Photosensitive resin composition for light-shielding film, light-shielding film, liquid crystal display device, method for manufacturing a light-shielding film having a spacer function, and method for manufacturing a liquid crystal display device

Abstract

To provide a photosensitive resin composition with which a light-shielding film can be manufactured having a high light-shielding property and insulating property and excellent in compressibility, elastic recovery rate, and breaking strength, and in forming a light-shielding film having a spacer function, a pattern shape making it possible to form a difference ΔH and further closer to perpendicular can be formed.SOLUTION: The present invention is a photosensitive resin composition for a light-shielding film containing components (A) to (E) as essential components. (A) a polymerizable unsaturated group-containing alkali-soluble resin that is a polymer containing a unit derived from a (meth)acrylic ester compound and a unit having a (meth)acryloyl group and a di- or tri-carboxylic acid residue, and having a weight average molecular weight of 3000 to 50000 and an acid value of 30 to 200 mg / KOH; (B) a photopolymerizable monomer having at least two ethylenically unsaturated bonds; (C) a photopolymerization initiator; (D) a light-shielding component that is a black organic pigment, mixed organic pigment, or a light-shielding material; (E) a solvent.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition for a light-shielding film and a light-shielding film cured therefrom. Specifically, the present invention relates to a photosensitive resin composition and a cured film thereof, which can form 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 by a photolithography method. The present invention further relates to a liquid crystal display device using the black matrix or the black column spacer obtained by curing the above. The present invention further relates to a method for manufacturing a light-shielding film and a liquid crystal display device using the above photosensitive resin composition.

Background Art

[0002] In recent years, color liquid crystal display devices (LCDs) have been used in various fields such as liquid crystal televisions, liquid crystal monitors, and color liquid crystal mobile phones. Among these, in order to improve the performance of LCDs, improvements aiming at improving characteristics such as viewing angle, contrast, and response speed have been actively carried out, and various panel structures have been developed even in thin film transistor (TFT)-LCDs that are currently widely used. Regarding TFT-LCDs, a method has mainly been adopted in which an array substrate on which a conventional TFT is formed and a color filter substrate are each manufactured, and the two substrates are bonded together while being kept at a constant interval by a spacer. However, LCD manufacturing processes aiming at cost reduction and yield improvement have also been developed. For example, a manufacturing process has been developed in which a color filter is directly formed on the TFT of the array substrate and a glass substrate is bonded as the opposing substrate. The structure formed in this way is called color filter on TFT (COT) and the like. Also in this COT, various LCD panel structures are being studied, such as a method of forming a black matrix that forms the boundary of each pixel such as red (R), green (G), and blue (B) of the color filter layer formed on the TFT before forming the RGB pixels, a method of forming the RGB pixels and then forming the black matrix on top of them, or a method of forming the black matrix on the opposing glass substrate.

[0003] Regarding a spacer that functions to keep the thickness of the liquid crystal layer (the distance between the array substrate and the color filter (CF) substrate in the conventional method), which is one of the factors affecting the performance of the LCD, conventionally, a method of sandwiching ball spacers with a constant particle size has been adopted. However, this method has a problem that the light transmittance per pixel becomes non-uniform due to the non-uniform dispersion state of the ball spacers. To address this problem, a method of forming column spacers by photolithography has been adopted. However, column spacers formed by photolithography are often transparent, and such column spacers have a problem that light incident from an oblique direction affects the electrical characteristics of the TFT, deteriorating the display quality. In response to such problems, an LCD panel structure applying a light-shielding column spacer, which is a light-shielding film having a spacer function formed by photolithography, has been proposed (Patent Document 1). Also in COT, a method of forming a so-called black column spacer (BCS) in which column spacers are formed of the same material as the black matrix has been studied (for example, Patent Document 2).

[0004] This light-shielding column spacer requires a film thickness of about 2 to 7 μm to function as a spacer. Also, it is necessary that light-shielding column spacers with different heights can be formed simultaneously at the locations where TFTs are formed and other locations. Also, for the light-shielding column spacer, it is required that the elastic modulus, deformation amount, elastic recovery rate, etc. be within an appropriate range as spacer functions (Patent Document 3). Furthermore, for the light-shielding column spacer, it is also required to improve the reduction of the curable component due to the addition of a light-shielding component (coloring agent) to the spacer and the loss of electrical characteristics due to the influence of impurities in the coloring agent, etc. (Patent Document 4).

[0005] In addition, when an LCD panel manufacturer actually attempts to apply BCS, depending on the panel design, there are various required BCS shapes. For example, there is a design (Patent Document 5) that uses a BCS with a trapezoidal or rectangular cross-sectional shape, and there is also a design (Patent Document 6) that uses a BCS with a combined shape of trapezoids or rectangles with different base lengths in cross-section. The reason for using a combined shape is to integrally form a portion that only requires a light-shielding film function and a portion that also serves as a spacer function. Requirements for a photosensitive resin composition for a light-shielding film used to integrally form such cross-sectional shapes have also emerged.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Summary of the Invention

Problems to be Solved by the Invention

[0007] In Patent Document 4, a mixed-color organic pigment is used, but the optical density of the light-shielding column spacer is not shown. Although the mixed-color organic pigment is effective in reducing the dielectric constant compared to inorganic pigments such as carbon black, it often has low light-shielding properties. In addition, since it is necessary to simultaneously form spacers with different heights, the light-shielding column spacer is also required to have mechanical properties such as compression ratio, elastic recovery rate, and breaking strength. Since the shape and mechanical properties of such a spacer are greatly affected by the light-shielding component, it is difficult to design a photosensitive resin composition for a light-shielding film. Therefore, the shape and mechanical properties of spacers using carbon black, mixed-color organic pigments, etc. are not yet sufficient, and further improvement is required.

[0008] Also, as described above, the light-shielding column spacer is manufactured with a film thickness of about 1 to 7 μm. With the recent miniaturization of liquid crystal display elements, it is desired that the light-shielding column spacer can form a fine spacer shape even with a film thickness of about 1 to 7 μm. In addition, while having the functions of a black matrix and a spacer, in order to accurately bond two substrates sandwiching the liquid crystal layer (there are various combinations such as an array substrate and a CF substrate, a COT substrate and a glass substrate with a light-shielding spacer, a COT substrate with a light-shielding spacer and a glass substrate, etc.), that is, to improve the alignment accuracy, it is necessary to provide two types of heights for the light-shielding spacer (formation of a step of ΔH). Furthermore, there are many requirements for patterning characteristics such as forming a light-shielding spacer that can rise as vertically as possible from the glass substrate (or COT substrate), and it is difficult to satisfy all the required characteristics.

[0009] The present invention has been made in view of the above problems, and can form a light-shielding film having high light-shielding properties and insulating properties, and further excellent in compression ratio, elastic recovery rate, and breaking strength, and when forming a light-shielding film having a spacer function, it is possible to form a step of ΔH and a pattern shape closer to vertical. An object of the present invention is to provide a photosensitive resin composition, a light-shielding film formed using the same, and a liquid crystal display device including the light-shielding film as a component.

[0010] Furthermore, there is provided a photosensitive resin composition capable of collectively forming a BCS having a trapezoidal or rectangular combined shape with different bottom lengths in cross-sectional shape, a light-shielding film formed using the same, and a liquid crystal display device including the light-shielding film as a component.

Means for Solving the Problems

[0011] As a result of investigations to solve the problems in the photosensitive resin composition for a light-shielding film as described above, the present inventors have found that a specific colorant is suitable as a light-shielding component of the photosensitive resin composition for the desired light-shielding film, and have completed the present invention.

[0012] (1) The present invention is a photosensitive resin composition for a light-shielding film, characterized by containing components (A) to (E) as essential components. (A) A polymerizable unsaturated group-containing alkali-soluble resin that contains 5 to 90 mol% of a unit represented by the general formula (1) and 10 to 95 mol% of a unit represented by the general formula (2) (the total of the unit represented by the general formula (1) and the unit represented by the general formula (2) is 100 mol%), has a weight average molecular weight of 3000 to 50000, and an acid value of 30 to 200 mg / KOH.

[0013] [Chemical formula]

[0014] [Chemical formula]

[0015] (However, R1, R3, and R4 each independently represent a hydrogen atom or a methyl group. R2 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. Also, in the unit represented by the general formula (1), 40 mol% or more of R2 is a dicyclopentanyl group or a dicyclopentenyl group. R5 represents a divalent hydrocarbon group having 2 to 10 carbon atoms. p represents a number of 0 or 1. X represents a hydrogen atom or -OC-Y-(COOH). q(However, Y represents a divalent or trivalent carboxylic acid residue, q represents a number from 1 to 2. represents. 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) A photoinitiator, (D) One or more light-shielding components selected from the group consisting of black organic pigments, mixed-color organic pigments, and light-shielding materials, and (E) A solvent (2) The present invention also provides that the polymerizable unsaturated group-containing alkali-soluble resin of component (A), in addition to the units of general formula (1) and general formula (2), may have a substituent on the phenyl group. It is a photosensitive resin composition according to (1), which is a copolymer containing a unit derived from styrene and / or a unit derived from a monomer maleimide compound. (3) The present invention also provides that as the light-shielding component (D), it contains a black organic pigment and / or a mixed-color organic pigment, and the average secondary particle diameter of the black organic pigment and / or the mixed-color organic pigment is 20 to 500 nm. It is a photosensitive resin composition according to (1) or (2). (4) The present invention also provides that component (B) is 5 to 400 parts by mass with respect to 100 parts by mass of component (A), (C) Component is 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of component (A) and component (B), When the components excluding component (E), including component (B) which becomes a solid content after photocuring, are taken as the solid content, (D) Component is 5 to 80% by mass in the total amount of the solid content, It is a photosensitive resin composition according to any one of (1) to (3), characterized by containing each. (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, and having a volume resistivity of 1 × 10 9 Ω·cm or more and a dielectric constant of 2 to 10, and it is a photosensitive resin composition according to any one of (1) to (4). (6) The present invention also relates to a photosensitive resin composition according to any one of (1) to (5), characterized in that a light-shielding film satisfying at least one of the following (i) to (iii) can be formed in a load-unloading test using a microhardness tester. (i) The breaking strength is 200 mN or more. (ii) The elastic recovery rate is 30% or more. (iii) The compression ratio is 40% or less. (7) The present invention also relates to a light-shielding film, characterized in that it is a cured product of the photosensitive resin composition according to any one of (1) to (6). (8) The present invention also relates to a liquid crystal display device, characterized in that it has the light-shielding film according to (7) as a black column spacer (BCS). (9) The present invention also relates to a liquid crystal display device according to (8), further characterized by having a thin film transistor (TFT). (10) The present invention also relates to a liquid crystal display device, characterized in that it has a cured product of the photosensitive resin composition according to any one of (1) to (6) as a black matrix. (11) The present invention also relates to a liquid crystal display device according to (10), further characterized by having a thin film transistor (TFT), and the black matrix is disposed between a substrate facing the array substrate on which the thin film transistor (TFT) is formed and liquid crystal. (12) The present invention also relates to a liquid crystal display device according to (10), further characterized by having 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 liquid crystal. (13) The present invention also relates to a method for manufacturing a light-shielding film formed on a substrate, comprising applying the photosensitive resin composition according to any one of (1) to (6) onto the substrate and curing the photosensitive resin composition by light irradiation. For the film thickness H1 for achieving an optical density as a light-shielding film of 0.5 / μm or more and less than 3 / μm, and the film thickness H2 of the light-shielding film having a spacer function, when H2 is 1 to 7 μm, a light-shielding film with a film thickness H1 and a film thickness H2 where ΔH = H2 - H1 is 0.1 to 6.9 is simultaneously formed. This is a method for manufacturing a light-shielding film having a spacer function. (14) The present invention also relates to the method for manufacturing a light-shielding film according to (13), wherein a light-shielding film containing a portion having the film thickness H1 and a portion having the film thickness H2 is formed by a single exposure. (15) The present invention also relates to a method for manufacturing a liquid crystal display device, characterized in that the light-shielding film manufactured by the method according to (13) or (14) is used as a black column spacer (BCS). (16) The present invention also relates to the manufacturing method according to (15), wherein the liquid crystal display device has a thin film transistor (TFT).

Advantages of the Invention

[0016] The photosensitive resin composition for a light-shielding film according to the present invention can obtain a cured product excellent in compressive modulus, elastic recovery rate, and fracture strength while maintaining light-shielding properties and insulating properties. Furthermore, 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.

Brief Description of the Drawings

[0017]

Figure 1

Figure 2

Figure 3

Figure 4

DETAILED DESCRIPTION OF THE INVENTION

[0018] Hereinafter, the present invention will be described in detail.

[0019] One aspect of the present invention relates to a photosensitive resin composition containing, as essential components, (A) a polymerizable unsaturated group-containing alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photoinitiator, (D) a light-shielding component, and (E) a solvent, which will be detailed below.

[0020] The polymerizable unsaturated group-containing alkali-soluble resin of component (A) is a polymer containing a unit represented by the general formula (1) and a unit represented by the general formula (2).

[0021]

CHEM.

[0022]

CHEM.

[0023] In the general formulas (1) and (2), R1, R3, and R4 independently represent a hydrogen atom or a methyl group. R2 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 therein. Further, in the unit represented by the general formula (1), 40 mol% or more of R2 is a dicyclopentanyl group or a dicyclopentenyl group. R5 represents a divalent hydrocarbon group having 2 to 10 carbon atoms. p represents a number of 0 or 1. X represents a hydrogen atom or -OC-Y-(COOH) q (However, Y represents a divalent or trivalent carboxylic acid residue, q represents a number from 1 to 2. Also, two or more types of X are contained in one molecule of the polymer).

[0024] Examples of the hydrocarbon group represented by R2 include saturated linear hydrocarbon groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, 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, etc.; unsaturated linear hydrocarbon groups such as vinyl group, allyl group, ethynyl group, etc.; cyclic aliphatic hydrocarbon groups such as cyclopropyl group, cyclopentyl group, cyclohexyl group, 2-methylcyclohexyl group, 4-methylcyclohexyl group, dicyclopentanyl group, dicyclopentenyl group, dicyclohexyl group, norbornyl group, isobornyl group, adamantyl group, and the substituent represented by the following general formula (3) (* indicates the bonding part with the ester moiety of general formula (1)); hydrocarbon groups having an aromatic ring such as phenyl group, tolyl group, mesityl group, naphthyl group, anthryl group, phenanthryl group, benzyl group, 2-phenylethyl group, 2-phenylvinyl group, decahydronaphthyl group, etc.; aliphatic ethers such as methoxyethyl group, 2-(methoxyethoxy)ethyl group, isoamyl group, etc.; aliphatic urethanes such as 2-(ethoxycarbonylamino)ethyl group, etc. In the present invention, it is essential that the hydrocarbon group represented by R2 includes a dicyclopentanyl group and a dicyclopentenyl group. The unit represented by general formula (1) may include a plurality of units in which R2 is different.

[0025]

Chemical formula

[0026] Examples of the hydrocarbon group represented by R5 include ethylene group, 1,2-propylene group, 1,4-butylene group, 1,6-hexamethylene group, etc. The hydrocarbon group represented by R5 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 R5 is different.

[0027] X is -OC-Y-(COOH) q (However, Y represents a divalent or trivalent carboxylic acid residue, and q represents a number from 1 to 2.) The structure is formed by reacting a divalent carboxylic acid, a trivalent carboxylic acid, or their acid anhydrides with the hydroxyl groups in the copolymer. The divalent or trivalent carboxylic acid residue refers to the portion excluding the COOH groups in a carboxylic acid compound having 2 or 3 COOH groups bonded. Examples of the divalent or trivalent carboxylic acids used here include divalent or trivalent carboxylic acids such as maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, chlorendic acid, trimellitic acid, etc., and their acid anhydrides can also be preferably used. More preferably, it is tetrahydrophthalic anhydride, succinic anhydride, or trimellitic anhydride.

[0028] When the total of the unit represented by the general formula (1) and the unit represented by the general formula (2) is taken as 100 mol%, the ratio of the unit represented by the general formula (1) and the unit represented by the general formula (2) may be such that the unit represented by the general formula (1) is 5 to 90 mol%, preferably 20 to 70 mol%. Also, the unit represented by the general formula (2) may be in an amount of 10 to 95 mol%, preferably 30 to 80 mol%.

[0029] (A) The polymerizable unsaturated group-containing alkali-soluble resin may contain other units in addition to the unit represented by the general formula (1) and the unit represented by the general formula (2). For example, (A) The polymerizable unsaturated group-containing alkali-soluble resin may further contain units derived from styrene or monomer maleimide which may have a substituent on the phenyl group. Examples of the substituent that styrene can have on the phenyl group include an alkyl group having 1 to 10 carbon atoms. Examples of the monomer maleimide include N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N-(4-hydroxyphenyl)maleimide, etc. Among these, styrene and N-phenylmaleimide are preferred.

[0030] When the total amount of the polymer is 100 mol%, the ratio of the other units described above can be 20 to 50 mol%.

[0031] In addition, as the polymerizable unsaturated group-containing alkali-soluble resin of (A), not only one kind can be used, but also a mixture of two or more polymers having different polymerization ratios can be used.

[0032] The method for producing the polymerizable unsaturated group-containing alkali-soluble resin of component (A) is not particularly limited. For example, as a first step, (meth)acrylate esters having the functional group described above as R2 and (meth)acrylate compounds having a glycidyl group such as glycidyl (meth)acrylate are radically copolymerized in a solvent to obtain a copolymer. Then, as a second step, a monocarboxylic acid compound such as (meth)acrylic acid (including those modified with alkylene oxide) is reacted with the glycidyl group in the copolymer. Subsequently, as a third step, there is a method of reacting a dicarboxylic acid compound, a tricarboxylic acid compound, or an acid anhydride of these carboxylic acid compounds with the hydroxyl group generated in the second step.

[0033] Examples of the (meth)acrylate esters that become the unit of the general formula (1) used in the first step include, as (meth)acrylate esters for introducing the dicyclopentanyl group or dicyclopentenyl group that is essential in the present invention as R2, dicyclopentanyl (meth)acrylate of the formula (4), dicyclopentenyl (meth)acrylate of the formula (5), ethylene glycol-modified dicyclopentanyl (meth)acrylate of the formula (6), ethylene glycol-modified dicyclopentenyl (meth)acrylate of the formula (7), and the like. Two or more of these can also be used in combination.

[0034]

Chemical formula

[0035]

Chemical formula

[0036]

Chem.

[0037]

Chem.

[0038] Note that R1 in General Formulas (4) to (7) represents a hydrogen atom or a methyl group, similar to R1 in General Formula (1).

[0039] Examples of other (meth)acrylic acid esters that form units of General Formula (1) include (meth)acrylic acid methyl, (meth)acrylic acid ethyl, (meth)acrylic acid - n - propyl, (meth)acrylic acid - iso - propyl, (meth)acrylic acid - n - butyl, (meth)acrylic acid - sec - butyl, (meth)acrylic acid - tert - butyl, (meth)acrylic acid pentyl, (meth)acrylic acid neopentyl, (meth)acrylic acid isoamyl, (meth)acrylic acid hexyl, (meth)acrylic acid 2 - ethylhexyl, (meth)acrylic acid dodecyl, (meth)acrylic acid cyclopentyl, (meth)acrylic acid cyclohexyl, (meth)acrylic acid 2 - methylcyclohexyl, (meth)acrylic acid dicyclohexyl, (meth)acrylic acid isobornyl, (meth)acrylic acid adamantyl, (meth)acrylic acid propargyl, (meth)acrylic acid phenyl, (meth)acrylic acid naphthyl, (meth)acrylic acid anthracenyl, (meth)acrylic acid benzyl, (meth)acrylic acid phenethyl, (meth)acrylic acid cresyl, (meth)acrylic acid triphenylmethyl, (meth)acrylic acid cumyl, etc. (meth)acrylic acid esters having a hydrocarbon group with 1 to 20 carbon atoms can be mentioned, and two or more types can be used in combination.

[0040] The usage amount of the above (meth)acrylic acid esters may be adjusted so that the (meth)acrylic acid esters for introducing a dicyclopentanyl group or a dicyclopentenyl group are 40 mol% or more based on the total (meth)acrylic acid esters.

[0041] Also, the usage amounts of the above (meth)acrylic acid esters and the (meth)acrylic acid ester compound having a glycidyl group may be adjusted so that the units derived from the (meth)acrylic acid esters in the copolymer are 5 to 90 mol% and the units derived from the (meth)acrylic acid ester compound having a glycidyl group are 10 to 95 mol%.

[0042] Examples of the dicarboxylic acid compound, tricarboxylic acid compound or acid anhydride of these carboxylic acid compounds used in the third step include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, chlorendic acid, trimellitic acid, and acid anhydrides thereof, and two or more of them can also be used in combination. Among these, tetrahydrophthalic anhydride, succinic anhydride, and trimellitic anhydride can be preferably used.

[0043] In the radical polymerization in the first step, known radical polymerization initiators such as azo compounds and peroxides can be used, and the degree of polymerization may be controlled by using known chain transfer agents, polymerization inhibitors, etc. The reaction temperature can be appropriately set in consideration of the half-life temperature of the radical polymerization initiator used.

[0044] For the addition reaction in the second step, for example, there is a method of heating and stirring at 90 to 120 °C while blowing air in the presence of a catalyst such as triethylbenzylammonium chloride, 2,6 - isobutylphenol, and tris(dimethylaminomethyl)phenol to cause a reaction.

[0045] For the third step, for example, there is a method of heating and stirring at 90 to 130 °C in the presence of a catalyst such as triethylamine, tetraethylammonium bromide, and triphenylphosphine to cause a reaction.

[0046] (A) As another method for producing a polymerizable unsaturated group-containing alkali-soluble resin, as a first step, the above-mentioned (meth)acrylate esters and a polymerizable unsaturated group-containing monocarboxylic acid compound such as (meth)acrylic acid are radically copolymerized in a solvent. As a second step, a (meth)acrylate ester having a glycidyl group such as glycidyl (meth)acrylate is reacted with the carboxyl group in the copolymer. As a third step, the above-mentioned dicarboxylic acid compound, tricarboxylic acid compound or acid anhydride of these carboxylic acid compounds is reacted with the hydroxyl group generated in the second step. There is also such a method.

[0047] When the polymerizable unsaturated group-containing alkali-soluble resin of component (A) has other units such as styrene or monomer maleimide described above, in any method, styrene or monomer maleimide etc. may be copolymerized in the first step.

[0048] (A) The weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) measurement of the alkali-soluble resin is usually 3,000 to 50,000, preferably 4,000 to 20,000. In the polymerizable unsaturated group-containing alkali-soluble resin having the unit structure of the present invention, when the weight average molecular weight is less than 3,000, the adhesion of the pattern during alkali development may decrease, and when the weight average molecular weight exceeds 50,000, the developability may be significantly reduced.

[0049] Also, the preferable range of the acid value of the alkali-soluble resin of (A) is 30 to 200 mgKOH / g, and more preferably 50 to 150 mgKOH / g. In the polymerizable unsaturated group-containing alkali-soluble resin having the unit structure of the present invention, if this value is less than 30 mgKOH / g, residues are likely to remain during alkali development, and if it exceeds 200 mgKOH / g, the penetration of the alkali developer becomes too fast and peeling development occurs, so neither is preferable. The acid value can be adjusted according to the amount of carboxyl groups present in X in the unit represented by the general formula (2).

[0050] In the present invention, for the weight average molecular weight of (A), a value obtained by dissolving a sampled solution in tetrahydrofuran and measuring the molecular weight distribution with an HLC-8220GPC manufactured by Tosoh Corporation and calculating the weight average molecular weight in terms of standard polystyrene is used. For the acid value of component A, a value obtained by dissolving a sampled solution in dioxane and performing neutralization titration with a 0.1 N aqueous potassium hydroxide solution, and calculating the acid value in terms of the solid content of the sample solution from the equivalence point is used.

[0051] Next, examples of the photopolymerizable monomer (B) having at least two ethylenically unsaturated bonds include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, glycerol (meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, or dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, alkylene oxide-modified hexa(meth)acrylate of phosphazene, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and other (meth)acrylic acid esters, polyhydric alcohols such as pentaerythritol and dipentaerythritol, vinyl benzyl ether compounds of polyhydric phenols such as phenol novolac, addition polymers of divinyl compounds such as divinylbenzene, and the like. These photopolymerizable monomers (B) having at least two ethylenically unsaturated bonds may use only one type of compound, or may be used in combination of a plurality. Note that the photopolymerizable monomer (B) having at least two ethylenically unsaturated bonds does not have a free carboxy group. More preferably, it has three or more functional groups.

[0052] (B) component's blending ratio is preferably 5 to 400 parts by mass, more preferably 10 to 150 parts by mass, relative to 100 parts by mass of (A) component. When the blending ratio of (B) component is more than 400 parts by mass relative to 100 parts by mass of (A) component, the cured product after photocuring becomes brittle, and in the unexposed part, the acid value of the coating film is low, so the solubility in the alkaline developer decreases, and problems such as the pattern edge becoming jagged and not sharp occur. On the other hand, when the blending ratio of (B) component is less than 5 parts by mass relative to 100 parts by mass of (A) component, the proportion of photoreactive functional groups in the resin is small and the formation of the crosslinked structure is not sufficient. Furthermore, since the acid value in the resin component is high, the solubility in the alkaline developer in the exposed part increases, so there is a risk that the formed pattern becomes thinner than the target line width or pattern dropout is likely to occur.

[0053] In addition, examples of the photopolymerization initiator as the component (C) include acetophenones such as acetophenone, 2,2 - diethoxyacetophenone, p - dimethylacetophenone, p - dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p - tert - butylacetophenone; benzophenones such as benzophenone, 2 - chlorobenzophenone, p,p’ - bisdimethylaminobenzophenone; benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether; imidazole - based compounds such as 2 - (o - chlorophenyl)-4,5 - diphenylimidazole, 2 - (o - chlorophenyl)-4,5 - di(m - methoxyphenyl)imidazole, 2 - (o - fluorophenyl)-4,5 - diphenylimidazole, 2 - (o - methoxyphenyl)-4,5 - diphenylimidazole, 2,4,5 - triarylimidazole; halomethyldiazole compounds such as 2 - trichloromethyl - 5 - styryl - 1,3,4 - oxadiazole, 2 - trichloromethyl - 5 - (p - cyanostyryl)-1,3,4 - oxadiazole, 2 - trichloromethyl - 5 - (p - methoxystyryl)-1,3,4 - oxadiazole; halomethyl - s - triazine - based compounds such as 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)-4,6 - bis(trichloromethyl)-1,3,5 - triazine, 2 - (4 - methylthioystyryl)-4,6 - bis(trichloromethyl)-1,3,5 - triazine; 1,2 - octanedione, 1 - [4 - (phenylthio)phenyl] -2-(O-benzoyloxime), 1-(4-phenylsulfanylphenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylsulfanylphenyl)butane-1,2-dione-2-oxime-O-acetate, 1-(4-methylsulfanylphenyl)butan-1-one oxime-O-acetate, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetoxime), methanone, (9-ethyl-6-nitro-9H-carbazol-3-yl)[4-(2-methoxy-1-methylethoxy)-2-methylphenyl]-, O-acetoxime, methanone, (2-methylphenyl)(7-nitro-9,9-dipropyl-9H-fluorene-2-yl)-, acetoxime, ethanone, 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluorene-2-yl]-, 1-(O-acetoxime), ethanone, 1-(-9,9-dibutyl-7-nitro-9H-fluorene-2-yl)-, 1-O-acetoxime and other O-acyl oxime compounds such as benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone and other sulfur compounds, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone and other anthraquinones, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide and other organic peroxides, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole and other thiol compounds and the like. Among these, from the viewpoint of easily obtaining a photosensitive resin composition for a highly sensitive light-shielding film, it is preferable to use O-acyl oxime compounds. These (C) photoinitiators may be used alone or in combination of a plurality. In addition, the photoinitiator referred to in the present invention is used in the meaning including a sensitizer.,

[0054] These photoinitiators and sensitizers can be used alone, or two or more of them can be used in combination. In addition, compounds that do not themselves act as photoinitiators or sensitizers but can increase the ability of photoinitiators or sensitizers when used in combination can also be added. Examples of such compounds include tertiary amines such as triethanolamine and triethylamine, which are effective when used in combination with benzophenone.

[0055] (C) The amount of the photoinitiator used is preferably 0.1 to 30 parts by mass, more preferably 1 to 25 parts by mass, based on 100 parts by mass in total of components (A) and (B). When the blending ratio of component (C) is less than 0.1 part by mass, the rate of photopolymerization becomes slow and the sensitivity decreases. On the other hand, when it exceeds 30 parts by mass, the sensitivity is too strong, the pattern line width becomes thicker than the pattern mask, and a faithful line width with respect to the mask cannot be reproduced, or problems such as the pattern edge becoming jagged and not sharp may occur.

[0056] (D) Component is a light-shielding component selected from black organic pigments, mixed-color organic pigments, and light-shielding materials, and is preferably excellent in insulation, heat resistance, light resistance, and solvent resistance. Here, examples of the black organic pigment include perylene black, aniline black, cyanine black, lactam black, etc. Examples of the mixed-color organic pigment include those obtained by mixing two or more pigments selected from red, blue, green, purple, yellow, cyanine, magenta, etc. to simulate blackening. Examples of the light-shielding material include chromium oxide, iron oxide, titanium black, etc. These (D) light-shielding components may be used alone or in combination of a plurality of them.

[0057] As the organic pigments used in the present invention, known compounds can be used without particular limitation, but those that have been micronized and have a specific surface area of 50 m 2Those having / g or more are preferred. 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, thioindigo pigments, etc. may be mentioned. Specifically, compounds with the following C.I. names may be mentioned, but are not limited thereto. 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.

[0058] Also, as the solvent for the component (E), for example, alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy-2-butanone, diacetone alcohol, etc., terpenes such as α- or β-terpineol, etc., ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, etc., aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, etc., glycol ethers such as cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, etc., esters such as ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-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, etc. can be mentioned. By dissolving and mixing these, a uniform solution-like composition can be obtained. Two or more of these solvents may be used to achieve necessary properties such as coatability.

[0059] And the light-shielding component (D) is preferably dispersed in a solvent together with the (F) dispersant in advance to form a light-shielding dispersion, and then incorporated as a photosensitive resin composition for a light-shielding film. Here, since the solvent for dispersion becomes a part of the component (E), any of those mentioned above for the component (E) can be used, but for example, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, etc. are preferably used.

[0060] Regarding the blending ratio of the light-shielding component (D) that forms the light-shielding dispersion liquid, it is preferably 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. Note that the above solid content means the components excluding the component (E) in the composition. The above solid content also includes the component (B) that becomes a solid content after photocuring. If it is less than 5% by mass, the desired light-shielding property cannot be set. If it exceeds 80% by mass, the content of the photosensitive resin that originally becomes a binder decreases, resulting in an undesirable problem of impairing the development characteristics and film-forming ability.

[0061] The average particle size (hereinafter referred to as "average secondary particle size") measured by a laser diffraction / scattering particle size distribution meter of the light-shielding component in this light-shielding dispersion liquid is preferably as follows. When using a black organic pigment and / or a mixed-color organic pigment, and / or a single-color organic pigment, the average secondary particle size of the dispersed particles is preferably 20 to 500 nm. Note that also in the photosensitive resin composition for the light-shielding film prepared by blending these light-shielding dispersion liquids, these light-shielding components preferably have the same average secondary particle size.

[0062] In addition, a (F) dispersant is used in the light-shielding dispersion liquid to stably disperse the light-shielding component, and for this purpose, known dispersants such as various polymer dispersants can be used. As examples of the dispersant, known compounds conventionally used for pigment dispersion (compounds commercially available under names such as dispersants, dispersion wetting agents, dispersion accelerators, etc.) can be used without particular limitation. For example, cationic polymer-based dispersants, anionic polymer-based dispersants, nonionic polymer-based dispersants, pigment derivative-type dispersants (dispersion aids), etc. can be mentioned. In particular, a cationic polymer-based dispersant having a cationic functional group such as an imidazolyl group, a pyrrolyl group, a pyridyl group, a primary, secondary or tertiary amino group as an adsorption point to the pigment, an amine value in the range of 1 to 100 mgKOH / g, and a number average molecular weight in the range of 1,000 to 100,000 is suitable. The blending amount of this (F) dispersant is preferably 1 to 30% by mass, more preferably 2 to 25% by mass, based on the light-shielding component.

[0063] Furthermore, when preparing the light-shielding dispersion liquid, by co-dispersing a part of the polymerizable unsaturated group-containing alkali-soluble resin of the component (A) in addition to the above (F) dispersant, when used as a photosensitive resin composition for a light-shielding film, it is possible to easily maintain a high exposure sensitivity and obtain a photosensitive resin composition with good adhesion during development and less likely to have residue problems. The blending amount of the component (A) is preferably 2 to 20% by mass, more preferably 5 to 15% by mass, in the light-shielding dispersion liquid. When the component (A) is less than 2% by mass, the effects of co-dispersion such as sensitivity improvement, adhesion improvement, and residue reduction cannot be obtained. Also, when it is 20% by mass or more, especially when the content of the light-shielding material is large, the viscosity of the light-shielding dispersion liquid is high, and it becomes difficult or very time-consuming to disperse it uniformly, making it difficult to obtain a photosensitive resin composition for obtaining a coating film in which the light-shielding component is uniformly dispersed.

[0064] The light-shielding dispersion liquid thus obtained can be made into a photosensitive resin composition for a light-shielding film by mixing with the component (A) (when the component (A) is co-dispersed during the preparation of the light-shielding dispersion liquid, the remaining component (A)), the component (B), the component (C), and the remaining component (E).

[0065] In addition, the photosensitive resin composition of the present invention may be blended with (H) additives such as a curing accelerator, a thermal polymerization inhibitor, an antioxidant, a plasticizer, a filler, a solvent, a leveling agent, an antifoaming agent, a coupling agent, and a surfactant, as necessary. Examples of the thermal polymerization inhibitor and the antioxidant include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, and hindered phenol-based compounds. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate. Examples of the filler include glass fiber, silica, mica, and alumina. Examples of the antifoaming agent and the leveling agent include silicone-based, fluorine-based, and acrylic-based compounds. Examples of the surfactant include fluorine-based surfactants and silicone-based surfactants. Examples of the coupling agent include silane coupling agents such as 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane.

[0066] The photosensitive resin composition of the present invention may be used in combination with other resin components that polymerize or cure by heat. As the other resin components, epoxy resins or epoxy compounds having (G) two or more epoxy groups are preferable, and examples thereof include 3,3',5,5'-tetramethyl-4,4'-biphenol type epoxy resin, bisphenol A type epoxy resin, bisphenol fluorene type epoxy resin, phenol novolac type epoxy resin, 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexene carboxylate, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, and epoxy silicone resin. These additional components may be used alone or in combination of a plurality of them.

[0067] The photosensitive resin composition of the present invention contains the above components (A) to (E) as main components. It is desirable that the total content of components (A) to (D) in the solid content is 70% by mass, preferably 80% by mass or more. The amount of the solvent (E) varies depending on the target viscosity, but it is preferably contained in the range of 60 to 90% by mass in the photosensitive resin composition.

[0068] The photosensitive resin composition for a light-shielding film in the present invention is excellent as a photosensitive resin composition for forming, for example, a light-shielding film having a spacer function. 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 a light-shielding film in the present invention is applied onto a substrate, and then after drying the solvent (pre-baking), a photomask is placed on the thus obtained film, irradiated with ultraviolet rays to cure the exposed portions, and further developed using an aqueous alkali solution to elute the unexposed portions to form a pattern, and further post-baking (thermal baking) is performed as post-drying.

[0069] The above substrate may be a transparent substrate, or may be a substrate other than a transparent substrate, such as an alignment film formed on a pixel, or on a planarization film on a pixel, or on a flat film on a pixel after forming pixels such as RGB. Further, the above substrate may be an array substrate on which a TFT is formed.

[0070] Which substrate to form a light-shielding film having a spacer function on varies depending on the design of the liquid crystal display device. For example, when the light-shielding film is a BCS, when providing a region that functions as a black matrix on a TFT, an array substrate may be used as the above substrate. Further, when providing a region that functions as the black matrix on a substrate facing the substrate on which a TFT is formed in a liquid crystal display device, or when manufacturing a liquid crystal display device without a TFT, a transparent substrate such as glass can be used as the above substrate.

[0071] As the transparent substrate on which the photosensitive resin composition is applied, in addition to a glass substrate, examples include those in which a transparent electrode such as ITO or gold is vapor-deposited or patterned on a transparent film (for example, polycarbonate, polyethylene terephthalate, polyethersulfone, etc.). As a method for applying the solution of the photosensitive resin composition on the transparent substrate, in addition to known solution immersion methods and spray methods, any method such as a method using a roller coater machine, a land coater machine, a slit coater machine, or a spinner machine can be adopted. By these methods, after coating to a desired thickness, a film is formed by removing the solvent (pre-baking). Pre-baking is performed by heating with an oven, a hot plate, etc. The heating temperature and heating time in pre-baking are appropriately selected according to the solvent used, and for example, it is performed at a temperature of 60 to 110 °C for 1 to 3 minutes.

[0072] The exposure performed after pre-baking is performed by an ultraviolet exposure apparatus, and only the resist in the portion corresponding to the pattern is sensitized by exposing through a photomask. The exposure apparatus 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., to photocure the photosensitive resin composition in the coating film. At this time, by providing regions with different exposure amounts using a halftone mask, etc., regions with different heights (such as the region with film thickness H1 and the region with film thickness H2 described later) can be formed simultaneously.

[0073] The alkali development after exposure is performed for the purpose of removing the resist in the unexposed portion, and a desired pattern is formed by this development. Examples of the developer suitable for this alkali development include an aqueous solution of a carbonate of an alkali metal or an alkaline earth metal, an aqueous solution of a hydroxide of an alkali metal, etc., and in particular, a weakly alkaline aqueous solution containing 0.05 to 3 mass% of a carbonate such as sodium carbonate, potassium carbonate, lithium carbonate, etc. is preferably used for development at a temperature of 23 to 28 °C, and a fine image can be precisely formed using a commercially available developing machine, an ultrasonic cleaner, etc.

[0074] After development, heat treatment (post-baking) is preferably performed at a temperature of 180 to 250 °C for 20 to 60 minutes. This post-baking is performed for purposes such as enhancing the adhesion between the patterned light-shielding film and the substrate. This is carried out by heating with an oven, hot plate, etc., similar to pre-baking. The patterned light-shielding film of the present invention is formed through the above steps by the photolithography method.

[0075] 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. Also, according to the above method, the volume resistivity when a voltage of 10 V is applied is 1×10 9 Ω·cm or more, preferably 1×10 12 Ω·cm or more of a light-shielding film can be formed. Also, 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. Also, according to the above method, in a mechanical property test, a light-shielding film satisfying a breaking strength of 200 mN or more, and / or an elastic recovery rate of 30% or more, and / or a compression rate of 40% or less can be formed. 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.

[0076] The substrate on which the light-shielding film or the cured film is formed can be bonded to another substrate with a liquid crystal layer interposed therebetween to form a liquid crystal display device (LCD). At this time, the light-shielding film or the cured film is formed on the array substrate on which the TFT is formed, and color resists such as red (R), green (G), and blue (B) are applied, exposed, developed, and baked to further form color filters of respective colors, and then bonded to a transparent substrate, whereby a liquid crystal display device with COT and BOA (Black Matrix on Array) can be obtained. Further, even if the light-shielding film or the cured film is formed on the transparent substrate and bonded to a COT substrate on which a color filter is formed on the TFT, a liquid crystal display device with COT can be obtained. On the other hand, the light-shielding film or the cured film and the color filter may be formed on the transparent substrate and bonded to the TFT substrate. Among these, for the liquid crystal display device with BOA, the light-shielding film or the cured film having a low dielectric constant can be preferably used.

[0077] Further, according to the above method, for the film thickness H1 for making the optical density of the light-shielding film be 0.5 / μm or more and less than 3 / μm, and the film thickness H2 of the light-shielding film having a spacer function, when H2 is 1 to 7 μm, ΔH = H2 - H1 is 0.1 to 6.9, and the light-shielding film with the film thickness H1 and the light-shielding film with the film thickness H2 can be formed simultaneously. A more preferable range is that H2 is 2 to 5 μm and ΔH is 0.1 to 4.9, and a further more preferable range is that H2 is 2 to 4 μm and ΔH is 0.1 to 2.9. The cured film formed by the above method can be used as a column spacer of the liquid crystal display device, and preferably can be used as a black column spacer. According to the cured film with the above ΔH within the above range, since black column spacers with a height difference can be formed from the same material at one time, the manufacturing of the liquid crystal display device can be performed more efficiently. At this time, for example, the cured film with the film thickness H2 can be made to function as a spacer, and the cured film with the film thickness H1 can be made to function as a black matrix.

[0078] Also, according to the above method, a black column spacer having a stepped portion with a cross-sectional shape being a combination of trapezoids or rectangles with different bottom lengths, and a trapezoid or rectangle with a smaller width having a lower side that is shorter than the upper side and is in contact with the upper side of the trapezoid or rectangle with a larger width can also be formed from the same material at once. Therefore, the manufacturing of the liquid crystal display device can be performed more efficiently. In other words, according to the above method, a black column spacer in which a portion with a film thickness H1 and a portion with a film thickness H2 are simultaneously included in the same light-shielding film can also be formed from the same material in one exposure at once. Therefore, the manufacturing of the liquid crystal display device can be performed more efficiently. Note that for the above combination shape, as long as the shape of the portion higher than the cross-sectional plane when cut at a certain height from the bottom surface of the black column spacer is "a combination shape of trapezoids or rectangles with different bottom lengths", the actual bottom surface may be shaped to cover the stepped portion without gaps or fill the recessed portion in accordance with the surface shape of the underlying TFT when the surface of the underlying TFT has stepped portions or recessed portions.

[0079] When forming the black column spacer with a difference in height or the black column spacer with a cross-sectional shape being a combination of trapezoids or rectangles with different bottom lengths, it is preferable to use a black organic pigment as the light-shielding component. In particular, it is more preferable to use 20 to 50% by mass of the black organic pigment in the solid content. It is also possible to collectively form black column spacers with an increased optical density by using an inorganic black pigment such as carbon black as part of the black organic pigment. At this time, the ratio of the inorganic black pigment is preferably in the range of 10 to 20% by mass within the total amount of the black organic pigment and the inorganic black pigment. The carbon black used at this time is preferably carbon black coated with a resin from the viewpoint of enhancing the insulation of the black column spacer and lowering the dielectric constant when the same amount is added.

[0080] The liquid crystal display device having the above light-shielding film or cured film is preferably a TFT-LCD provided with thin film transistors.

[0081] The liquid crystal display device having the light-shielding film or the cured film has high light-shielding properties and insulation properties, further has a spacer function excellent in compression ratio, elastic recovery rate, and breaking strength, and can form a fine spacer shape even when the film thickness is about 1 to 7 μm.

Example

[0082] Hereinafter, embodiments of the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited thereto.

[0083] First, a synthesis example of the polymerizable unsaturated group-containing alkali-soluble resin of the present invention is shown. The evaluation of the resin in the synthesis example was performed as follows.

[0084] [Solid content concentration] 1 g of the resin solution obtained in the synthesis example was impregnated into a glass filter [weight: W0 (g)] and weighed [W1 (g)], and the weight after heating at 160 ° C for 2 hours [W2 (g)] was determined from the following formula. Solid content concentration (weight%) = 100 × (W2 - W0) / (W1 - W0).

[0085] [Acid value] The resin solution was dissolved in dioxane and titrated with a 1 / 10N-KOH aqueous solution using a potentiometric titrator [manufactured by Hiranuma Sangyo Co., Ltd., trade name COM-1600].

[0086] [Molecular weight] Gel permeation chromatography (GPC) [manufactured by Tosoh Corporation, trade name HLC-8220GPC, solvent: tetrahydrofuran, column: TSKgel Super H-2000 (2 pieces) + TSKgel Super H-3000 (1 piece) + TSKgel Super H-4000 (1 piece) + TSKgel Super-H5000 (1 piece) [manufactured by Tosoh Corporation], temperature: 40 ° C, speed: 0.6 ml / min], and the weight average molecular weight (Mw) was determined as a standard polystyrene [PS-oligomer kit manufactured by Tosoh Corporation] conversion value.

[0087] [Measurement of average secondary particle size] For a solution in which the light-shielding dispersion liquid was diluted with a solvent (PGMEA in this example) to a concentration of the light-shielding component of about 0.1% by mass, the average secondary particle size was measured using a particle size distribution meter by the laser diffraction / scattering method (Microtrac MT-3000, manufactured by Nikkiso Co., Ltd.).

[0088] 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: Tris(dimethylaminomethyl)phenol HQ: Hydroquinone TPP: Triphenylphenol DTBPC: 2,6-Di-tert-butyl-p-cresol TEA: Triethylamine PGMEA: Propylene glycol monomethyl ether acetate

[0089] [Synthesis Example 1] Into a 1 L four-necked flask equipped with a reflux condenser, 300 g of PGMEA was placed, and after purging the inside of the flask system with nitrogen, the temperature was raised to 120°C. A monomer mixture (a mixture in which 10 g of AIBN was dissolved in 52.9 g (0.30 mol) of BzMA, 77.1 g (0.35 mol) of DCPMA, and 49.8 g (0.35 mol) of GMA) was added dropwise from a dropping funnel over 2 hours, and further stirred at 120°C for 2 hours to obtain a copolymer solution. Next, after replacing the inside of the flask system with air, 24.0 g of AA (95% of the glycidyl groups), 0.8 g of TDMAMP, and 0.15 g of HQ were added to the obtained copolymer solution, and the mixture was stirred at 120 °C for 6 hours to obtain a copolymer solution containing polymerizable unsaturated groups. Further, 45.7 g of THPA (90% of the number of moles of AA added) and 0.5 g of TEA were added to the obtained copolymer solution containing polymerizable unsaturated groups, and the reaction was carried out at 120 °C for 4 hours to obtain a polymerizable unsaturated group-containing alkali-soluble copolymer resin solution (A)-1. The solid content concentration of the resin solution was 47% by mass, the acid value (in terms of solid content) was 62 mg KOH / g, and Mw by GPC analysis was 8200.

[0090] [Synthesis Example 2] 300 g of PGMEA was placed in a 1 L four-necked flask equipped with a reflux condenser. After replacing the inside of the flask system with nitrogen, the temperature was raised to 120 °C. A monomer mixture (a mixture in which 10 g of AIBN was dissolved in 35.2 g (0.20 mol) of BzMA, 77.1 g (0.35 mol) of DCPMA, 49.8 g (0.35 mol) of GMA, and 10.4 g (0.10 mol) of St) was added dropwise from a dropping funnel over 2 hours, and the mixture was further stirred at 120 °C for 2 hours to obtain a copolymer solution.

[0091] Next, after replacing the inside of the flask system with air, 24.0 g of AA (95% of the glycidyl groups), 0.8 g of TDMAMP, and 0.15 g of HQ were added to the obtained copolymer solution, and the mixture was stirred at 120 °C for 6 hours to obtain a copolymer solution containing polymerizable unsaturated groups.

[0092] Furthermore, 45.7 g of THPA (90% of the number of moles of AA added) and 0.5 g of TEA were added to the obtained copolymer solution containing polymerizable unsaturated groups, and the reaction was carried out at 120 °C for 4 hours to obtain a polymerizable unsaturated group-containing alkali-soluble copolymer resin solution (A)-2. The solid content concentration of the resin solution was 46% by mass, the acid value (in terms of solid content) was 68 mg KOH / g, and Mw by GPC analysis was 7900.

[0093] [Synthesis Example 3] 300 g of PGMEA was placed in a 1 L four-necked flask equipped with a reflux condenser. After purging the inside of the flask system with nitrogen, the temperature was raised to 120 °C. A monomer mixture (a mixture in which 10 g of AIBN was dissolved in 77.1 g (0.35 mol) of DCPMA, 49.8 g (0.35 mol) of GMA, and 31.2 g (0.30 mol) of St) was added dropwise from a dropping funnel into this flask over 2 hours, and the mixture was further stirred at 120 °C for 2 hours to obtain a copolymer solution.

[0094] Next, after purging the inside of the flask system with air, 24.0 g (95% of glycidyl groups) of AA, 0.8 g of TDMAMP, and 0.15 g of HQ were added to the obtained copolymer solution, and the mixture was stirred under heating at 120 °C for 6 hours to obtain a copolymer solution containing polymerizable unsaturated groups.

[0095] Furthermore, 30.0 g (90% of the number of moles of AA added) of SA 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 to obtain a polymerizable unsaturated group-containing alkali-soluble copolymer resin solution (A)-3. The solid content concentration of the resin solution was 46% by mass, the acid value (in terms of solid content) was 76 mgKOH / g, and Mw by GPC analysis was 5300.

[0096] [Comparative Synthesis Example 1] 370 g of PGMEA was placed in a 1 L four-necked flask equipped with a reflux condenser. After purging the inside of the flask system with nitrogen, the temperature was raised to 90 °C. A monomer mixture (a mixture in which 6 g of AIBN was dissolved in 38.8 g (0.22 mol) of BzMA, 38.4 g (0.38 mol) of MMA, and 51.7 g (0.60 mol) of MAA) was added dropwise from a dropping funnel into this flask over 2 hours, and the mixture was further stirred at 90 °C for 8 hours to obtain a copolymer solution.

[0097] Next, after replacing the inside of the flask system with air, 39.2 g of GMA (50% of the carboxyl groups), 1.4 g of TPP, and 0.06 g of DTBPC were added to the obtained copolymer solution, and the mixture was stirred at 90 °C 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 mg KOH / g, and the Mw by GPC analysis was 18,100.

[0098] (Polymerizable unsaturated group-containing alkali-soluble resin) (Component (A)-1: The alkali-soluble resin solution obtained in Synthesis Example 1 above) (Component (A)-2: The alkali-soluble resin solution obtained in Synthesis Example 2 above) (Component (A)-3: The alkali-soluble resin solution obtained in Synthesis Example 3 above) (Component (A)-4: The alkali-soluble resin solution obtained in Comparative Synthesis Example 1 above)

[0099] (Photopolymerizable monomer) (B): A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name DPHA)

[0100] (Photopolymerization initiator) (C): Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetoxyoxime) (manufactured by BASF Japan Ltd., product name Irgacure OXE02)

[0101] (Light-shielding dispersible pigment) (D)-1: A PGMEA dispersion (solid content 19.5%, average secondary particle diameter of black pigment 241 nm) of 15.0% by mass of a black pigment (Lactam Black BASF Co., Ltd. Irgaphor S0100CF) and 4.5% by mass of a polymer dispersant (D)-2: 7.0 mass% of C.I. Pigment Orange 64 (manufactured by BASF), 3.0 mass% of C.I. Pigment Violet 23 (manufactured by Clariant), 7.0 mass% of C.I. Pigment Blue 15:6 (manufactured by Clariant), 4.0 mass% of polymer dispersant concentration, 2.0 mass% of sulfonated azo-based dispersion aid, 2.0 mass% of benzyl methacrylate / methacrylic acid copolymer in PGMEA dispersion (solid content 25.0%) (D)-3: 20.0 mass% of carbon black, 5.0 mass% of polymer dispersant concentration in PGMEA dispersion (solid content 25.0%, average secondary particle diameter of carbon black 162 nm) (D)-4: 25.0 mass% of resin-coated carbon black, 5.0 mass% of polymer dispersant concentration in PGMEA dispersion (solid content 30.0%, average secondary particle diameter of carbon black 90 nm)

[0102] (Solvent) (E)-1: PGMEA (E)-2: 3-methoxy-3-methylbutyl acetate

[0103] (Surfactant) (H): PGMEA solution of BYK-330 (manufactured by BYK-Chemie) (solid content 1.0%)

[0104] The above-mentioned compounding components were compounded at the ratios shown in Table 1 to prepare the photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 2. The numerical values in Table 1 all represent the compounding amounts (g). Also, (E)-1 in the solvent column represents the amount that does not contain PGMEA (the same as (E)-1) in the unsaturated group-containing resin solution (polymerizable unsaturated group-containing alkali-soluble resin solution) and PGMEA (the same as (E)-1) in the light-shielding dispersion liquid.

[0105]

Table 1

[0106] [Evaluation] Using the photosensitive resin compositions for light-shielding films of Examples 1 to 7 and Comparative Examples 1 to 2, the evaluations described below were carried out. The results of these evaluations are shown in Table 2.

[0107] <Development characteristics> Each photosensitive resin composition 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 heat curing treatment was 3.0 μm, and pre-baked at 90°C for 1 minute. Thereafter, a photomask was closely attached, and irradiated with ultraviolet rays of 100 mJ / cm 2 from an ultra-high pressure mercury lamp with an illuminance of 30 mW / cm 2 at a wavelength of 365 nm to carry out a photocuring reaction of the photosensitive portion.

[0108] Next, the glass substrate after this exposure was developed for 60 seconds at 24°C and a pressure of 0.1 MPa using a 0.05% aqueous potassium hydroxide solution to remove the unexposed portion of the coating film. Thereafter, heat curing treatment was carried out at 230°C for 30 minutes using a hot air dryer to obtain a cured film of the photosensitive resin composition. The formation of fine lines in the obtained cured film pattern was confirmed with an optical microscope and evaluated in the following three levels. The results are shown in Table 2. ○: Patterns with L / S of 10 μm / 10 μm or more are formed without residue △: Patterns with L / S of 30 μm / 30 μm or more are formed without residue ×: Patterns with L / S less than 50 μm / 50 μm are not formed, or the trailing or residue of the pattern is prominent

[0109] <Optical density> Each photosensitive resin composition 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 heat curing treatment was 1.1 μm, and pre-baked at 90°C for 1 minute. Thereafter, heat curing treatment was carried out 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 by the optical density per unit film thickness.

[0110] <Volume resistivity> Each of the photosensitive resin compositions obtained above was applied using a spin coater to the portion of a glass substrate with a thickness of 1.2 mm on which Cr was vapor-deposited, excluding the electrodes, so that the film thickness after heat curing treatment was 3.5 μm, and pre-baked at 90°C for 1 minute. Then, 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. Then, an aluminum electrode was formed on the cured film to prepare a substrate for measuring volume resistivity. Next, using an electrometer (manufactured by Keithley Instruments, Inc., "Model 6517A"), the volume resistivity at applied voltages from 1 V to 10 V was measured. The measurement was performed under the condition of holding the voltage for 60 seconds at each applied voltage in 1 V steps, and the volume resistivity at 10 V application is shown in Table 2.

[0111] <Dielectric constant> Each of the photosensitive resin compositions obtained above was applied using a spin coater to the portion of a glass substrate with a thickness of 1.2 mm, excluding the electrodes, so that the film thickness after heat curing treatment was 3.5 μm, and pre-baked at 90°C for 1 minute. Then, 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. Then, an aluminum electrode was formed on the cured film to prepare a substrate for measuring dielectric constant. Next, using an electrometer (manufactured by Keithley Instruments, Inc., "Model 6517A"), the capacitance at frequencies from 1 Hz to 100,000 Hz was measured, and the dielectric constant was calculated from the capacitance. The calculated dielectric constant is shown in Table 2.

[0112] <Half-tone (HT) characteristics of spacer> Each of the photosensitive resin compositions obtained above was applied using a spin coater to a glass substrate with a thickness of 1.2 mm so that the film thickness after heat curing treatment was 3.0 μm, and pre-baked at 90°C for 1 minute. Then, a photomask having a dot pattern was adhered, and irradiated with ultraviolet light of 5 mJ / cm 2 or 100 mJ / cm 2 from an ultra-high pressure mercury lamp with an illuminance of 30 mW / cm 2 at a wavelength of 365 nm to perform a photocuring reaction on the photosensitive portion. Next, the glass substrate after this exposure was developed for 60 seconds at 24°C and a pressure of 0.1 MPa using a 0.05% potassium hydroxide aqueous solution to remove the unexposed portion of the coating film. Thereafter, a 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.

[0113] The halftone characteristics of the spacer were evaluated by calculating the difference (ΔH) between the film thickness (H1) of the light-shielding film at an exposure amount of 5 mJ / cm 2 and the film thickness (H2) of the spacer at 100 mJ / cm 2 and evaluating in the following four grades. 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

[0114] <Compression ratio, elastic recovery rate, and fracture strength of the 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 heat curing treatment was 3.0 μm, and pre-baked at 90°C for 1 minute. Thereafter, a photomask having a dot pattern was brought into close contact, and ultraviolet light of 100 mJ / cm 2 was irradiated with an ultra-high pressure mercury lamp having an illuminance of 30 mW / cm 2 at a wavelength of 365 nm to perform a photocuring reaction on the photosensitive portion.

[0115] Next, the glass substrate after this exposure was developed for 60 seconds at 24°C and a pressure of 0.1 MPa using a 0.05% potassium hydroxide aqueous solution to remove the unexposed portion of the coating film. Thereafter, a 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.

[0116] The spacer properties of the obtained cured film pattern were evaluated using a microhardness tester (Fisherscope HM2000Xyp, manufactured by Fisher Instruments). A flat indenter with a 100-μm square was pressed in at a loading rate of 5.0 mN / second, and a load up to 50 mN was applied. Then, the load was removed at a unloading rate of 5.0 mN / second to create a displacement curve. The compression ratio was calculated from the following formula, with the displacement at a load of 50 mN during loading being L1. Compression ratio (%) = L1 / Spacer height × 100

[0117] The elastic recovery rate was calculated from the following formula, with the displacement at a load of 50 mN during loading being L1 and the displacement during unloading being L2. Elastic recovery rate (%) = (L1 - L2) / L1 × 100

[0118] The fracture strength was evaluated using a microhardness tester (Fisherscope HM2000Xyp, manufactured by Fisher Instruments). A flat indenter with a 100-μm square was pressed in at a loading rate of 5.0 mN / second, and a load up to 300 mN was applied. The load at which the spacer broke was measured and evaluated in the following four grades. The results are shown in Table 2. ○: When the fracture strength is 300 mN or more △: When the fracture strength is 200 mN or less ×: When the fracture strength is 100 mN or less

[0119] <Spacer shape> 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 heat curing treatment was 3.0 μm, and pre-baked at 90°C for 1 minute. Then, a photomask having a dot pattern was adhered, and ultraviolet light with an illuminance of 30 mW / cm at a wavelength of 365 nm 2 from an ultra-high pressure mercury lamp was irradiated at 100 mJ / cm 2 to carry out a photocuring reaction in the photosensitive part.

[0120] Next, the glass substrate after this exposure was developed for 60 seconds at 24°C and a pressure of 0.1 MPa using a 0.05% potassium hydroxide aqueous solution to remove the unexposed portions 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.

[0121] The shape of the spacer was evaluated by the inner corner (taper angle) of the spacer end using a scanning electron microscope. When the taper angle was 70° or more and 90° or less, it was rated as ◎; when it was 50° or more and less than 70°, it was rated as 〇; when it was 50° or less, it was rated as △; and when it was 90° or more, it was rated as ×.

[0122]

Table 2

[0123] From the results of Examples 1 to 7 and Comparative Examples 1 to 2, when the cured product of the photosensitive resin composition of the present invention is used as a black column spacer, it has high light shielding properties (optical density) and insulation properties (volume resistivity), and can form a light shielding film having an excellent spacer function in terms of compressive rate, elastic recovery rate, and breaking strength, and can form a step of ΔH and a pattern shape closer to vertical.

[0124] Next, in order to confirm whether pattern formation by exposure and development is possible such that the cross-sectional shape is a combination shape of trapezoids or rectangles with different bottom lengths, the photosensitive resin compositions of Examples 8 and 9 and Comparative Examples 3 and 4 were blended as shown in Table 3 to obtain photosensitive resin compositions.

[0125]

Table 3

[0126] The same evaluations as those of the photosensitive resin compositions and spacers of Examples 1 to 7 and Comparative Examples 1 and 2 were performed using the photosensitive resin compositions of Examples 8 and 9 and Comparative Examples 3 and 4, and the evaluation results were summarized in Table 4. For the shape of the spacer, the detailed cross-sectional shape of the formed pattern was observed by a separate evaluation method shown below.

[0127]

Table 4

[0128] <Detailed cross-sectional shape of the spacer> Each photosensitive resin composition obtained in Examples 8 and 9 and Comparative Examples 3 and 4 was applied onto a glass substrate with a thickness of 1.2 mm using a spin coater so that the film thickness after heat curing treatment became 3.0 μm, and pre-baked at 90°C for 1 minute. Then, a photomask (halftone mask) having line patterns with total light transmittances different from 20% and 100% was fixed at an interval of 200 μm from the film surface, and irradiated with ultraviolet light of 100 mJ / cm 2 from an ultra-high pressure mercury lamp with an illuminance of 30 mW / cm 2 to perform the photocuring reaction of the photosensitive part. The photomask was a halftone mask in which the region 25 μm to the left and right from the center of the mask opening had a total light transmittance of 100%, and the region 25 μm to 100 μm from the center of the outside had a total light transmittance of 20%.

[0129] Next, the exposed glass substrate was developed for 180 seconds at 24°C and a pressure of 0.1 MPa using a 0.05% potassium hydroxide aqueous solution to remove the unexposed part of the coating film. Then, 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.

[0130] The cross-sectional shape of the spacer was obtained by acquiring the height profile of the pattern in the white vertical scanning interference measurement mode (VSI) using a three-dimensional white light interference type optical microscope (Contour GT-K manufactured by Bruker Corporation), and the two-dimensionally plotted one was used as the cross-sectional shape. Figures 1 to 4 show the two-dimensionally plotted cross-sectional shapes. Figure 1 is the height profile of the pattern formed using the photosensitive resin composition of Example 8, Figure 2 is the height profile of the pattern formed using the photosensitive resin composition of Example 9, Figure 3 is the height profile of the pattern formed using the photosensitive resin composition of Comparative Example 3, and Figure 4 is the height profile of the pattern formed using the photosensitive resin composition of Comparative Example 4. In Figures 1 to 4, the horizontal axis represents the distance from the mask opening, and the vertical axis represents the film thickness. The line indicated by M shows the center of the mask opening. The line indicated by R shows the center of the region with a total line transmittance of 20%. The line indicated by R appears on both sides with respect to the center of the mask opening, but only one side is shown in Figures 1 to 4.

[0131] As shown in Figures 1 and 2, by using the photosensitive resin composition of the present invention and performing exposure and development using a halftone mask, as shown in Figures 1 and 2, it was possible to collectively form a BCS having a cross-sectional shape that is a combination of trapezoids or rectangles with different bottom lengths.

[0132] As shown in Figures 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, it was not possible to collectively form a BCS having a cross-sectional shape that is a combination of trapezoids or rectangles with different bottom lengths, and only patterns having a trapezoidal or rectangular cross-sectional shape or semicircular cross-sectional shape patterns were obtained.

Claims

1. Comprising components (A) to (E) and component (G) as essential components, wherein (A) is a polymerizable unsaturated group-containing alkali-soluble resin having a weight average molecular weight of 3,000 to 50,000 and an acid value of 30 to 200 mg / KOH, containing 5 to 90 mol% of the unit represented by the general formula (1) and 10 to 95 mol% of the unit represented by the general formula (2) (the total of the unit represented by the general formula (1) and the unit represented by the general formula (2) is 100 mol%), excluding those having a residue derived from the compound represented by the following general formula (X)), 【Chemical Formula 1】 [Chemical 2] (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, an ester bond or a urethane bond therein. Further, R ２ is such that 40 mol% or more in the unit represented by the general formula (1) is a dicyclopentanyl group or a dicyclopentenyl group. R ５ represents a divalent hydrocarbon group having 2 to 10 carbon atoms. p represents a number of 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. Further, two or more kinds of X are contained in one molecule of the polymer.). [Chemical Formula 3] (In the formula, Ra to Re each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.) (B) A photopolymerizable monomer having at least two ethylenically unsaturated bonds, (C) A photoinitiator, (D) One or more light-shielding components selected from the group consisting of black organic pigments, mixed-color organic pigments, and light-shielding materials, (E) A solvent, and (G) An epoxy resin or an epoxy compound having two or more epoxy groups Component (B) is 10 to 150 parts by mass with respect to 100 parts by mass of component (A), Component (C) is 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of component (A) and component (B), When the components excluding component (E) containing component (B) which becomes a solid content after photocuring are taken as the solid content, Component (D) is 5 to 80% by mass in the total amount of the solid content, Each containing, The solid content contains 80% by mass or more in total of components (A) to (D), A photosensitive resin composition for a light-shielding film.

2. The photosensitive resin composition according to claim 1, wherein the weight average molecular weight of component (A) is 3,000 to 8,200.

3. The photosensitive resin composition according to claim 1 or 2, containing at least two kinds of solvents as component (E).

4. The photosensitive resin composition according to any one of claims 1 to 3, containing a surfactant (H).

5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the polymerizable unsaturated group-containing alkali-soluble resin of component (A) is a copolymer containing a unit derived from styrene which may have a substituent on the phenyl group and / or a unit derived from a monomer maleimide compound in addition to the units of the general formula (1) and the general formula (2).

6. The photosensitive resin composition according to any one of claims 1 to 5, containing a black organic pigment and / or a mixed-color organic pigment as the light-shielding component, and the average secondary particle diameter of the black organic pigment and / or the mixed-color organic pigment being 20 to 500 nm.

7. A light-shielding film having an optical density OD of 0.5 / μm or more and 3 / μm or less, and having a volume resistivity of 1 × 10 ９ Ω·cm or more and a dielectric constant of 2 to 10, the photosensitive resin composition according to any one of claims 1 to 6, characterized in that the light-shielding film can be formed.

8. The photosensitive resin composition according to any one of claims 1 to 7, characterized in that a light-shielding film satisfying at least one of the following (i) to (iii) can be formed in a load-unloading test using a microhardness tester. (i) The breaking strength is 200 mN or more. (ii) The elastic recovery rate is 30% or more. (iii) The compression rate is 40% or less.

9. A light-shielding film, characterized in that it is a cured product of the photosensitive resin composition according to any one of claims 1 to 8.

10. A liquid crystal display device, characterized in that it has the light-shielding film according to claim 9 as a black column spacer (BCS).

11. The liquid crystal display device according to claim 10, further characterized by having a thin film transistor (TFT).

12. A liquid crystal display device, characterized in that it has a cured product of the photosensitive resin composition according to any one of claims 1 to 8 as a black matrix.

13. The liquid crystal display device according to claim 12, further characterized by having a thin film transistor (TFT), and the black matrix is disposed between a substrate facing the array substrate on which the thin film transistor (TFT) is formed and liquid crystal.

14. The liquid crystal display device according to claim 12, further characterized by having 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 liquid crystal.

15. A method for manufacturing a light-shielding film formed on a substrate, the method comprising applying the photosensitive resin composition according to any one of claims 1 to 8 to the substrate and curing the photosensitive resin composition by light irradiation. For 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 having a spacer function, when H2 is 1 to 7 μm, a light-shielding film having a film thickness H1 and a film thickness H2 such that ΔH = H2 - H1 is 0.1 to 6.9 μm is formed simultaneously. A method for manufacturing a light-shielding film having a spacer function.

16. The method for manufacturing a light-shielding film according to claim 15, wherein a light-shielding film containing a portion having the film thickness H1 and a portion having the film thickness H2 is formed by a single exposure.

17. A method for manufacturing a liquid crystal display device, characterized in that the light-shielding film manufactured by the method according to claim 15 or 16 is used as a black column spacer (BCS).

18. The method for manufacturing a liquid crystal display device according to claim 17, wherein the liquid crystal display device has thin film transistors (TFTs).

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