JP7396786B2 - Photosensitive resin composition for light-shielding film, light-shielding film, liquid crystal display device, method for producing light-shielding film having spacer function, and method for producing liquid crystal display device - Google Patents

Description

The present invention relates to a photosensitive resin composition for a light-shielding film and a light-shielding film obtained by curing the same, and more specifically, to a black matrix of a liquid crystal display device, or a black column spacer having both a spacer function and a black matrix function in a liquid crystal display device. The present invention relates to a photosensitive resin composition and a cured film thereof, which can be formed by photolithography. The present invention further relates to a liquid crystal display device using the black matrix or black column spacer obtained by the above-mentioned curing. The present invention further relates to a method for manufacturing a light-shielding film and a liquid crystal display device using the photosensitive resin composition.

In recent years, color liquid crystal displays (LCDs) have been used in various fields such as liquid crystal televisions, liquid crystal monitors, and color liquid crystal mobile phones. In order to improve the performance of LCDs, improvements are being actively made to improve characteristics such as viewing angle, contrast, and response speed. A new panel structure has been developed. For TFT-LCDs, the conventional method of manufacturing an array substrate on which TFTs are formed and a color filter substrate and bonding the two substrates together with a spacer keeping them at a constant distance has been adopted, but cost reduction , LCD manufacturing processes aimed at improving yields have also been developed. For example, a manufacturing process has been developed in which a color filter is directly formed on the TFT of an array substrate and a glass substrate is bonded to the TFT as an opposing substrate. The structure formed in this way is called a color filter-on-TFT (COT) or the like. In this COT as well, there is a method in which a black matrix is formed as a boundary between each pixel of red (R), green (G), blue (B), etc. of the color filter layer formed on the TFT before the RGB pixels are formed. Various LCD panel structures are being considered, such as a method in which the LCD panel is formed on top of RGB pixels, or a method in which the LCD panel is formed on an opposing glass substrate.

Spacers, which function to keep the thickness of the liquid crystal layer constant (in the conventional method, the distance between the array substrate and the color filter (CF) substrate), which is one factor that affects the performance of LCDs, have traditionally been kept constant. The method used was to insert a particle-sized ball spacer. However, this method has a problem in that the amount of light transmitted from pixel to pixel is not constant due to non-uniform dispersion of the ball spacers. To solve this problem, a method of forming column spacers by photolithography has been adopted. However, column spacers formed by photolithography are often transparent, and light incident on such column spacers from oblique directions affects the electrical characteristics of TFTs, degrading display quality. There is a problem. To address these problems, an LCD panel structure has been proposed that uses a light-shielding column spacer, which is a light-shielding film having a spacer function and formed by photolithography (Patent Document 1). Also in COT, a method of forming a so-called black column spacer (BCS), in which the column spacer is formed of the same material as the black matrix, has been studied (for example, Patent Document 2).

This light-shielding column spacer needs a film thickness of about 2 to 7 μm in order to function as a spacer. Furthermore, it is necessary that light-shielding column spacers having different heights can be simultaneously formed at the location where the TFT is formed and at other locations. In addition, the light-shielding column spacer is also required to have elastic modulus, deformation amount, elastic recovery rate, etc. within appropriate ranges as a spacer function (Patent Document 3). Furthermore, light-shielding column spacers are required to reduce the amount of curable components by adding a light-shielding component (coloring agent) to the spacer, and to improve the loss of electrical properties due to the effects of impurities in the colorant. (Patent Document 4).

Furthermore, when an LCD panel manufacturer actually applies BCS, there are various required BCS shapes depending on the panel design. For example, there is a design that uses a BCS with a trapezoidal or rectangular cross-sectional shape (Patent Document 5), and there is also a design that uses a BCS with a cross-sectional shape that is a combination of trapezoids or rectangles with different base lengths (Patent Document 6). be. The reason for the combination shape is to simultaneously form a portion that only functions as a light-shielding film and a portion that also functions as a spacer. There has also been a demand for photosensitive resin compositions for light-shielding films that are used to collectively form such cross-sectional shapes.

Japanese Patent Application Publication No. 08-234212 US Patent Application Publication No. 2009/0303407 Japanese Patent Application Publication No. 2009-031778 International Publication No. 2013/062011 Korean Published Patent No. 10-2013-0062123 Korean Published Patent No. 10-2008-0034545

In Patent Document 4, a color-mixing organic pigment is used, but the optical density of the light-shielding column spacer is not disclosed. Color-mixing organic pigments are more effective in lowering the dielectric constant than inorganic pigments such as carbon black, but they often have low light-shielding properties. Furthermore, since it is necessary to form spacers with different heights at the same time, the light-shielding column spacer is also required to have mechanical properties such as compressibility, elastic recovery rate, and breaking strength. The shape and mechanical properties of such a spacer are greatly influenced by the light-shielding component, making it difficult to design a photosensitive resin composition for a light-shielding film. Therefore, the shape and mechanical properties of spacers using carbon black, color-mixing organic pigments, etc. are still not sufficient, and further improvements are required.

Furthermore, as described above, the light-shielding column spacer is manufactured with a film thickness of about 1 to 7 μm. With the miniaturization of liquid crystal display elements in recent years, it is desired that a light-shielding column spacer can be formed into a fine spacer shape even if the film thickness is about 1 to 7 μm. In addition, in addition to having the functions of a black matrix and a spacer, we also offer various types of substrates that sandwich the liquid crystal layer (array substrate and CF substrate, COT substrate and glass substrate with light-shielding spacer, COT substrate with light-shielding spacer and glass substrate, etc.). There is a combination of There are many demands for patterning characteristics, such as forming a light-shielding spacer with as vertical a rise as possible, and it is difficult to satisfy all required characteristics.

The present invention has been made in view of the above-mentioned problems, and it is possible to form a light-shielding film that has high light-shielding properties and insulation properties, has excellent compressibility, elastic recovery rate, and breaking strength, and has a spacer function. When forming a light-shielding film with An object of the present invention is to provide a liquid crystal display device that achieves the following.

Furthermore, we provide a photosensitive resin composition that can collectively form a BCS whose cross-sectional shape is a combination of trapezoids or rectangles with different base lengths, a light-shielding film formed using the same, and the light-shielding film. An object of the present invention is to provide a liquid crystal display device as a component.

The present inventors conducted studies to solve the above-mentioned problems in photosensitive resin compositions for light-shielding films, and found that a specific colorant was used to block light-shielding photosensitive resin compositions for light-shielding films. They found that it is suitable as a component and completed the present invention.

(1) The present invention is a photosensitive resin composition for a light-shielding film, which is characterized by containing components (A) to (E) as essential components.
(A) Contains 5 to 90 mol% of units represented by general formula (1) and 10 to 95 mol% of units represented by general formula (2) (units represented by general formula (1) and general an alkali-soluble resin containing a polymerizable unsaturated group, which is a polymer having a weight average molecular weight of 3000 to 50000 and an acid value of 30 to 200 mg/KOH;

(However, R ₁ , R ₃ and R ₄ independently represent a hydrogen atom or a methyl group. _{R 2} represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group has an ether bond inside, It may contain an ester bond or a urethane bond.In addition, 40 mol% or more of the units represented by the general formula (1) in _R2 is a dicyclopentanyl group or a dicyclopentenyl _group.R5 is a carbon Represents a divalent hydrocarbon group of numbers 2 to 10. p represents a number of 0 or 1. X is a hydrogen atom or -OC-Y-(COOH) _q (However, Y is a divalent or trivalent carboxylic acid Represents a residue, and q represents a number from 1 to 2.In addition, two or more types of X are contained in one molecule of the polymer.)
(B) a photopolymerizable monomer having at least two ethylenically unsaturated bonds;
(C) photopolymerization initiator,
(D) one or more light-shielding components selected from the group consisting of a black organic pigment, a color-mixing organic pigment, and a light-shielding material; and (E) a solvent. In addition to the units of general formula (1) and general formula (2), the alkali-soluble resin contains a unit derived from styrene and/or a unit derived from a monomaleimide compound, which may have a substituent on the phenyl group. The photosensitive resin composition according to (1) is a copolymer.
(3) The present invention also includes (D) a black organic pigment and/or a color-mixing organic pigment as a light-shielding component, and the average secondary particle size of the black organic pigment and/or color-mixing organic pigment is 20 to 500 nm. The photosensitive resin composition according to (1) or (2), characterized by:
(4) The present invention also provides 5 to 400 parts by mass of component (B) per 100 parts by mass of component (A),
0.1 to 30 parts by mass of component (C) per 100 parts by mass of the total amount of components (A) and (B),
When the solid content is a component including the component (B) that becomes a solid content after photocuring, but excluding the component (E),
(D) component, 5 to 80% by mass of the total solid content,
The photosensitive resin composition according to any one of (1) to (3), characterized in that it contains each of the following.
(5) The present invention also provides a light shielding film having an optical density OD of 0.5/μm or more and 3/μm or less, a volume resistivity of 1×10 ⁹ Ω·cm or more when a voltage of 10 V is applied, and a dielectric The photosensitive resin composition according to any one of (1) to (4), which is capable of forming a light-shielding film having a light-shielding ratio of 2 to 10.
(6) The present invention is also characterized in that it can form a light-shielding film that satisfies at least one of the following (i) to (iii) in a loading-unloading test using a microhardness meter. The photosensitive resin composition according to any one of 5).
(i) Breaking strength is 200 mN or more (ii) Elastic recovery rate is 30% or more (iii) Compressibility is 40% or less (7) The present invention also provides (1) to (6) ) A light-shielding film characterized by being a cured product of the photosensitive resin composition according to any one of the above.
(8) The present invention is also a liquid crystal display device characterized by having the light shielding film described in (7) as a black column spacer (BCS).
(9) The present invention also provides the liquid crystal display device according to (8), further comprising a thin film transistor (TFT).
(10) The present invention also provides a liquid crystal display device comprising a cured product of the photosensitive resin composition according to any one of (1) to (6) as a black matrix.
(11) The present invention further includes a thin film transistor (TFT), and the black matrix is disposed between the liquid crystal and a substrate facing the array substrate on which the thin film transistor (TFT) is formed. The liquid crystal display device according to (10) is characterized in that the liquid crystal display device is characterized in that:
(12) The present invention further includes a thin film transistor (TFT), and the black matrix is disposed between the array substrate on which the thin film transistor (TFT) is formed and the liquid crystal. The liquid crystal display device according to (10).
(13) The present invention also provides a photosensitive resin composition formed on a substrate by applying the photosensitive resin composition according to any one of (1) to (6) to the substrate and curing the photosensitive resin composition by light irradiation. This is a method for producing a light shielding film, in which the film thickness H1 for making the optical density of the light shielding film 0.5/μm or more and less than 3/μm, and the film thickness H2 of the light shielding film that plays a spacer function, H2 is 1. ~7 μm, a method for producing a light shielding film having a spacer function, characterized by simultaneously forming a light shielding film with a thickness H1 and a thickness H2 in which ΔH=H2−H1 is 0.1 to 6.9. be.
(14) The present invention also provides the method of forming a light-shielding film including a portion having the thickness H1 and a portion having the thickness H2 in a single light-shielding film in one exposure. 13) is the method for producing a light-shielding film.
(15) The present invention also provides a method for manufacturing a liquid crystal display device, characterized in that the light shielding film manufactured by the method described in (13) or (14) is used as a black column spacer (BCS).
(16) The present invention also provides the manufacturing method according to (15), wherein the liquid crystal display device includes a thin film transistor (TFT).

The photosensitive resin composition for a light-shielding film according to the present invention can provide a cured product with excellent compressibility, elastic recovery rate, and breaking strength while maintaining light-shielding properties and insulation properties. Further, the photosensitive resin composition for a light-shielding film according to the present invention can form a fine spacer shape even when the film thickness is about 1 to 7 μm.

FIG. 1 is a height profile of a pattern formed using the photosensitive resin composition of Example 8. FIG. 2 is a height profile of a pattern formed using the photosensitive resin composition of Example 9. FIG. 3 is a height profile of a pattern formed using the photosensitive resin composition of Comparative Example 3. FIG. 4 is a height profile of a pattern formed using the photosensitive resin composition of Comparative Example 4.

The present invention will be explained in detail below.

One aspect of the present invention includes (A) an alkali-soluble resin containing a polymerizable unsaturated group, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, (D) a light-shielding component, and (E) each described in detail below. ) A photosensitive resin composition containing a solvent as an essential component.

The polymerizable unsaturated group-containing alkali-soluble resin of component (A) is a polymer containing a unit represented by general formula (1) and a unit represented by general formula (2).

In general formulas (1) and (2), R ₁ , R ₃ and R ₄ independently represent a hydrogen atom or a methyl group.
R ₂ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may contain an ether bond, an ester bond, or a urethane bond inside. Further, R ₂ is a dicyclopentanyl group or a dicyclopentenyl group in a proportion of 40 mol % or more in the unit represented by the general formula (1).
R ₅ represents a divalent hydrocarbon group having 2 to 10 carbon atoms. p represents the number 0 or 1. X is a hydrogen atom or -OC-Y-(COOH) _q (However, Y represents a divalent or trivalent carboxylic acid residue, and q represents a number of 1 to 2. contains two or more types).

Examples of the hydrocarbon group represented by R ₂ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, and neopentyl group. , tert-pentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group and other saturated linear hydrocarbon groups , unsaturated linear hydrocarbon groups such as vinyl group, allyl group, ethynyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 2-methylcyclohexyl group, 4-methylcyclohexyl group, dicyclopentanyl group, Cyclopentenyl group, dicyclohexyl group, norbornyl group, isobornyl group, adamantyl group, a substituent represented by the following general formula (3) (* indicates the bonding part with the ester moiety of general formula (1)), etc. Carbohydrates having aromatic rings such as aliphatic hydrocarbon groups, phenyl groups, tolyl groups, mesityl groups, naphthyl groups, anthryl groups, phenanthryl groups, benzyl groups, 2-phenylethyl groups, 2-phenylvinyl groups, decahydronaphthyl groups, etc. Examples include aliphatic ethers such as a hydrogen group, methoxyethyl group, 2-(methoxyethoxy)ethyl group, and isoamyl group, and aliphatic urethanes such as 2-(ethoxycarbonylamino)ethyl group. In the present invention, it is essential that the hydrocarbon group represented by R ₂ includes a dicyclopentanyl group or a dicyclopentenyl group. The unit represented by general formula (1) may include a plurality of units in which R ₂ is different.

Examples of the hydrocarbon group represented by R ₅ include ethylene group, 1,2-propylene group, 1,4-butylene group, and 1,6-hexamethylene group. The hydrocarbon group represented by R ₅ is preferably an ethylene group, a 1,2-propylene group, or a 1,4-butylene group. The unit represented by general formula (2) may include a plurality of units in which R ₅ is different.

The structure where X is -OC-Y-(COOH) _q (wherein, Y represents a divalent or trivalent carboxylic acid residue, and q represents a number of 1 to 2) is based on the hydroxyl group in the copolymer. It is formed by reacting a divalent carboxylic acid, a trivalent carboxylic acid, or an acid monoanhydride thereof. A divalent or trivalent carboxylic acid residue refers to a portion of a carboxylic acid compound in which two or three COOH groups are bonded, excluding the COOH group. Examples of divalent or trivalent carboxylic acids used here include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, chlorendic acid, and trimellitic acid. Examples include carboxylic acids of various valences, and acid monoanhydrides thereof can also be preferably used. More preferred are tetrahydrophthalic anhydride, succinic anhydride, or trimellitic anhydride.

The ratio of the units represented by general formula (1) and the units represented by general formula (2) is the sum of the units represented by general formula (1) and the units represented by general formula (2). The amount of units represented by general formula (1) may be 5 to 90 mol%, preferably 20 to 70 mol%, when 100 mol%. Further, the amount of units represented by general formula (2) may be 10 to 95 mol%, preferably 30 to 80 mol%.

The polymerizable unsaturated group-containing alkali-soluble resin of component (A) may contain other units than the unit represented by the general formula (1) and the unit represented by the general formula (2). For example, the polymerizable unsaturated group-containing alkali-soluble resin of component (A) may further include a unit derived from styrene or monomaleimide, which may have a substituent on the phenyl group. Examples of substituents that styrene may have on the phenyl group include alkyl groups having 1 to 10 carbon atoms. Examples of the monomaleimide include N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, and N-(4-hydroxyphenyl)maleimide.
Among these, styrene and N-phenylmaleimide are preferred.

The ratio of the other units mentioned above can be 20 to 50 mol% when the entire polymer is 100 mol%.

In addition, only one type of polymerizable unsaturated group-containing alkali-soluble resin (A) may be used, or a mixture of two or more types of polymers having different polymerization ratios may be used.

The method for producing component (A), a polymerizable unsaturated group-containing alkali-soluble resin, is not particularly limited. For example, as a first step, a (meth)acrylic acid ester having the above-mentioned functional group as _R2 and a (meth)acrylic acid ester compound having a glycidyl group such as glycidyl (meth)acrylate are radically copolymerized in a solvent. After obtaining the copolymer, the second step is to react the glycidyl groups in the copolymer with a monocarboxylic acid compound such as (meth)acrylic acid (including those modified with alkylene oxide), followed by the third step. As a method, there is a method in which the hydroxyl group generated in the second step is reacted with a dicarboxylic acid compound, a tricarboxylic acid compound, or an acid monoanhydride of these carboxylic acid compounds.

The (meth)acrylic acid esters serving as the unit of general formula (1) used in the first step are first used to introduce a dicyclopentanyl group or a dicyclopentenyl group, which is essential in the present invention, as _R2 . Examples of (meth)acrylic acid esters include dicyclopentanyl (meth)acrylate of formula (4), dicyclopentenyl (meth)acrylate of formula (5), and ethylene glycol-modified dicyclopentanyl (formula (6)). Examples include meth)acrylate, ethylene glycol-modified dicyclopentenyl (meth)acrylate of formula (7), and two or more of these can also be used in combination.

Note that R ₁ in the general formulas (4) to (7) represents a hydrogen atom or a methyl group similarly to R ₁ in the general formula (1).

Other (meth)acrylic esters serving as units of general formula (1) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and (meth)acrylic acid. -iso-propyl, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, neopentyl (meth)acrylate, ( Isoamyl meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-(meth)acrylate Methylcyclohexyl, dicyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, (meth)acrylic acid Hydrocarbon groups having 1 to 20 carbon atoms such as anthracenyl, benzyl (meth)acrylate, phenethyl (meth)acrylate, cresyl (meth)acrylate, triphenylmethyl (meth)acrylate, cumyl (meth)acrylate, etc. Examples include (meth)acrylic esters having the following, and two or more types can also be used in combination.

The amount of the (meth)acrylic esters used is 40 mol% of the (meth)acrylic esters to introduce the dicyclopentanyl group or dicyclopentenyl group based on the total amount of the (meth)acrylic esters. Adjustment may be made so that the above value is achieved.

In addition, the amount of the above-mentioned (meth)acrylic esters and (meth)acrylic ester compounds having a glycidyl group used is such that the unit derived from the (meth)acrylic ester in the copolymer is 5 to 90 mol%, glycidyl The amount of units derived from the (meth)acrylic acid ester compound having the group may be adjusted to 10 to 95 mol%.

Examples of dicarboxylic acid compounds, tricarboxylic acid compounds, or acid monoanhydrides of these carboxylic acid compounds used in the third step include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and chlorendo. They are acids, trimellitic acid, and acid monoanhydrides thereof, and two or more types can also be used in combination. Among these, tetrahydrophthalic anhydride, succinic anhydride, and trimellitic anhydride can be preferably used.

In the first step of radical polymerization, known radical polymerization initiators such as azo compounds and peroxides can be used, and the degree of polymerization can be controlled using known chain transfer agents, polymerization inhibitors, etc. It's okay. The reaction temperature can be appropriately set in consideration of the half-life temperature of the radical polymerization initiator used.

The addition reaction in the second step is carried out by heating to 90 to 120°C and stirring while blowing air in the presence of a catalyst such as triethylbenzylammonium chloride, 2,6-isobutylphenol, trisdimethylaminomethylphenol, etc. There is a way.

The third step is, for example, a method of heating at 90 to 130° C. and stirring in the presence of a catalyst such as triethylamine, tetraethylammonium bromide, triphenylphosphine, and the like.

In another method for producing the alkali-soluble resin containing a polymerizable unsaturated group as component (A), as a first step, the above-mentioned (meth)acrylic acid ester and a polymerizable unsaturated resin such as (meth)acrylic acid are used. A group-containing monocarboxylic acid compound is radically copolymerized in a solvent, and as a second step, a (meth)acrylic acid ester having a glycidyl group such as glycidyl (meth)acrylate is reacted with the carboxyl group in the copolymer. As a third step, there is also a method in which the hydroxyl group generated in the second step is reacted with the above-mentioned dicarboxylic acid compound, tricarboxylic acid compound, or acid monoanhydride of these carboxylic acid compounds.

In addition, when the polymerizable unsaturated group-containing alkali-soluble resin of component (A) has other units such as the above-mentioned styrene or monomaleimide, in any method, the above-mentioned styrene or monomaleimide is added in the first step. What is necessary is to copolymerize.

The weight average molecular weight (Mw) of the alkali-soluble resin (A) measured by gel permeation chromatography (GPC) in terms of polystyrene is usually 3,000 to 50,000, preferably 4,000 to 20,000. In the polymerizable unsaturated group-containing alkali-soluble resin having a unit structure of the present invention, if the weight average molecular weight is less than 3,000, the adhesion of the pattern during alkali development may decrease, and if the weight average molecular weight exceeds 50,000. In this case, the developability may be significantly reduced.

Further, the preferred range of the acid value of the alkali-soluble resin (A) is 30 to 200 mgKOH/g, more preferably 50 to 150 mgKOH/g. In the alkali-soluble resin containing a polymerizable unsaturated group having a unit structure of the present invention, if this value is less than 30 mgKOH/g, a residue tends to remain during alkaline development, and if it exceeds 200 mgKOH/g, the alkaline developer penetrates quickly. Both are unfavorable since peeling development occurs if the film is too thick. The acid value can be adjusted by the amount of carboxyl group present in X in the unit represented by general formula (2).

In the present invention, the weight average molecular weight of (A) is the value obtained by dissolving the sampled solution in tetrahydrofuran, measuring the molecular weight distribution with HLC-8220GPC manufactured by Tosoh Corporation, and calculating the weight average molecular weight in terms of standard polystyrene. For the acid value of component A, use the value obtained by dissolving the sampled solution in dioxane, performing neutralization titration with a 0.1N aqueous potassium hydroxide solution, and calculating the acid value in terms of solid content of the sample solution from the equivalence point. .

Next, (B) photopolymerizable monomers having at least two ethylenically unsaturated bonds include, for example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, Tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate 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, alkylene oxide-modified hexa(meth)acrylate of phosphazene, (meth)acrylic acid esters such as caprolactone-modified dipentaerythritol hexa(meth)acrylate, polyhydric alcohols such as pentaerythritol, dipentaerythritol, etc. Examples include vinylbenzyl ether compounds of polyhydric phenols such as phenol novolak, and addition polymers of divinyl compounds such as divinylbenzene. As these (B) photopolymerizable monomers having at least two ethylenically unsaturated bonds, only one type of compound may be used, or a plurality of them may be used in combination. Note that (B) the photopolymerizable monomer having at least two ethylenically unsaturated bonds does not have a free carboxyl group. Trifunctional or higher functionality is more preferred.

The blending ratio of component (B) is preferably 5 to 400 parts by weight, preferably 10 to 150 parts by weight, per 100 parts by weight of component (A). If the blending ratio of component (B) is more than 400 parts by mass per 100 parts by mass of component (A), the cured product after photocuring will become brittle, and the acid value of the coating film will be low in the unexposed areas. The solubility in an alkaline developer decreases, causing problems such as pattern edges becoming jagged and not sharp. On the other hand, if the blending ratio of component (B) is less than 5 parts by mass per 100 parts by mass of component (A), the proportion of photoreactive functional groups in the resin will be small and the formation of a crosslinked structure will not be sufficient, and Due to the high acid value of the resin component, the solubility in the alkaline developer in the exposed area increases, resulting in the formed pattern being thinner than the target line width or more likely to be missing. Problems may occur.

In addition, as the photopolymerization initiator of component (C), for example, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, 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-triazine systems 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-phenylsulfanylphenyl)butane-1,2-dione-2- Oxime-O-benzoate, 1-(4-methylsulfanylphenyl)butan-1,2-dione-2-oxime-O-acetate, 1-(4-methylsulfanylphenyl)butan-1-one oxime-O-acetate , ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(0-acetyloxime), methanone, (9-ethyl-6-nitro-9H -carbazol-3-yl)[4-(2-methoxy-1-methylethoxy)-2-methylphenyl]-, O-acetyloxime, methanone, (2-methylphenyl)(7-nitro-9,9- dipropyl-9H-fluoren-2-yl)-, acetyloxime, ethanone, 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]-, 1-(O- acetyloxime), ethanone, O-acyloxime compounds such as 1-(-9,9-dibutyl-7-nitro-9H-fluoren-2-yl)-,1-O-acetyloxime, benzyl dimethyl ketal, Sulfur compounds such as thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone , anthraquinones such as 2,3-diphenylanthraquinone, organic peroxides such as azobisisobutylnitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, etc. Examples include thiol compounds. Among these, it is preferable to use O-acyloxime compounds from the viewpoint of easily obtaining a photosensitive resin composition for a highly sensitive light-shielding film. These photopolymerization initiators (C) may be used alone or in combination. Note that the photopolymerization initiator as used in the present invention is used to include a sensitizer.

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

The amount of photopolymerization initiator used as component (C) is preferably 0.1 to 30 parts by weight, preferably 1 to 25 parts by weight based on the total of 100 parts by weight of components (A) and (B). It is better to be a member of the department. If the blending ratio of component (C) is less than 0.1 part by mass, the speed of photopolymerization will be slow and the sensitivity will decrease, while if it exceeds 30 parts by mass, the sensitivity will be too strong. The pattern line width becomes thicker than the pattern mask, which may cause problems such as the line width not being able to be reproduced faithfully to the mask, or the pattern edges being jagged and not being sharp.

Component (D) is a light-shielding component selected from black organic pigments, color-mixing organic pigments, and light-shielding materials, and preferably has excellent insulation, heat resistance, light resistance, and solvent resistance. Here, examples of the black organic pigment include perylene black, aniline black, cyanine black, and lactam black. Examples of mixed-color organic pigments include those obtained by mixing two or more pigments selected from red, blue, green, purple, yellow, cyanine, magenta, etc. to create a pseudo-black color. Examples of the light shielding material include chromium oxide, iron oxide, titanium black, and the like. As these (D) light-shielding components, only one type of compound may be used, or a plurality of them may be used in combination.

As the organic pigment used in the present invention, any known compound can be used without particular limitation, but it is preferable to use one that has been subjected to atomization processing and has a specific surface area of 50 m ² /g or more by the BET method. Specifically, azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, threne pigments, perylene pigments, perinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, Examples include thioindigo pigments, and specifically, the following C.I. I. Examples include, but are not limited to, compounds of the same name.
C. I. Pigment Red 2, 3, 4, 5, 9, 12, 14, 22, 23, 31, 38, 112, 122, 144, 146, 147, 149, 166, 168, 170, 175, 176, 177, 178 , 179, 184, 185, 187, 188, 202, 207, 208, 209, 210, 213, 214, 220, 221, 242, 247, 253, 254, 255, 256, 257, 262, 264, 266, 272 , 279 etc.;
C. I. Pigment Orange 5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81, etc.;
C. I. Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 55, 73, 74, 81, 83, 93, 95, 97, 109, 110, 111, 117, 120, 126, 127, 128, 129 , 130, 136, 138, 139, 150, 151, 153, 154, 155, 173, 174, 175, 176, 180, 181, 183, 185, 191, 194, 199, 213, 214, etc.;
C. I. Pigment Green 7, 36, 58, etc.;
C. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, 80, etc.;
C. I. Pigment violet 19, 23, 37, etc.

Examples of the solvent for component (E) include methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy-2-butanone, Alcohols such as diacetone alcohol, terpenes such as α- or β-terpineol, ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, etc., aromatic carbonization of toluene, xylene, tetramethylbenzene, etc. Hydrogens, 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, Glycol ethers such as triethylene glycol monomethyl ether and triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve Examples include esters such as acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc., and by dissolving and mixing them, a uniform The composition can be in the form of a solution. Two or more types of these solvents may be used in order to achieve necessary properties such as coatability.

The light-shielding component (D) is preferably dispersed in advance together with the dispersant (F) in a solvent to form a light-shielding dispersion, and then blended into the photosensitive resin composition for the light-shielding film. Here, the solvent for dispersion becomes a part of component (E), so any solvent listed for component (E) above can be used, such as propylene glycol monomethyl ether acetate, 3-methoxybutyl Acetate and the like are preferably used.

Regarding the blending ratio of the light-shielding component (D) forming the light-shielding dispersion, it is used in the range of 5 to 80% by mass based on the total solid content of the photosensitive resin composition for the light-shielding film of the present invention. good. In addition, the solid content means components other than component (E) in the composition. The solid content also includes component (B) which becomes a solid content after photocuring. If it is less than 5% by mass, it will not be possible to set the desired light-shielding properties. If it exceeds 80% by mass, the content of the photosensitive resin that is the original binder decreases, resulting in undesirable problems such as impairing development characteristics and film-forming ability.

It is preferable that the average particle diameter (hereinafter referred to as "average secondary particle diameter") of the light-shielding component in this light-shielding dispersion as measured by a laser diffraction/scattering particle size distribution analyzer is as follows. When using a black organic pigment, a mixed color organic pigment, and/or a monochrome organic pigment, the average secondary particle size of the dispersed particles is preferably 20 to 500 nm. In addition, also in the photosensitive resin composition for a light-shielding film prepared by blending these light-shielding dispersions, it is preferable that these light-shielding components have the same average secondary particle size.

In addition, (F) a dispersant is used in the light-shielding dispersion liquid in order to stably disperse the light-shielding component, and for this purpose, known dispersants such as various polymer dispersants can be used. . As examples of dispersants, known compounds conventionally used for pigment dispersion (compounds commercially available under the names of dispersants, dispersion wetting agents, dispersion accelerators, etc.) can be used without particular limitation. Examples of the dispersant include cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, pigment derivative dispersants (dispersing 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, has an amine value of 1 to 100 mgKOH/g, and has a number average molecular weight. A cationic polymer dispersant having a molecular weight in the range of 1,000 to 100,000 is suitable. The blending amount of the dispersant (F) is preferably 1 to 30% by mass, preferably 2 to 25% by mass based on the light shielding component.

Furthermore, when preparing a light-shielding dispersion liquid, in addition to the above-mentioned (F) dispersant, a part of the alkali-soluble resin containing a polymerizable unsaturated group of component (A) is co-dispersed. When used as a photosensitive resin composition, the photosensitive resin composition can easily maintain high exposure sensitivity, has good adhesion during development, and is less likely to cause problems with residue. The blending amount of component (A) in the light-shielding dispersion is preferably 2 to 20% by mass, more preferably 5 to 15% by mass. If the amount of component (A) is less than 2% by mass, the effects of codispersion such as improved sensitivity, improved adhesion, and reduced residue cannot be obtained. In addition, if the content is 20% by mass or more, the viscosity of the light-shielding dispersion liquid will be high, especially when the content of the light-shielding material is large, and it will be difficult or very time-consuming to disperse the light-shielding material uniformly. It becomes difficult to obtain a photosensitive resin composition for obtaining a coating film in which components are dispersed.

The light-shielding dispersion thus obtained contains the (A) component (if the (A) component is co-dispersed when preparing the light-shielding dispersion, the remaining (A) component), (B) A photosensitive resin composition for a light-shielding film can be obtained by mixing the above component, the component (C), and the remaining component (E).

In addition, the photosensitive resin composition of the present invention may optionally contain a curing accelerator, a thermal polymerization inhibitor, an antioxidant, a plasticizer, a filler, a solvent, a leveling agent, an antifoaming agent, a coupling agent, an interface. (H) additives such as activators can be blended. Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, and hindered phenol compounds. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, and phosphorus. Examples of fillers include glass fiber, silica, mica, alumina, etc., and antifoaming agents and leveling agents include silicone-based, fluorine-based, and acrylic compounds. be able to. In addition, examples of the surfactant include fluorine-based surfactants and silicone-based surfactants, and examples of the coupling agent include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, Examples include silane coupling agents such as 3-isocyanatopropyltriethoxysilane and 3-ureidopropyltriethoxysilane.

The photosensitive resin composition of the present invention may also contain other resin components that are polymerized or cured by heat. As other resin components, (G) epoxy resins or epoxy compounds having two or more epoxy groups are preferred, such as 3,3',5,5'-tetramethyl-4,4'-biphenol type epoxy resins, bisphenol Type A epoxy resin, bisphenol fluorene type epoxy resin, phenol novolac type epoxy resin, 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate, 2,2-bis(hydroxymethyl)-1-butanol 1,2-epoxy-4-(2-oxiranyl)cyclohexane adducts, epoxy silicone resins, and the like. As these additional components, only one type of compound may be used, or a plurality of them may be used in combination.

The photosensitive resin composition of the present invention contains the above-mentioned components (A) to (E) as main components. It is desirable that the solid content contains components (A) to (D) in a total of 70% by mass, preferably 80% by mass or more. (E) The amount of the solvent varies depending on the target viscosity, but it is preferably contained in the photosensitive resin composition in the range of 60 to 90% by mass.

The photosensitive resin composition for a light-shielding film in the present invention is excellent as a photosensitive resin composition for forming a light-shielding film having a spacer function, for example. As a method for forming a light-shielding film having a spacer function, there is the following photolithography method. First, the photosensitive resin composition for the light-shielding film of the present invention is applied onto a base material, and then the solvent is dried (prebaking). A photomask is applied onto the film thus obtained, and ultraviolet light is applied. An example of this method is to irradiate the pattern to harden the exposed area, perform development to elute the unexposed area using an alkaline aqueous solution to form a pattern, and then perform post-bake (thermal baking) as post-drying.

The above-mentioned base material may be a transparent substrate, or a transparent substrate such as an alignment film formed on the pixel, on a flattening film on the pixel, or on a flattening film on the pixel after forming pixels such as RGB. Other base materials may also be used. Furthermore, the substrate may be an array substrate on which TFTs are formed.

The type of base material on which a light-shielding film having a spacer function is formed depends on the design of the liquid crystal display device. For example, when the light-shielding film is BCS and a region functioning as a black matrix is provided on the TFT, an array substrate may be used as the substrate. In addition, when the region functioning as the black matrix is provided on a substrate opposite to the substrate on which TFTs are formed in a liquid crystal display device, or when manufacturing a liquid crystal display device without TFTs, the substrate may be glass or the like. A transparent substrate can be used.

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

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 device and its exposure irradiation conditions are appropriately selected, and exposure is performed using a light source such as an ultra-high-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a far-ultraviolet lamp, etc., and the photosensitive resin composition in the coating film is photocured. At this time, by providing regions with different exposure amounts using a halftone mask or the like, regions with different heights (such as a region with a film thickness H1 and a region with a film thickness H2, which will be described later) can be formed at the same time.

Alkaline development after exposure is performed for the purpose of removing the resist in unexposed areas, and a desired pattern is formed by this development. Examples of developing solutions suitable for this alkaline development include aqueous solutions of carbonates of alkali metals and alkaline earth metals, aqueous solutions of alkali metal hydroxides, and particularly sodium carbonate, potassium carbonate, lithium carbonate, etc. It is best to develop at a temperature of 23 to 28°C using a weakly alkaline aqueous solution containing 0.05 to 3% by mass of carbonates such as carbonates. Can be formed precisely.

After development, heat treatment (post-bake) 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 increasing the adhesion between the patterned light-shielding film and the substrate. Similar to pre-baking, this is done by heating with an oven, hot plate, etc. The patterned light-shielding film of the present invention is formed through the steps of the photolithography method described above.

According to the above method, a light shielding film having an optical density of 0.5/μm to 3/μm, preferably 1.5/μm to 2.5/μm can be formed. Further, according to the above method, it is possible to form a light shielding film having a volume resistivity of 1×10 ⁹ Ω·cm or more, preferably 1×10 ¹² Ω·cm or more when a voltage of 10 V is applied. Further, according to the above method, a light shielding film having a dielectric constant of 2 to 10, preferably 2 to 8, more preferably 3 to 6 can be formed. Further, according to the above method, it is possible to form a light-shielding film that has a breaking strength of 200 mN or more, an elastic recovery rate of 30% or more, and/or a compressibility of 40% or less in a mechanical property test. . The light shielding film formed by the above method can be used as a column spacer of a liquid crystal display device, and preferably can be used as a black column spacer.

The substrate on which the light-shielding film or cured film is formed can be bonded to another substrate with a liquid crystal layer interposed therebetween to form a liquid crystal display (LCD). At this time, the above-mentioned light-shielding film or cured film is formed on the array substrate on which the TFTs are formed, and color resists such as red (R), green (G), and blue (B) are applied, exposed, developed, and baked. By bonding a color filter of each color to a transparent substrate, a COT and BOA (Black Matrix on Array) liquid crystal display device can be obtained. Furthermore, a COT liquid crystal display device can be obtained by forming the above-mentioned light-shielding film or cured film on a transparent substrate and bonding it to a COT substrate on which a color filter is formed on a TFT. On the other hand, the above-described light-shielding film or cured film and color filter may be formed on a transparent substrate and bonded to the TFT substrate. Among these, the above-mentioned light-shielding film or cured film having a low dielectric constant can be preferably used in a BOA liquid crystal display device.

In addition, according to the above method, the film thickness H1 for making the optical density of the light-shielding film 0.5/μm or more and less than 3/μm, and the film thickness H2 of the light-shielding film that plays a spacer function, H2 is 1 to 1. When the thickness is 7 μm, a light shielding film having a thickness H1 and a light shielding film having a thickness H2 in which ΔH=H2−H1 is 0.1 to 6.9 can be simultaneously formed. A more preferable range is H2 of 2 to 5 μm and ΔH of 0.1 to 4.9, and an even more preferable range of H2 is 2 to 4 μm and ΔH of 0.1 to 2.9. The cured film formed by the above method can be used as a column spacer of a liquid crystal display device, and preferably can be used as a black column spacer. According to the cured film in which the ΔH is within the above range, black column spacers having different heights can be formed at once from the same material, so that liquid crystal display devices can be manufactured more efficiently. At this time, for example, the cured film having a thickness of H2 may function as a spacer, and the cured film having a thickness of H1 may function as a black matrix.

Further, according to the above method, the cross-sectional shape is a combination of trapezoids or rectangles with different base lengths, and the upper side of the trapezoid or rectangle having a larger width is the lower side of the trapezoid or rectangle having a smaller width. A black column spacer with a stepped portion, in which the bottom side is in contact with the top side and has a shorter length than the above-mentioned top side, can also be formed at the same time from the same material, making the manufacturing of liquid crystal display devices more efficient. can do well. In other words, according to the above method, a black column spacer in which a portion with a thickness H1 and a portion with a thickness H2 are simultaneously included in the same light-shielding film is also made of the same material. Since it can be formed at once with one exposure, it is possible to manufacture a liquid crystal display device more efficiently. In addition, in the above combination shape, when the black column spacer is cut at a certain height from the bottom surface, the shape of the part higher than the cut surface is "a combination of trapezoidal or rectangular cross-sectional shapes with different base lengths". If the surface of the underlying TFT has a step or recess, the actual bottom surface should be made to cover the step or fill the recess without any gaps, according to the surface shape of the TFT. It may be of any shape.

In addition, when forming black column spacers with the above-mentioned height differences or black column spacers whose cross-sectional shape is a combination of trapezoids or rectangles with different base lengths, a black organic pigment should be used as the light-shielding component. is preferred, and it is particularly preferred to use 20 to 50% by mass of black organic pigment in the solid content. It is also possible to collectively form a black column spacer with a higher optical density by using an inorganic black pigment such as carbon black as a part of the black organic pigment, but in this case, the ratio of the inorganic black pigment is The total amount of organic pigment and inorganic black pigment is preferably in the range of 10 to 20% by mass. The carbon black used at this time is preferably resin-coated carbon black from the viewpoint of increasing the insulation of the black column spacer and lowering the dielectric constant when the same amount is added.

The liquid crystal display device having the light shielding film or the cured film is preferably a TFT-LCD provided with a thin film transistor.

The liquid crystal display device having the above-mentioned light-shielding film or cured film has high light-shielding properties and insulation properties, has a spacer function with excellent compressibility, elastic recovery rate, and breaking strength, and has a film thickness of about 1 to 7 μm. A fine spacer shape can be formed even if

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

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

[Solid content concentration]
A glass filter [weight: W0 (g)] was impregnated with 1 g of the resin solution obtained in the synthesis example and weighed [W1 (g)], and the weight after heating at 160 ° C. for 2 hours [W2 (g)] It was calculated from the following formula.
Solid content concentration (wt%) = 100 x (W2-W0)/(W1-W0).

[Acid value]
It was determined by dissolving a resin solution in dioxane and titrating it with a 1/10N-KOH aqueous solution using a potentiometric titration device [manufactured by Hiranuma Sangyo Co., Ltd., trade name COM-1600].

[Molecular weight]
Gel permeation chromatography (GPC) [trade name HLC-8220GPC manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2 pieces) + TSKgelSuperH-3000 (1 piece) + TSKgelSuperH-4000 (1 piece) + TSKgelSuper-H5 000 (1 bottle) [manufactured by Tosoh Corporation], temperature: 40°C, speed: 0.6ml/min], and the weight average molecular weight (Mw) was calculated as a standard polystyrene [PS-oligomer kit manufactured by Tosoh Corporation]. I asked for

[Average secondary particle size measurement]
The light-shielding dispersion liquid was diluted with a solvent (PGMEA in this example), and a solution with a light-shielding component concentration of about 0.1% by mass was measured using a laser diffraction/scattering particle size distribution analyzer (manufactured by Nikkiso Co., Ltd., Microtrac MT). -3000) was used to measure the average secondary particle size.

Further, the abbreviations used in the synthesis examples and comparative synthesis examples are as follows.
BzMA: Benzyl methacrylate DCPMA: Dicyclopentanyl methacrylate GMA: Glycidyl methacrylate St: Styrene MMA: Methyl methacrylate MAA: Methacrylic acid AA: Acrylic acid THPA: Tetrahydrophthalic anhydride SA: Succinic anhydride AIBN: Azobisisobutyronitrile TDMAMP : Trisdimethylaminomethylphenol HQ: Hydroquinone TPP: Triphenylphenol DTBPC: 2,6-di-tert-butyl-p-cresol TEA: Triethylamine PGMEA: Propylene glycol monomethyl ether acetate

[Synthesis example 1]
300 g of PGMEA was placed in a 1 L four-necked flask equipped with a reflux condenser, and the temperature was raised to 120° C. after purging the inside of the flask with nitrogen. A monomer mixture (a mixture of 52.9 g (0.30 mol) of BzMA, 77.1 g (0.35 mol) of DCPMA, and 10 g of AIBN dissolved in 49.8 g (0.35 mol) of GMA) was added to this flask from the dropping funnel for 2 hours. The mixture was added dropwise, and further stirred at 120°C for 2 hours to obtain a copolymer solution.
Next, after purging the inside of the flask with air, 24.0 g of AA (95% of glycidyl groups), 0.8 g of TDMAMP, and 0.15 g of HQ were added to the obtained copolymer solution, and the mixture was heated at 120°C for 6 hours. The mixture was stirred to obtain a polymerizable unsaturated group-containing copolymer solution. Furthermore, 45.7 g of THPA (90% of the number of moles added of AA) and 0.5 g of TEA were added to the obtained copolymer solution containing a polymerizable unsaturated group, and the mixture was reacted at 120°C for 4 hours. A soluble copolymer resin solution (A)-1 was obtained. The solid content concentration of the resin solution was 47% by mass, the acid value (solid content equivalent) was 62 mgKOH/g, and the Mw by GPC analysis was 8200.

[Synthesis example 2]
300 g of PGMEA was placed in a 1 L four-necked flask equipped with a reflux condenser, and the temperature was raised to 120° C. after purging the inside of the flask with nitrogen. In this flask, 10 g of AIBN was added to a monomer mixture (35.2 g (0.20 mol) of BzMA, 77.1 g (0.35 mol) of DCPMA, 49.8 g (0.35 mol) of GMA, 10.4 g (0.10 mol) of St). The dissolved mixture) was added dropwise from the dropping funnel over 2 hours, and the mixture was further stirred at 120°C for 2 hours to obtain a copolymer solution.

Next, after purging the inside of the flask with air, 24.0 g of AA (95% of glycidyl groups), 0.8 g of TDMAMP, and 0.15 g of HQ were added to the obtained copolymer solution, and the mixture was heated at 120°C for 6 hours. The mixture was stirred to obtain a polymerizable unsaturated group-containing copolymer solution.

Furthermore, 45.7 g of THPA (90% of the number of moles added of AA) and 0.5 g of TEA were added to the obtained copolymer solution containing polymerizable unsaturated groups, and the mixture was reacted at 120°C for 4 hours. An alkali-soluble copolymer resin solution (A)-2 was obtained. The solid content concentration of the resin solution was 46% by mass, the acid value (solid content equivalent) was 68 mgKOH/g, and the Mw by GPC analysis was 7900.

[Synthesis example 3]
300 g of PGMEA was placed in a 1 L four-necked flask equipped with a reflux condenser, and the temperature was raised to 120° C. after purging the inside of the flask with nitrogen. A monomer mixture (a mixture of 77.1 g (0.35 mol) of DCPMA, 49.8 g (0.35 mol) of GMA, and 10 g of AIBN dissolved in 31.2 g (0.30 mol) of St) was added to this flask from the dropping funnel for 2 hours. The mixture was added dropwise, and further stirred at 120°C for 2 hours to obtain a copolymer solution.

Next, after purging the inside of the flask with air, 24.0 g of AA (95% of glycidyl groups), 0.8 g of TDMAMP, and 0.15 g of HQ were added to the obtained copolymer solution, and the mixture was heated at 120°C for 6 hours. The mixture was stirred to obtain a polymerizable unsaturated group-containing copolymer solution.

Furthermore, 30.0 g of SA (90% of the number of moles added of AA) and 0.5 g of TEA were added to the obtained copolymer solution containing polymerizable unsaturated groups, and the mixture was reacted at 120° C. for 4 hours. An alkali-soluble copolymer resin solution (A)-3 was obtained. The solid content concentration of the resin solution was 46% by mass, the acid value (solid content equivalent) was 76 mgKOH/g, and the Mw by GPC analysis was 5300.

[Comparative synthesis example 1]
370 g of PGMEA was placed in a 1 L four-necked flask equipped with a reflux condenser, and the temperature was raised to 90° C. after purging the inside of the flask with nitrogen. A monomer mixture (a mixture of 38.8 g (0.22 mol) of BzMA, 38.4 g (0.38 mol) of MMA, and 6 g of AIBN dissolved in 51.7 g (0.60 mol) of MAA) was added into this flask using a dropping funnel. The mixture was added dropwise over 2 hours, and further stirred at 90°C for 8 hours to obtain a copolymer solution.

Next, after purging the inside of the flask with air, 39.2 g of GMA (50% of carboxyl groups), 1.4 g of TPP, and 0.06 g of DTBPC were added to the obtained copolymer solution, and the mixture was heated at 90°C. The mixture was stirred for 6 hours to obtain a polymerizable unsaturated group-containing alkali-soluble copolymer resin solution (A)-4. The solid content concentration of the resin solution was 32% by mass, the acid value (in terms of solid content) was 110 mgKOH/g, and the Mw by GPC analysis was 18,100.

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

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

(Photopolymerization initiator)
(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 dispersed pigment)
(D)-1: PGMEA dispersion containing 15.0% by mass of black pigment (lactam black Irgaphor S0100CF manufactured by BASF) and 4.5% by mass of polymer dispersant (solid content 19.5%, average secondary particles of black pigment) diameter 241nm)
(D)-2:C. I. Pigment Orange 64 (manufactured by BASF) 7.0% by mass, C.I. I. Pigment Violet 23 (manufactured by Clariant) 3.0% by mass, C.I. I. Pigment Blue 15:6 (manufactured by Clariant) 7.0% by mass, polymer dispersant concentration 4.0% by mass, sulfonated azo dispersion aid 2.0% by mass, benzyl methacrylate/methacrylic acid copolymer 2 .0 mass % PGMEA dispersion (25.0% solids)
(D)-3: PGMEA dispersion with carbon black 20.0% by mass and polymer dispersant concentration 5.0% by mass (solid content 25.0%, average secondary particle size of carbon black 162 nm)
(D)-4: PGMEA dispersion with resin-coated carbon black 25.0% by mass and polymer dispersant concentration 5.0% by mass (solid content 30.0%, average secondary particle size of carbon black 90 nm)

(solvent)
(E)-1: PGMEA
(E)-2:3-methoxy-3-methylbutyl acetate

(surfactant)
(H): PGMEA solution of BYK-330 (manufactured by BYK Chemie) (solid content 1.0%)

Photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 2 were prepared by blending the above ingredients in the proportions shown in Table 1. In addition, all the numerical values in Table 1 represent the compounding amount (g). In addition, (E)-1 in the solvent column refers to PGMEA (same as (E)-1) in an unsaturated group-containing resin solution (polymerizable unsaturated group-containing alkali-soluble resin solution) and a light-shielding dispersion. This is the amount that does not contain PGMEA (same as (E)-1).

[evaluation]
The following evaluations were conducted using the photosensitive resin compositions for light-shielding films of Examples 1 to 7 and Comparative Examples 1 to 2. These evaluation results are shown in Table 2.

<Development characteristics>
Each of the photosensitive resin compositions obtained above was applied onto a glass substrate with a thickness of 1.2 mm using a spin coater so that the film thickness after thermosetting was 3.0 μm, and heated at 90°C for 1. Prebaked for a minute. Thereafter, a photomask was placed in close contact with the film, and ultraviolet rays of 100 mJ/cm ² were irradiated with an ultra-high pressure mercury lamp having a wavelength of 365 nm and an illumination intensity of 30 mW/cm ² to perform a photocuring reaction on the photosensitive areas.

Next, this exposed glass substrate was developed using a 0.05% potassium hydroxide aqueous solution at 24° C. and a pressure of 0.1 MPa for 60 seconds to remove the unexposed portion of the coating film. Thereafter, heat curing treatment was performed at 230° C. for 30 minutes using a hot air dryer to obtain a cured film of the photosensitive resin composition. Formation of fine lines in the obtained cured film pattern was confirmed using an optical microscope and evaluated on the following three scales. The results are shown in Table 2.
○: A pattern with an L/S of 10 μm/10 μm or more is formed without any residue. △: A pattern with an L/S of 30 μm/30 μm or more is formed without a residue. ×: L/S is less than 50 μm/50 μm. No pattern has been formed, or the pattern has noticeable hemming or residue.

<Optical density>
Each of the photosensitive resin compositions obtained above was coated onto a glass substrate with a thickness of 1.2 mm using a spin coater so that the film thickness after heat curing treatment was 1.1 μm, and the coating was heated at 90°C for 1.2 μm. Prebaked for a minute. Thereafter, heat curing treatment was performed at 230° C. for 30 minutes using a hot air dryer to obtain a cured film of the photosensitive resin composition. Next, the optical density of the obtained cured film was measured using a Macbeth transmission densitometer, and evaluated in terms of optical density per unit film thickness.

<Volume resistivity>
Each of the photosensitive resin compositions obtained above was applied onto a 1.2 mm thick Cr-deposited glass substrate, excluding the electrodes, using a spin coater so that the film thickness after heat curing was 3.5 μm. It was coated so as to have the following properties, and prebaked at 90°C for 1 minute. Thereafter, heat curing treatment was performed at 230° C. for 30 minutes using a hot air dryer to obtain a cured film of the photosensitive resin composition. Thereafter, an aluminum electrode was formed on the cured film to create a substrate for measuring volume resistivity. Next, the volume resistivity was measured at an applied voltage of 1 V to 10 V using an electrometer (manufactured by Keithley, Model 6517A). Measurement was performed under the condition that each applied voltage was held for 60 seconds in 1 V steps, and the volume resistivity when 10 V was applied is shown in Table 2.

<Permittivity>
Each of the photosensitive resin compositions obtained above was applied onto a 1.2 mm thick Cr-deposited glass substrate, excluding the electrodes, using a spin coater so that the film thickness after heat curing was 3.5 μm. It was coated so as to have the following properties, and prebaked at 90°C for 1 minute. Thereafter, heat curing treatment was performed at 230° C. for 30 minutes using a hot air dryer to obtain a cured film of the photosensitive resin composition. Thereafter, an aluminum electrode was formed on the cured film to create a substrate for dielectric constant measurement. Next, the capacitance at a frequency of 1 Hz to 100,000 Hz was measured using an electrometer (manufactured by Keithley, Model 6517A), and the dielectric constant was calculated from the capacitance. The calculated dielectric constants are shown in Table 2.

<Spacer halftone (HT) characteristics>
Each of the photosensitive resin compositions obtained above was applied onto a glass substrate with a thickness of 1.2 mm using a spin coater so that the film thickness after thermosetting was 3.0 μm, and heated at 90°C for 1. Prebaked for a minute. Thereafter, a photomask with a dot pattern was placed in close contact with the photosensitive area, and ultraviolet rays of 5 mJ/cm ² or 100 mJ/cm ² were irradiated using an ultra-high pressure mercury lamp with a wavelength of 365 nm and an illuminance of 30 mW/cm ² to perform a photocuring reaction on the photosensitive area. .
Next, this exposed glass substrate was developed using a 0.05% potassium hydroxide aqueous solution at 24° C. and a pressure of 0.1 MPa for 60 seconds to remove the unexposed portion of the coating film. Thereafter, heat curing treatment was performed at 230° C. for 30 minutes using a hot air dryer to obtain a cured film of the photosensitive resin composition.

The halftone characteristics of the spacer are determined by calculating the difference (ΔH) between the thickness of the light-shielding film (H1) at an exposure dose of 5 mJ/ ^cm2 and the film thickness (H2 ⁾ of the spacer at an exposure dose of 100 mJ/cm2, and using the following four steps. evaluated. The results are shown in Table 2.
○: When ΔH is 1.0 μm to 2.0 μm △: When ΔH is 0.1 μm to 2.9 μm ×: When ΔH is less than 0.1 μm or greater than 2.9 μm

<Spacer compressibility, elastic recovery rate, and fracture strength>
Each of the photosensitive resin compositions obtained above was applied onto a glass substrate with a thickness of 1.2 mm using a spin coater so that the film thickness after thermosetting was 3.0 μm, and heated at 90°C for 1. Prebaked for a minute. Thereafter, a photomask having a dot pattern was placed in close contact with the film, and ultraviolet rays of 100 mJ/cm ² were irradiated with an ultra-high pressure mercury lamp having a wavelength of 365 nm and an illuminance of 30 mW/cm ² to perform a photocuring reaction on the photosensitive areas.

Next, this exposed glass substrate was developed using a 0.05% potassium hydroxide aqueous solution at 24° C. and a pressure of 0.1 MPa for 60 seconds to remove the unexposed portion of the coating film. Thereafter, heat curing treatment was performed at 230° C. for 30 minutes using a hot air dryer to obtain a cured film of the photosensitive resin composition.

The spacer properties of the obtained cured film pattern were evaluated using an ultra-micro hardness meter (Fisherscope HM2000Xyp, manufactured by Fischer Instruments). A 100 μm square flat indenter was pushed in at a loading rate of 5.0 mN/sec, a load of up to 50 mN was applied, and then the load was unloaded at an unloading rate of 5.0 mN/sec to create a displacement curve. The compression ratio was calculated from the following formula, with L1 being the amount of displacement under a load of 50 mN.
Compression rate (%) = L1/spacer height x 100

The elastic recovery rate was calculated from the following formula, where L1 is the amount of displacement at a load of 50 mN during loading, and L2 is the amount of displacement at unloading.
Elastic recovery rate (%) = (L1-L2)/L1×100

The breaking strength was evaluated using an ultra-microhardness meter (Fisherscope HM2000Xyp, manufactured by Fisher Instruments). A 100 μm square flat indenter was pushed in at a loading rate of 5.0 mN/sec, a load of up to 300 mN was applied, and the load at which the spacer broke was measured and evaluated on the following four levels. The results are shown in Table 2.
○: When the breaking strength is 300 mN or more △: When the breaking strength is 200 mN or less ×: When the breaking strength is 100 mN or less

<Shape of spacer>
Each of the photosensitive resin compositions obtained above was applied onto a glass substrate with a thickness of 1.2 mm using a spin coater so that the film thickness after thermosetting was 3.0 μm, and heated at 90°C for 1. Prebaked for a minute. Thereafter, a photomask having a dot pattern was placed in close contact with the film, and ultraviolet rays of 100 mJ/cm ² were irradiated with an ultra-high pressure mercury lamp having a wavelength of 365 nm and an illuminance of 30 mW/cm ² to perform a photocuring reaction on the photosensitive areas.

Next, this exposed glass substrate was developed using a 0.05% potassium hydroxide aqueous solution at 24° C. and a pressure of 0.1 MPa for 60 seconds to remove the unexposed portion of the coating film. Thereafter, heat curing treatment was performed at 230° C. for 30 minutes using a hot air dryer to obtain a cured film of the photosensitive resin composition.

The shape of the spacer was evaluated by the internal angle (taper angle) of the spacer end using a scanning electron microscope. If the taper angle is 70° or more and 90° or less, it is ◎, if it is 50° or more and less than 70°, it is ○, if it is 50° or less, it is △, and if it is 90° or more, it is marked ×.

From the results of Examples 1 to 7 and Comparative Examples 1 to 2, the cured products of the photosensitive resin compositions of the present invention have high light shielding properties (optical density) and insulation properties (volume resistivity) when used as black column spacers. It is possible to form a light-shielding film having a spacer function with excellent compressibility, elastic recovery rate, and breaking strength, and it is also possible to form a step of ΔH to form a pattern shape that is more nearly vertical.

Next, in order to confirm whether it is possible to form a pattern by exposure and development so that the cross-sectional shape is a combination of trapezoids or rectangles with different base lengths, we tested Examples 8 and 9 and Comparative Examples 3 and 4. A photosensitive resin composition was blended as shown in Table 3 to obtain a photosensitive resin composition.

Similar evaluations were carried out using the photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 and 2, except for the shape of the spacer, and the photosensitive resin compositions of Examples 8 and 9 and Comparative Examples 3 and 4. Table 4 summarizes the evaluation results. As for the shape of the spacer, the detailed cross-sectional shape of the formed pattern was observed using a separate evaluation method described below.

<Detailed cross-sectional shape of spacer>
The photosensitive resin compositions obtained in Examples 8 and 9 and Comparative Examples 3 and 4 were coated on a glass substrate with a thickness of 1.2 mm using a spin coater so that the film thickness after thermosetting was 3.0 μm. It was coated so as to have the following properties, and prebaked at 90°C for 1 minute. After that, a photomask (halftone mask) having line patterns with different total light transmittances of 20% and 100% was fixed at a distance of 200 μm from the film surface, and ultra-high pressure mercury was used with an illuminance of 30 mW/cm ² at a wavelength of 365 nm. Ultraviolet rays of 100 mJ/cm ² were irradiated with a lamp to perform a photocuring reaction on the photosensitive areas. The photomask was a halftone mask in which the area 25 μm to the left and right from the center of the mask opening had a total ray transmittance of 100%, and the area outside the mask opening 25 μm to 100 μm from the center had a total ray transmittance of 20%.

Next, this exposed glass substrate was developed using a 0.05% potassium hydroxide aqueous solution at 24° C. and a pressure of 0.1 MPa for 180 seconds to remove the unexposed portion of the coating film. Thereafter, heat curing treatment was performed at 230° C. for 30 minutes using a hot air dryer to obtain a cured film of the photosensitive resin composition.

The cross-sectional shape of the spacer was determined by obtaining the height profile of the pattern using a three-dimensional white light interference optical microscope (Contour GT-K manufactured by Bruker) in the white vertical scanning interferometry mode (VSI), and plotting it in two dimensions. The processed material was obtained as a cross-sectional shape. 1 to 4 show cross-sectional shapes subjected to the two-dimensional plot processing. FIG. 1 is a height profile of a pattern formed using the photosensitive resin composition of Example 8, and FIG. 2 is a height profile of a pattern formed using the photosensitive resin composition of Example 9. 3 is the height profile of the pattern formed using the photosensitive resin composition of Comparative Example 3, and FIG. 4 is the height profile of the pattern formed using the photosensitive resin composition of Comparative Example 4. It is a profile. In FIGS. 1 to 4, the horizontal axis shows the distance from the mask opening, and the vertical axis shows the film thickness. Note that the line indicated by M indicates the center of the mask opening. The line indicated by R indicates the central part of the area where the total light transmittance is 20%. The line marked R appears on both sides with respect to the center of the mask opening, but only one side is shown in FIGS. 1-4.

As shown in FIGS. 1 and 2, by performing exposure and development using a halftone mask using the photosensitive resin composition of the present invention, the cross-sectional shape has different base lengths as shown in FIGS. 1 and 2. BCS having a trapezoidal or rectangular combination shape could be formed all at once.

As shown in FIGS. 3 and 4, in Comparative Examples 3 and 4 using resins other than the polymerizable unsaturated group-containing alkali-soluble resin of the present invention, the cross-sectional shape was a combination of trapezoids or rectangles with different base lengths. It was not possible to form the BCS at once, and only patterns with a trapezoidal or rectangular cross-section or a semicircular cross-section could be obtained.

Claims (16)

Contains components (A) to (E) as essential components (but does not include carbon black that is not coated with resin) ,
(A) Contains 5 to 90 mol% of units represented by general formula (1) and 10 to 95 mol% of units represented by general formula (2) (units represented by general formula (1) and general (the total with the unit represented by formula (2) is 100 mol%), a weight average molecular weight of 3000 to 50000, and an acid value of 30 to 200 mg/KOH. (excluding those having a residue derived from a compound represented by general formula (X)),

(However, R ₁ , R ₃ and R ₄ independently represent a hydrogen atom or a methyl group. _{R 2} represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group has an ether bond inside, It may contain an ester bond or a urethane bond.In addition, 40 mol% or more of the units represented by the general formula (1) in _R2 is a dicyclopentanyl group or a dicyclopentenyl _group.R5 is a carbon It represents a divalent hydrocarbon group of numbers 2 to 10. p represents the number 0 or 1. X is a hydrogen atom or -OC-Y-(COOH)q (however, Y is a divalent or trivalent carboxylic acid Represents a residue, and q represents a number from 1 to 2. Also, two or more types of X are contained in one molecule of the polymer.)

(In the formula, Ra to Re each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms that may have a substituent.)
(B) a photopolymerizable monomer having at least two ethylenically unsaturated bonds;
(C) photopolymerization initiator,
(D) one or more light-shielding components selected from the group consisting of a black organic pigment having an average secondary particle size of 20 to 500 nm and a light-shielding material ; and (E) a solvent.
10 to 150 parts by mass of component (B) per 100 parts by mass of component (A),
0.1 to 30 parts by mass of component (C) per 100 parts by mass of the total amount of components (A) and (B),
When the solid content is a component including the component (B) that becomes a solid content after photocuring, but excluding the component (E),
(D) component, 5 to 80% by mass of the total solid content,
Each includes
A photosensitive resin composition for a light-shielding film, comprising a total of 80% by mass or more of components (A) to (D) in solid content. Contains components (A) to (E) as essential components,
(A) Contains 5 to 90 mol% of units represented by general formula (1) and 10 to 95 mol% of units represented by general formula (2) (units represented by general formula (1) and general (the total with the unit represented by formula (2) is 100 mol%), a weight average molecular weight of 3000 to 50000, and an acid value of 30 to 200 mg/KOH. (excluding those having a residue derived from a compound represented by general formula (X)),

(However, R ₁ ,R ₃ and R ₄ independently represent a hydrogen atom or a methyl group. R ₂ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may contain an ether bond, ester bond, or urethane bond inside. Also, R ₂ In the unit represented by the general formula (1), 40 mol% or more is a dicyclopentanyl group or a dicyclopentenyl group. R ₅ represents a divalent hydrocarbon group having 2 to 10 carbon atoms. p represents the number 0 or 1. X is a hydrogen atom or -OC-Y-(COOH)q (where, Y represents a divalent or trivalent carboxylic acid residue, and q represents a number of 1 to 2. contains two or more types.)

(In the formula, Ra to Re each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms that may have a substituent.)
(B) a photopolymerizable monomer having at least two ethylenically unsaturated bonds;
(C) photopolymerization initiator,
(D) mixed color organic pigment, and
(E) solvent;
10 to 150 parts by mass of component (B) per 100 parts by mass of component (A),
0.1 to 30 parts by mass of component (C) per 100 parts by mass of the total amount of components (A) and (B),
When the solid content is a component including the component (B) that becomes a solid content after photocuring, but excluding the component (E),
(D) component, 5 to 80% by mass of the total solid content,
Each includes
Contains 80% by mass or more of components (A) to (D) in total in solid content
A photosensitive resin composition for a light-shielding film, characterized by: The photosensitive resin composition according to claim 2, wherein the color mixing organic pigment has an average secondary particle size of 20 to 500 nm. The polymerizable unsaturated group-containing alkali-soluble resin of component (A) contains, in addition to the units of general formulas (1) and (2), units derived from styrene which may have a substituent on the phenyl group; The photosensitive resin composition according to any one of claims 1 to 3 , which is a copolymer containing a unit derived from a monomaleimide compound. A light shielding film having an optical density OD of 0.5/μm or more and 3/μm or less, a volume resistivity of 1×10 ⁹ Ω・cm or more when a voltage of 10 V is applied, and a dielectric constant of 2 to 10. The photosensitive resin composition according to any one of claims 1 to 4 , which is capable of forming a film. The method according to any one of claims 1 to 5 , which is capable of forming a light-shielding film that satisfies at least one of the following (i) to (iii) in a loading-unloading test using a microhardness meter. Photosensitive resin composition.
(i) Breaking strength is 200 mN or more (ii) Elastic recovery rate is 30% or more (iii) Compressibility is 40% or less A light-shielding film characterized by being a cured product of the photosensitive resin composition according to any one of claims 1 to 6 . A liquid crystal display device comprising the light shielding film according to claim 7 as a black column spacer (BCS). 9. The liquid crystal display device according to claim 8 , further comprising a thin film transistor (TFT). A liquid crystal display device comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 6 as a black matrix. 11. The black matrix further comprises a thin film transistor (TFT), and the black matrix is disposed between the liquid crystal and a substrate facing the array substrate on which the thin film transistor (TFT) is formed. The liquid crystal display device described. The liquid crystal display according to claim 10 , further comprising a thin film transistor (TFT), and wherein the black matrix is disposed between the array substrate on which the thin film transistor (TFT) is formed and the liquid crystal. Device. A method for producing a light-shielding film formed on a substrate, comprising applying the photosensitive resin composition according to any one of claims 1 to 6 to a substrate, and curing the photosensitive resin composition by irradiation with light. Regarding the film thickness H1 of the light shielding film formed as a light shielding film having an optical density of 0.5/μm or more and less than 3/μm, and the film thickness H2 of the light shielding film serving as a spacer function, when H2 is 1 to 7 μm, A method for producing a light-shielding film having a spacer function, characterized by simultaneously forming a light-shielding film having a thickness H1 and a thickness H2 in which ΔH=H2-H1 is 0.1 to 6.9 μm. 14. The light-shielding film according to claim 13 , wherein a light-shielding film including a portion having the thickness H1 and a portion having the thickness H2 in a single light-shielding film is formed in one exposure. Production method. A method for manufacturing a liquid crystal display device, characterized in that the light shielding film manufactured by the method according to claim 13 or 14 is used as a black column spacer (BCS). 16. The method of manufacturing a liquid crystal display device according to claim 15 , wherein the liquid crystal display device includes a thin film transistor (TFT).

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