid to which an optional substituent is further introduced. Its acid dianhydride. In addition, for example, alicyclic tetracarboxylic acid or its acid dianhydride includes cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, and norbornane tetracarboxylic acid. It may be a tetracarboxylic acid or an acid dianhydride to which an optional substituent is further introduced. In addition, Examples of the aromatic tetracarboxylic acid or its acid dianhydride include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic acid or its acid dianhydride. Optional tetracarboxylic acid or its acid dianhydride.

Molar ratio of (a) dicarboxylic acid or tricarboxylic acid or its anhydride to (b) tetracarboxylic acid or its acid dianhydride used in epoxy (meth)acrylate acid adduct (a)/( b) As described above, it is 0.01 to 0.5, preferably 0.02 or more and less than 0.1. If the molar ratio (a)/(b) deviates from the above range, the most suitable molecular weight of the photosensitive resin composition for producing the high-light-shielding, high-resistance, and good light patternability of the present invention cannot be obtained. , So it is not preferred. In addition, the smaller the molar ratio (a)/(b), the greater the alkali solubility and the greater the molecular weight tends to be.

The epoxy (meth)acrylate acid adduct can pass the above-mentioned steps using known methods (for example, the method described in Japanese Patent Laid-Open No. 8-278629 or Japanese Patent Laid-Open No. 2008-9401, etc.) ) While manufacturing. First, a method of reacting (meth)acrylic acid with an epoxy compound of the general formula (I) includes, for example, adding a molar (meth)acrylic acid such as an epoxy group with an epoxy compound to a solvent, in a catalyst In the presence of (triethylbenzyl ammonium chloride, 2,6-diisobutylphenol, etc.), a method of reacting by heating and stirring at 90°C to 120°C while blowing air. Next, as a method of reacting the acid anhydride with the hydroxyl group of the reaction product epoxy acrylate compound, there is a method in which a predetermined amount of the epoxy acrylate compound and the acid dianhydride and acid monoanhydride are added to the solvent, and the catalyst (tetraethyl bromide In the presence of ammonium chloride, triphenylphosphine, etc.), the method of heating, stirring and reacting at 90 ℃ ~ 130 ℃.

About the weight of the alkali-soluble resin (A) containing a polymerizable unsaturated group The average molecular weight (Mw) is preferably in the range of 4,000 to 20,000, and more preferably in the range of 4,500 to 7,000. If the weight average molecular weight (Mw) is less than 4000, it is found that it is difficult to maintain the high resistance of the photosensitive resin composition using (A) between 1V and 10V, and if the weight average molecular weight (Mw) exceeds 20,000, the In the case of a highly light-shielding photosensitive resin composition, it becomes easy to leave a developing residue or a residual film in an unexposed portion. In addition, the acid value of (A) is in the range of 80 mgKOH/g to 120 mgKOH/g. If the value is less than 80 mgKOH/g, residues tend to remain during alkaline development using the photosensitive resin composition of (A); if it exceeds 120 mgKOH/g, the alkaline developer has high light shielding using (A) The penetration in the photosensitive resin composition becomes too fast and peeling occurs, which is not preferable. In addition, as for the alkali-soluble resin containing a polymerizable unsaturated group of (A), only one type thereof may be used, or a mixture of two or more types may be used.

Next, (B) the photopolymerizable monomer having at least one ethylenically unsaturated bond includes, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (methyl ) 2-hydroxyhexyl acrylate and other (meth)acrylates with hydroxyl groups, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth) Base) acrylate, tetraethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth) Base) 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 (Meth)acrylates such as hexa(meth)acrylate, phosphazene alkylene oxide modified hexa(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, etc. can be used 1 or 2 or more. In addition, (B) the photopolymerizable monomer having at least one ethylenically unsaturated bond does not have a free carboxyl group.

The mixing ratio of these components (A) and (B) can be 50/50 to 90/10 in terms of mass ratio (A)/(B), preferably 60/40 to 80/20. If the compounding ratio of (A) component is less than 50/50 in terms of (A)/(B), the following problems arise: the cured product after photocuring becomes brittle, and the acid value of the coating film in the unexposed portion Low, so the solubility in alkaline developer is reduced, and the edges of the pattern become jagged and unclear; and if it is more than 90/10 in terms of (A)/(B), the following problems may occur: The proportion of photoreactive functional groups in the resin is small and the cross-linked structure is not sufficiently formed. In addition, the acid value in the resin component is too high, and the solubility in the exposed portion with respect to the alkaline developer becomes high, so The formed pattern becomes thinner than the target line width, and it becomes easy to cause pattern notch and the like.

Furthermore, the photopolymerization initiator of the component (C) includes, for example, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminophenylacetone, and dichloro Acetophenone, trichloroacetophenone, p-tert-butylacetophenone and other acetophenones, benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone Benzophenones such as ketone, benzoin, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin ethers, 2-(o-chlorophenyl)-4,5-phenylbiimidazole , 2-(o-chlorophenyl)-4,5-bis(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-4,5-diphenylbiimidazole, 2-(o-methyl Oxyphenyl)-4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole and other biimidazole-based compounds Class, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxo Halogenated methyl diazole compounds such as diazole, 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole, 2,4,6-tri(tri (Chloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis (Trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-( 4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloro Methyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-( 3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthiostyryl)-4, 6-bis(trichloromethyl)-1,3,5-triazine and other halogenated methyl s-triazine compounds, 1,2-octanedione, 1-[4-(phenylthio)phenyl ]-,2-(O-benzoyl oxime), 1-(4-benzenesulfonyl phenyl) butane-1,2-dione-2-oxime-O-benzoate, 1-( 4-Methanesulfonylphenyl)butane-1,2-dione-2-oxime-O-acetate, 1-(4-methylsulfonylphenyl)butane-1-oneoxime-O -Acetate and other O-acyl oxime compounds, benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone Sulfur compounds such as ketones, 2-isopropylthioxanthone, anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-diphenylanthraquinone, Organic peroxides such as azobisisobutylnitrile, benzoyl peroxide, cumene peroxide, thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, etc. . Among them, from the viewpoint of easily obtaining a photosensitive resin composition for a light-shielding film with high sensitivity, it is preferable to use O-acyl oxime-based compounds. Furthermore, two or more kinds of these photopolymerization initiators can also be used. In addition, the "photopolymerization initiator" in the present invention is used to include a sensitizer.

Only one of these photopolymerization initiators or sensitizers may be used alone, or two or more of them may be used in combination. Furthermore, it is also possible to add a compound that can increase the ability of the photopolymerization initiator or sensitizer by using it in combination although it does not function as a photopolymerization initiator or sensitizer. Examples of such compounds include tertiary amines such as triethanolamine and triethylamine which have an effect when used in combination with benzophenone.

As for the usage amount of the photopolymerization initiator of the component (C), based on the total of 100 parts by mass of the component (A) and the component (B), it may be 2 to 30 parts by mass, preferably 5 parts by mass. 25 parts by mass. When the blending ratio of the component (C) is less than 2 parts by mass, the photopolymerization rate becomes slower and the sensitivity decreases; on the other hand, when it exceeds 30 parts by mass, the following problems may occur: In a state where the line width of the pattern is thickened relative to the pattern mask, the faithful line width cannot be reproduced relative to the mask, or the edge of the pattern becomes jagged and cannot be sharpened.

(D) The component is a light-shielding component selected from black organic pigments, mixed-color organic pigments, or light-shielding materials, and may be a component excellent in heat resistance, light resistance, and solvent resistance. Here, examples of the black organic pigment include perylene black, aniline black, and cyanine black. Examples of the mixed color organic pigment include pigments obtained by mixing two or more pigments selected from the group consisting of red, blue, green, purple, yellow, cyanine, and magenta to simulate blackening. Examples of the light-shielding material include carbon black, chromium oxide, iron oxide, and titanium black. The light-shielding component can also be used by appropriately selecting two or more kinds, and in particular, carbon black is preferable in terms of good light-shielding properties, surface smoothness, dispersion stability, and compatibility with resins. Moreover, when you want to use carbon black When the resistance value of the light-shielding film is further increased, it is also possible to use a carbon black surface-coated surface coated with a dye, pigment, resin, or the like.

Furthermore, the solvent of the component (E) includes, for example, alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol, terpenes such as α-terpineol or β-terpineol, and acetone. , Methyl ethyl ketone, 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 Glycol ethers such as 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 acetates are dissolved and mixed by using these solvents , Can be made into a uniform solution composition.

Furthermore, these light-shielding components are preferably dispersed in a solvent together with the (F) dispersant in advance to prepare a light-shielding dispersion liquid, and then formulated into a photosensitive resin composition for a light-shielding film. Here, the solvent in which it is dispersed becomes part of the (E) component, so it can be used if it is the compound listed in the (E) component, for example, propylene glycol monomethyl ether acetate, acetic acid-3 can be suitably used -Methoxybutyl ester, etc. The formulation ratio of the (D) light-shielding component forming the light-shielding dispersion liquid can be used in the range of 40% by mass to 70% by mass relative to all solid components of the photosensitive resin composition for light-shielding film of the present invention. Particularly, the range of 40% by mass to 60% by mass is preferable. If it is less than 40% by mass, the light-shielding property becomes insufficient for high light-shielding use. If super If it exceeds 70% by mass, the content of the photosensitive resin originally used as a binder is reduced, and thus there is a problem that development characteristics are impaired, film formation ability, etc. are impaired, which is not preferable.

Furthermore, in the light-shielding dispersion liquid, the (F) dispersant is used in order to stably disperse the light-shielding component, and for this purpose, various well-known dispersants such as various polymer dispersants can be used. As examples of the dispersant, known compounds used in the dispersion of existing pigments (compounds commercially available under the names of dispersants, dispersing wetting agents, dispersion accelerators, etc.) can be used without particular limitation, and examples include cationic Polymer-based dispersant, anionic polymer-based dispersant, nonionic polymer-based dispersant, pigment derivative-type dispersant (dispersion aid), etc. Particularly suitable is to have an imidazolyl group, a pyrrolyl group, a pyridyl group, a primary amine group, a secondary amine group or a tertiary amine group and other cationic functional groups as the adsorption point on the pigment, the amine value is 1mgKOH/g~100mgKOH/g 1. Cationic polymer-based dispersant whose number average molecular weight is in the range of 1,000 to 100,000. The blending amount of the dispersant is 1% by mass to 30% by mass, preferably 2% by mass to 25% by mass relative to the light-shielding component.

In addition, when preparing the light-shielding dispersion liquid, a part of the alkali-soluble resin containing the polymerizable unsaturated group of the component (A) is co-dispersed in addition to the dispersant, thereby forming a photosensitive resin composition for the light-shielding film In the case of a photosensitive resin composition, a photosensitive resin composition that can easily maintain the exposure sensitivity at a high sensitivity, has good adhesion during development, and is less likely to cause residue problems. (A) The formulation amount of the component is preferably 2% by mass to 20% by mass in the light-shielding dispersion liquid, and more preferably 5% by mass to 15% by mass. If the component (A) is less than 2% by mass, the effect of co-dispersion (effects such as improved sensitivity, improved adhesion, and reduced residue) cannot be obtained. Moreover, if it is 20% by mass or more, then In particular, when the content of the light-shielding material is large, the viscosity of the light-shielding dispersion liquid is high, and it becomes difficult to uniformly disperse or it takes much time, and it becomes difficult to obtain a photosensitive resin composition for obtaining a coating film with high resistance. Moreover, the obtained light-shielding dispersion liquid can be made into the photosensitive resin composition for light-shielding films by mixing with the remaining (A) component, (B) component, (C) component, and remaining (E) component.

Furthermore, in the photosensitive resin composition of the present invention, a hardening accelerator, a thermal polymerization inhibitor, a plasticizer, a filler, a solvent, a leveling agent, a defoaming agent, a coupling agent, and a surfactant can be formulated as necessary And other additives. Examples of thermal polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tertiary butyl catechol, and phenothiazine, and plasticizers include dibutyl phthalate, Dioctyl phthalate, tricresyl phosphate, etc., fillers include glass fiber, silica, mica, alumina, etc., antifoaming agent or leveling agent include silicone, fluorine, acrylic Compound. Further, the surfactant includes fluorine-based surfactants, silicone surfactants, and the like, and the coupling agent includes 3-(glycidoxy)propyltrimethoxysilane, 3-isocyanatopropyltris Silane coupling agent such as ethoxysilane, 3-ureidopropyltriethoxysilane.

The photosensitive resin composition of this invention contains the said (A) component-(E) component as a main component. The solid component excluding the solvent (the solid component includes a monomer that becomes a solid component after curing) contains components (A) to (D) in a total amount of 80% by mass, preferably 90% by mass or more. (E) The amount of solvent varies depending on the target viscosity, and the photosensitive resin composition may contain (E) the solvent in the range of 70% by mass to 90% by mass.

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 light-shielding film of a color filter, and a method for forming a light-shielding film includes a photolithography method as described below. The following methods may be mentioned: first, the photosensitive resin composition is applied on a transparent substrate, and secondly, the solvent is dried (pre-baking), and then a photomask is placed on the coating film obtained as described above, and ultraviolet rays are irradiated to The exposed portion is hardened, and further developed by using an alkaline aqueous solution to elute the unexposed portion to form a pattern, and further post-baked (thermally fired) for post-drying.

In addition to the glass substrate, the transparent substrate coated with the photosensitive resin composition may be exemplified by ITO or gold deposited on a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether ash, etc.) or patterned on it. Transparent electrode substrate, etc. The method of applying the solution of the photosensitive resin composition on the transparent substrate may be any method such as a method using a roll coater, a sand coater, a slit coater, or a rotary machine in addition to the well-known solution dipping method and spray method. After coating to a desired thickness by these methods, the solvent is removed (pre-baked), thereby forming a coating. The pre-baking can be performed by heating using an oven, a hot plate, or the like. The heating temperature and heating time of the pre-baking can be appropriately selected according to the solvent used, for example, at a temperature of 60°C to 110°C for 1 minute to 3 minutes.

The exposure performed after the pre-baking can be performed using an ultraviolet exposure device and exposed through a photomask, thereby only sensitizing the resist corresponding to the pattern. The exposure device and its exposure and irradiation conditions can be appropriately selected. An ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a far-ultraviolet lamp, and other light sources are used for exposure to light-harden the photosensitive resin composition in the coating film.

The alkaline development after exposure is performed for the purpose of removing the resist of the unexposed portion, and the desired pattern is formed by the development. Examples of the developing solution suitable for the alkaline development include aqueous solutions of carbonates of alkali metals or alkaline earth metals, and aqueous solutions of hydroxides of alkali metals. In particular, sodium carbonate and carbonic acid containing 0.05% by mass to 3% by mass can be used. The weakly alkaline aqueous solution of carbonate such as potassium and lithium carbonate is developed at a temperature of 23°C to 28°C, and a fine image can be precisely formed using a commercially available developing machine or ultrasonic cleaner.

After development, it is preferable to perform heat treatment (post-baking) at a temperature of 180°C to 250°C and a condition of 20 minutes to 60 minutes. This post-baking is performed for the purpose of improving the adhesion between the patterned light-shielding film and the substrate. It is performed by heating with an oven, a hot plate, etc. like pre-baking. The patterned light-shielding film of the present invention is formed through the above steps using photolithography.

The photosensitive resin composition of the present invention is suitable for forming fine patterns by operations such as exposure and alkaline development as described above. Furthermore, 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 a light-shielding ink for color filters used in liquid crystal display devices or imaging devices, thereby forming light-shielding The film can be used as a color filter, a black matrix for liquid crystal projection, a light-shielding film, a light-shielding film for touch panel, etc.

The high light-shielding and high-resistance light-shielding film obtained in the present invention becomes 1×10 ¹² Ω at an applied voltage of 10V when the OD is 3.5/μm or more and the OD is less than 4.0/μm. Volume resistivity above cm. Moreover, even in a light-shielding level with an OD of 4.0/μm or more, 1×10 ¹¹ Ω can be ensured under an applied voltage of 10V. The volume resistivity of cm or more is preferably 1×10 ¹² Ω under an applied voltage of 10V. Volume resistivity above cm. In addition, the pattern formed using the photosensitive resin composition of the present invention is difficult to overheat during post-baking, and the cross-sectional shape of the pattern is maintained as a rectangular shape, which is suitable for forming a light-shielding film pattern in which the side surface of the pattern is perpendicular to the substrate.

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

[Example]

First, a synthetic example of the (A) alkali-soluble resin containing a polymerizable unsaturated group of the present invention is shown. The evaluation of the resin in the synthesis example can be carried out as follows.

[Solid content concentration]

1 g of the resin solution obtained in the synthesis example was impregnated into a glass filter [weight: W ₀ (g)] and weighed [W ₁ (g)], and the weight [W ₂ ( g)], obtained 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 it was determined by titration with a 1/10N-KOH aqueous solution using a potentiometric titration device [Hiramu Industries Co., Ltd., trade name COM-1600].

[Molecular weight]

Gel permeation chromatography (GPC) [manufactured by Tosoh Co., Ltd., trade name HLC-8220GPC, solvent: tetrahydrofuran, column: TSKgel SuperH-2000 (2 pieces) + TSKgel SuperH- 3000 (1 root) + TSKgel SuperH-4000 (1 root) + TSKgel Super-H5000 (1 root) [manufactured by Tosoh Corporation], temperature: 40°C, speed: 0.6 ml/min] Styrene [manufactured by Tosoh Co., Ltd., PS-oligomer kit] was converted to a weight average molecular weight (Mw).

The abbreviations used in Synthesis Examples and Comparative Synthesis Examples are as follows.

BPFE: the reactant of 9,9-bis(4-hydroxyphenyl) stilbene and chloromethyloxirane. In the compound of the general formula (I), X is a compound of 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]

In a 1 L four-necked flask with a reflux condenser, 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 added, and the mixture was heated for 12 hours under heating at 100°C to 105°C. The reaction product is obtained.

Next, BPDA 94.15g (0.32mol) and THPA 22.82g (0.15mol) were added to the resulting reaction product, and stirred under heating at 115°C to 120°C for 6hr to obtain an alkali soluble resin solution containing a polymerizable unsaturated group (A)-1. 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 analyzed by GPC was 5200.

[Synthesis Example 2]

In a 1L four-necked flask with a reflux condenser, add 244.3g (0.50 mol), 72.1 g (1.0 mol) of acrylic acid, 0.45 g of TPP, and 318 g of PGMEA were stirred under heating at 100° C. to 105° C. for 12 hr to obtain a reaction product.

Next, BPDA 94.15g (0.32mol) and THPA 3.04g (0.02mol) were added to the resulting reaction product, and stirred under heating at 115°C to 120°C for 6hr to obtain an alkali-soluble resin containing a polymerizable unsaturated group. Solution (A)-2. 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 analyzed by GPC was 4600.

[Synthesis Example 3]

In a 1L four-necked flask equipped with a reflux condenser, add 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, and stir for 12 hours under heating at 100 to 105° The reaction product is obtained.

Next, BPDA 94.15g (0.32mol) and THPA 3.04g (0.02mol) were added to the resulting reaction product, and stirred for 6 hours under heating at 115°C to 120°C to obtain an alkali soluble resin solution containing a polymerizable unsaturated group (A)-3. 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 analyzed by GPC was 5500.

[Comparative Synthesis Example 1]

In a 1L four-necked flask with a reflux condenser, add 244.3g (0.50mol) of BPFE, 72.1g (1.0mol) of acrylic acid, 0.45g of TPP, and 329g of PGMEA, and stir for 12 hours under heating at 100°C to 105°C. The reaction product is obtained.

Next, BPDA 73.56g (0.25mol) and THPA 38.03g (0.25mol) were added to the resulting reaction product, and heating was performed at 115°C to 120°C for 6hr Stir to obtain a solution (A)-4 of an alkali-soluble resin containing a polymerizable unsaturated group. 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 analyzed by GPC was 3600.

[Preparation Example 1] Preparation of dye-coated carbon black

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

(Example 1 to Example 4, Comparative Example 1)

Next, the present invention will be specifically described based on Examples and Comparative Examples of the production of the photosensitive resin composition for a light-shielding film and its cured product, but the present invention is not limited to these examples. Here, the raw materials and abbreviations used in the production of the photosensitive resin composition for light-shielding films and cured products thereof in the following Examples and Comparative Examples are shown below.

(Alkali-soluble resin containing polymerizable unsaturated groups)

(A)-1 component: the solution of the alkali-soluble resin obtained in Synthesis Example 1

(A)-2 Component: the solution of the alkali-soluble resin obtained in Synthesis Example 2

(A)-3 component: the solution of the alkali-soluble resin obtained in Synthesis Example 3

(A)-4 component: the solution of the alkali-soluble resin obtained in Comparative Synthesis Example 1

(Photopolymerizable monomer)

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

(Photopolymerization initiator)

(C): Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1-(O-acetoacetoxime) (Japan (Made by BASF, the product name is Irgacure OXE02)

(Light-shielding dispersed pigment)

(D)-1: Propylene glycol monomethyl ether acetate dispersion liquid (solid content 30.0%) with carbon black concentration of 25.0% by mass and polymer dispersant concentration of 5.0% by mass

(D)-2: 300.0 g of the dye-coated carbon black prepared in Preparation Example 1, 24.0 g of the urethane-based dispersant, and 146.0 g of the solution of the alkali-soluble resin obtained in Synthesis Example 2 using a bead mill, Dispersion liquid obtained by dispersing 729.6 g of propylene glycol monomethyl ether acetate (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 (Bike Chemical Company)

The formulation components were blended in the ratios shown in Table 1 to prepare the photosensitive resin compositions of Examples 1 to 4 and Comparative Example 1. In addition, the numerical values in Table 1 all represent parts by mass. Furthermore, (E)-1 in the column of solvent is PGMEA (same as (E)-1) in a solution containing no unsaturated group-containing resin (a solution containing a polymerizable unsaturated group-containing alkali-soluble resin), And the amount of PGMEA (same as (E)-1) in the light-shielding dispersion liquid.

[Evaluation]

The photosensitive resin compositions for light-shielding films of Examples 1 to 4 and Comparative Example 1 were used for the evaluation described below. The results of these evaluations are shown in Table 2.

<Evaluation of development characteristics (pattern line width/pattern linearity)>

Each photosensitive resin composition obtained above was applied onto a 125 mm×125 mm glass substrate (Corning 1737) with a spin coater so that the film thickness after baking was 1.1 μm, and pre-bake at 90° C. for 1 minute grilled. After that, the exposure pitch is adjusted to 100 μm, a negative coating of 10 μm or 6 μm is covered on the dried coating film, and the ultraviolet light of 80 mJ/cm ² is irradiated with an ultra-high pressure mercury lamp with an i-ray illuminance of 30 mW/cm ² to perform the photosensitive part. Photo-hardening reaction.

Next, the exposed coated plate was subjected to a development time (image-out time = BT) +20 seconds from the start of the pattern at 25° C. in a 0.05% potassium hydroxide aqueous solution under a spray development pressure of 1 kgf/cm ² . After +30 seconds of development, a spray water wash with a pressure of 5 kgf/cm ^{2 was} performed to remove the unexposed part of the coating film to form a pixel pattern on the glass substrate, and thereafter, a hot air dryer was used to heat at 230° C. for 30 minutes. After post-baking, the line width and pattern linearity with respect to the mask width of the 10 μm line and the 6 μm line were evaluated. When the pattern image does not appear even if the development time exceeds 80 seconds, it is assumed that the development cannot be performed. In addition, each evaluation method is as follows.

Pattern line width: The pattern line width of the mask width of 10 μm and 6 μm was measured using a length measuring microscope (“XD-20” manufactured by Nikon Corporation).

Pattern linearity: Observe the mask pattern of 10 μm or 6 μm after post-baking with a microscope, and no peeling from the substrate or jagged edges of the pattern will be found The case evaluation was "○", the case where a part was found was evaluated as "△", and the case where the whole was found was evaluated as "×".

<Evaluation of OD/μm>

Each photosensitive resin composition obtained above was applied onto a 125 mm×125 mm glass substrate (Corning 1737) with a spin coater so that the film thickness after baking was 1.1 μm, and pre-bake at 90° C. for 1 minute grilled. After that, the ultra-high-pressure mercury lamp with an i-ray illuminance of 30 mW/cm ² was irradiated with 80 mJ/cm ² of ultraviolet rays without covering the negative-type photomask, and the photo-curing reaction of the photosensitive part proceeded.

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

<Evaluation of adhesion to glass substrate>

Each photosensitive resin composition obtained above was applied onto a 125 mm×125 mm glass substrate (Corning 1737) with a spin coater so that the film thickness after baking was 1.1 μm, and pre-bake at 90° C. for 1 minute grilled. Thereafter, without using a negative light mask, an ultrahigh-pressure mercury lamp with an i-line illuminance of 30 mW/cm ² and an overall exposure of 80 mJ/cm ² were used, and hot post-drying was performed at 230° C. for 30 minutes using a hot air dryer . Next, regarding the obtained post-baked substrate, the adhesion strength with the glass substrate was evaluated as follows using the evaluation method based on the three-point bending adhesion test method of JIS K6856-1994. The post-baked substrate with a coating film and the glass substrate (Corning 1737) without a resin composition (a substrate without a coating film) were cut into strips of 20 mm × 63 mm to prepare a test sheet. The substrate with a coating film and the substrate without a coating film that have been post-baked are bonded together via a certain amount of sealant epoxy-based adhesive so that the overlap width becomes 8 mm. The sealant epoxy-based adhesive when superimposed has a circular shape and a diameter of approximately 5 mm. Thereafter, the superimposed test pieces were subjected to pre-baking at 90°C for 20 minutes, followed by post-baking at 150°C for 2 hours to prepare three-point bending test pieces. Further, a sample for comparison test in which 20 mm×63 mm uncoated substrate test pieces were also bonded to each other by the same method as described above was prepared.

In the obtained test piece, a sample obtained by laminating a substrate with a coating film and a substrate without a coating film, or a sample for a comparative test, is supported by a two-point support body so that the overlapping portion becomes the center (The spacing between the support points at 2 points is 3 cm), using a brand name UCT-100 of ORIENTEC (manufactured by ORIENTEC) and applying a load at a speed of 1 mm/min from directly above and below the overlapping portion to make it fit Department. At this time, the load at the time of peeling was read and divided by the coating area of the sealant epoxy adhesive, and the load per unit area was taken as the adhesion strength. Furthermore, after performing a pressure cooker test (PCT) under the conditions of 121° C., 100% RH, 2 atm, and 5 hours, the same adhesion strength test was performed to determine the adhesion strength before and after PCT. When the adhesion strengths of the samples for comparative tests before and after PCT were each set to 100, the adhesion strength in each composition was expressed as a relative value. Before and after the PCT, the case of 70 or more is regarded as "○".

<Evaluation of volume resistivity>

The photosensitive resin composition obtained above was applied onto a 125 mm×125 mm glass substrate (Corning 1737) with a spin coater so that the film thickness after baking was 3.0 μm, and pre-baked at 90° C. for 1 minute. grilled. After that, hot post-drying was performed at 230°C for 180 minutes using a hot air dryer, and then using an electrometer (Keithley (Keithley), "6517A model"), the volume resistance of the applied voltage of 1V to 10V was measured rate. The measurement was carried out under the condition that each of the applied voltages maintained a voltage of 60 seconds at an interval of 1V, and the volume resistivity at the time of applying 1V and at the time of applying 10V was shown in Table 2.

When the photosensitive resin composition for light-shielding films of Examples 1 to 4 is used, the line width tends to become thicker to a certain extent at BT+20 seconds, and it is necessary to increase the development time to a certain extent, but It has sufficient optical patternability. When the OD is 3.8/μm, the volume resistivity when the applied voltage is 10V becomes 1×10 ¹³ Ω. cm, it can be seen that the required 1×10 ¹² Ω can be achieved. Volume resistivity above cm. Among them, especially in Example 4, even when the OD of the improved shading degree is 4.0/μm, the volume resistivity is maintained at 1×10 ¹³ Ω. cm, it can be seen that high light shielding and high resistance can be achieved, and the adhesion strength (sealed adhesion) with the glass substrate is also high. It can be seen that these effects can be achieved by co-dispersing the unsaturated group-containing alkali-soluble resin in the carbon black dispersion to improve development adhesion and the like, and can sufficiently exhibit high resistance and are suitable for dye-coated carbon black with high seal adhesion. Characteristics.

In Comparative Example 1, although the volume resistivity can ensure 1×10 ¹² Ω when 1V is applied. cm or more, but less than 1×10 ¹² Ω when 10V is applied. cm, the volume resistivity is reduced, and it can be seen that it does not satisfy the required characteristics of high light shielding and high resistance in current color filter applications for liquid crystal displays.

Claims (7)

A photosensitive resin composition for a light-shielding film, which contains the following components (A) to (E) as essential components: (A) An alkali-soluble resin containing a polymerizable unsaturated group, which is represented by the following general formula (I ) The reactant of the compound represented by (meth)acrylic acid is further reacted with a polycarboxylic acid or its anhydride, (B) a photopolymerizable monomer having at least one ethylenically unsaturated bond, (C) photopolymerization The 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, and (E) solvents; characterized in that (A) component is Polycarboxylic acid or its anhydride (a) dicarboxylic acid or tricarboxylic acid or its anhydride, and (b) tetracarboxylic acid or its acid dianhydride with a molar ratio (a)/(b) of 0.01 to 0.5 The alkali soluble resin containing polymerizable unsaturated group and the acid value of 80mgKOH/g~120mgKOH/g is obtained by the reaction within the range; wherein: the mass ratio of (A) component to (B) component (A)/(B) 50/50~90/10, containing 2 parts by mass to 30 parts by mass of (C) component relative to the total of 100 parts by mass of (A) component and (B) component, and the photosensitive resin composition for a light-shielding film The solid component that contains the component that becomes a solid component due to photohardening contains (D) component in an amount of 40% by mass to 70% by mass;

Among them, 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, X represents a fluorene-9,9-diyl group, and n represents an average value 0~10. The photosensitive resin composition for a light-shielding film as described in item 1 of the patent application range, further comprising (F) a dispersant, and predispersing the (D) component together with a part of the (A) component and the (F) dispersant In a part of (E) component, it is manufactured by mixing with the remaining (A) component, (B) component, (C) component, and the remaining (E) component. The photosensitive resin composition for a light-shielding film as described in item 1 of the patent application range, wherein (D) the light-shielding component is carbon black. The photosensitive resin composition for a light-shielding film as described in item 1 of the patent application range, which is used to form a volume resistivity of 1 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 ×10 ¹² Ω. Coating film above cm. The photosensitive resin composition for a light-shielding film as described in item 1 of the patent application range, which is used to form a volume resistivity of 1×10 ¹¹ Ω when a 10V voltage is applied when the optical density OD is 4.0/μm or more. Coating film above cm. A light-shielding film characterized by being formed by hardening the photosensitive resin composition for a light-shielding film according to any one of claims 1 to 5. A color filter, characterized by comprising a light-shielding film, wherein the light-shielding film is coated with a photosensitive resin composition for a light-shielding film as described in any one of claims 1 to 5 on a transparent substrate After pre-baking, it is produced by exposure with an ultraviolet exposure device, development with an alkaline aqueous solution, and post-baking.