TW201837061A - Photosensitive resin composition, light shielding film, liquid crystal display device, and method for manufacturing light shielding film and liquid crystal display device having the function of a spacer maintains light shielding and insulation properties - Google Patents

Abstract

The present invention relates to a photosensitive resin composition for a light-shielding film having the function of a spacer, comprising (A) component to (E) component as essential components: (A) an alkali-soluble resin containing a polymerizable unsaturated group; (B) a photopolymerizable monomer having at least three ethylenically unsaturated bonds; (C) a photopolymerization initiator; (D) a light shielding component, wherein a film is formed by filming to have an optical density of 4/[mu]m and a surface resistivity of 1 * 10<SP>8</SP> [omega]/&squ or more, containing insulating carbon black; and (E) a solvent. In addition, the pencil hardness of a cured product of a composition other than the component (D) is HB or more. It is possible to obtain a spacer which not only maintains light shielding and insulation properties but also is excellent in spacer properties such as compression ratio, elastic recovery ratio, and breaking strength, and capable of forming a level difference of [Delta]H and has an excellent pattern shape.

Description

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

The present invention relates to a photosensitive resin composition and a light-shielding film obtained by curing the photosensitive resin composition. More specifically, the present invention relates to a photo-development method capable of forming a spacer function and a black matrix function in a liquid crystal display device. Photosensitive resin composition of black column spacers and its cured film. The present invention further relates to a liquid crystal display device using the black column spacer obtained by the curing. The present invention further relates to a method for manufacturing the liquid crystal display device.

In recent years, a color liquid crystal display (LCD) has been used in all fields such as liquid crystal televisions, liquid crystal monitors, and color liquid crystal mobile phones. Among them, in order to improve the performance of LCDs, improvements have been actively made to improve characteristics such as viewing angle, contrast, and response speed. At present, a large number of thin film transistors (TFTs) -LCDs are also being developed for various panel structures . As for the TFT-LCD, the following methods are mainly used: separately manufacturing an array substrate and a color filter substrate for forming an existing TFT, and bonding the two substrates in a state where a spacer is used to maintain a fixed interval.

A spacer that has a function of maintaining a constant thickness of the liquid crystal layer, which is one of the factors that affect the performance of the LCD (in the conventional method, the distance between the array substrate and the color filter (CF) substrate), previously The method of holding a ball spacer with a fixed particle diameter is adopted. However, in the method described above, there is a problem that the dispersion state through the ball spacer becomes non-uniform, and the amount of light transmission per pixel becomes unstable. In order to solve the problem, a method of forming a column spacer by a photo development method is adopted. However, most of the column spacers formed by the photo development method are transparent, and such a column spacer has the following problems: the light incident from the oblique direction affects the electrical characteristics of the TFT and deteriorates the display quality. In response to such a problem, an LCD panel structure using a light-shielding column spacer, which is a light-shielding film having a spacer function formed by a photo development method, has been proposed (Patent Document 1).

In order for the light-shielding column spacer to function as a spacer, a film thickness of about 1 μm to 7 μm is required. In addition, it is necessary that the light-shielding column spacers having different heights can be formed at the same time in the portion where the TFT is formed and other portions. In addition, the light-shielding column spacer is also required to have an appropriate range of elastic modulus, deformation amount, elastic recovery rate, and the like functioning as the spacer (Patent Document 3). Further, the light-shielding column spacer is also required to improve the reduction of the hardening component caused by adding a light-shielding component (colorant) to the spacer, or the loss of electrical characteristics caused by the influence of impurities in the coloring agent, and the like. Et al. (Patent Document 4). [Prior Art Literature]

[Patent Literature] [Patent Literature 1] Japanese Patent Laid-Open No. 08-234212 [Patent Literature 2] US Patent Application Publication No. 2009/0303407 Specification [Patent Literature 3] Japanese Patent Laid-Open No. 2009-031778 [Patent Literature] 4] International Publication No. 2013/062011

[Problems to be Solved by the Invention] Although a mixed color organic pigment is used in Patent Document 4, the optical density of the light-shielding column spacer is not shown. Compared to inorganic pigments such as carbon black, mixed-color organic pigments are effective in lowering the dielectric constant, but they are often light-shielding. In addition, the spacers must form spacers having different heights at the same time. Therefore, for the light-shielding column spacer, mechanical characteristics such as compression rate, elastic recovery rate, and breaking strength are required. The shape or mechanical characteristics of the spacer are greatly affected by the light-shielding component, so it is difficult to design a photosensitive resin composition for a light-shielding film. Therefore, the shape or mechanical characteristics of a spacer using carbon black, a color-mixed organic pigment, or the like are still insufficient, and further improvement is required.

As described above, the light-shielding column spacer is manufactured with a film thickness of about 1 μm to 7 μm. With the recent miniaturization of liquid crystal display elements, it is desirable for the light-shielding column spacer to be formed into a spacer shape that is fine even if the film thickness is about 1 to 7 μm. In addition, in order to improve the alignment accuracy of the two substrates holding the liquid crystal layer on the basis of the functions of the black matrix and the spacer, it is necessary to set the height of the two light-shielding spacers (formed ΔH Step), and further, patterning characteristics such as a light-shielding spacer, etc., which are formed as vertically as possible with respect to the erection of the glass substrate, are also increasing, making it difficult to satisfy all required characteristics.

The present invention has been made in view of the above-mentioned problems, and provides a light-shielding film having a spacer function that can form a light-shielding film having high light-shielding properties and insulation properties, and further has excellent compression ratio, elastic recovery rate, and breaking strength, and can form a ΔH step A photosensitive resin composition capable of forming an excellent pattern shape, a light-shielding film having a spacer function formed using the same, and a liquid crystal display device using the light-shielding film as a constituent element. [Technical means to solve the problem]

The present inventors have conducted research in order to solve the problems in the photosensitive resin composition for a light-shielding film as described above, and have found that a specific coloring agent is suitable as a light-shielding component of the photosensitive resin composition for a target light-shielding film. Thus, the present invention has been completed.

(1) The present invention is a photosensitive resin composition, which is a photosensitive resin composition for a light-shielding film having a spacer function, and includes the following components (A) to (E) as essential components: ( A) alkali-soluble resin containing a polymerizable unsaturated group; (B) a photopolymerizable monomer having at least three ethylenically unsaturated bonds; (C) a photopolymerization initiator; (D) an optical density of 4 / A film formed with a thickness of μm has a surface resistivity of 1 × 10 ⁸ Ω / □ or more and a light-shielding component containing insulating carbon black; and (E) a solvent; and (D) curing of a composition other than the component The pencil hardness of the object is above HB. (2) The present invention is the photosensitive resin composition according to (1), characterized in that it contains 5 to 400 parts by mass of the component (B) relative to 100 parts by mass of the component (A), and (E) contains (A) component and (B) component in a total amount of 100 parts by mass and contains 0.1 to 40 parts by mass of the (C) component, and (E) containing (B) component which becomes a solid component after photocuring, (E ) When a component other than a component is a solid component, (D) component is included in the total amount of solid content from 5 to 60 mass%. (3) The present invention is the photosensitive resin composition according to (1) or (2), wherein an alkali-soluble resin containing a polymerizable unsaturated group represented by the general formula (II) is used as ( A) ingredients.

[Chemical 1]

In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R ₅ represents a hydrogen atom or a methyl group, and X represents -CO- , -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, 芴 -9,9-diyl Or a straight bond, Y represents a tetravalent carboxylic acid residue, and Z each independently represents a hydrogen atom or -OC-W- (COOH) _l (where W represents a divalent carboxylic acid residue or a trivalent carboxylic acid residue, l Represents a number from 1 to 2), and n represents a number from 1 to 20.

(4) The present invention is the photosensitive resin composition according to any one of (1) to (3), wherein a light-shielding film can be formed, and an optical density OD (Optical Density) is 0.5 / [mu] m or more, a volume resistivity of 4 / μm or less, and applying a voltage of 10 V 1 × 10 ⁹ Ω · cm or more, and a dielectric constant of 2 to 10. (5) The present invention is the photosensitive resin composition according to any one of (1) to (4), characterized in that in a load-unload test using a micro hardness meter, The light-shielding film of at least one of (i) to (iii). (I) The compression ratio is below 40%; (ii) The elastic recovery ratio is above 30%; (iii) The breaking strength is above 200 mN. (6) The present invention is a light-shielding film having a spacer function, which is formed by curing the photosensitive resin composition according to any one of (1) to (5). (7) In addition, the present invention is a liquid crystal display device, including the light shielding film according to (6) as a black column spacer (Black Column Spacer, BCS). (8) The present invention is a liquid crystal display device according to (7), further including a thin film transistor (TFT). (9) The present invention is a method for manufacturing a light-shielding film, characterized in that the photosensitive resin composition according to any one of (1) to (5) is coated on a substrate, and the substrate is irradiated with light. In the method for producing a light-shielding film formed on a substrate by curing the photosensitive resin composition, a film thickness H1 for setting the optical density of the light-shielding film to be 0.5 / μm or more and 4 / μm or less, and to bear The film thickness H2 of the light-shielding film with a spacer function forms a light-shielding film with a film thickness H1 and a film thickness H2 of ΔH = H2-H1 of 0.1-6.9 when H2 is 1 μm to 7 μm. (10) In addition, the present invention is a method for manufacturing a liquid crystal display device, characterized in that a light-shielding film manufactured by the method for manufacturing a light-shielding film according to (9) is used as a black column spacer. (11) The present invention is a method for manufacturing a liquid crystal display device according to (10), wherein the liquid crystal display device includes a thin film transistor (TFT).

Since the photosensitive resin composition for a light-shielding film of the present invention contains a specific insulating carbon black as a colorant, compared with the conventional photosensitive resin composition, compression can be obtained while maintaining light-shielding properties and insulation properties. Hardened product with excellent yield, elastic recovery and breaking strength. Furthermore, the photosensitive resin composition for a light-shielding film of the present invention can have a fine spacer shape even when the film thickness is about 1 μm to 7 μm.

Hereinafter, the present invention will be described in detail. The polymerizable unsaturated group-containing alkali-soluble resin of the component (A) can be used without particular limitation. It has an acidic group such as a polymerizable unsaturated double bond that contributes to the photohardening reaction in the molecule, and a carboxyl group that contributes to alkali developability. Of resin. Among these, the first example which is preferably used is (a) a tetracarboxylic acid or an acid dianhydride thereof and (b) a dicarboxylic acid or a tricarboxylic acid or an anhydride thereof and a hydroxyl-containing compound containing a polymerizable unsaturated group. (C) an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule obtained by performing a reaction, and the hydroxyl-containing compound (c) is a (meth) acrylic acid (which is "acrylic acid and / or The meaning of "methacrylic acid" is obtained by reacting an epoxy compound having two glycidyl ether groups derived from bisphenols, preferably an epoxy compound represented by general formula (I). (A) Since the component has a polymerizable unsaturated double bond and a carboxyl group, it imparts excellent photocurability, good developability, and patterning characteristics to the photosensitive resin composition, and improves the physical properties of the light-shielding film.

[Chemical 2]

However, in the general formula (I), R ₁ , R ₂ , R ₃ and R ₄ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and X represents -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, 芴 -9,9-diyl or single bond The average value of m is in a range of 0 to 10, preferably 0 to 3.

Examples of the bisphenols providing the epoxy compound of the general formula (I) include bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, and bis (4-hydroxy -3,5-dichlorophenyl) ketone, bis (4-hydroxyphenyl) fluorene, bis (4-hydroxy-3,5-dimethylphenyl) fluorene, bis (4-hydroxy-3,5- Dichlorophenyl) fluorene, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-3,5-di (Chlorophenyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3,5-dimethylphenyl) dimethylsilane, bis (4-hydroxy-3, 5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dimethylphenyl) methane, bis (4-hydroxy-3,5- Dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4 -Hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane , Bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl) ether, 9,9- Bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorobenzene Phenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9- Bis (4-hydroxy-3,5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene, 4,4'-biphenol, 3,3 ' -Biphenol and the like. These bisphenols may be used alone or in combination. Among them, bisphenols in which X in the general formula (I) is a fluorene-9,9-diyl group can be particularly preferably used.

The compound of general formula (I) used to derive the alkali-soluble resin (A) is an epoxy compound having two glycidyl ether groups obtained by reacting the bisphenols with epichlorohydrin. During the reaction, oligomerization of the diglycidyl ether compound is usually performed, and m is an integer of 0 to 10 in each molecule. Since the molecules are usually mixed in a plurality of molecules, the average value is 0 to 10 (not limited to An integer), but the average value of m is preferably 0 to 3. If the average value of m exceeds the upper limit value, when a photosensitive resin composition using an alkali-soluble resin synthesized using the epoxy compound is formed, the viscosity of the composition becomes too large, and coating cannot be performed smoothly, or Alkali solubility cannot be sufficiently provided, and alkali developability becomes very poor.

Next, the polymerizable unsaturated group-containing hydroxyl group-containing compound (c) can be reacted with an acid component to obtain an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule, and the hydroxyl-containing compound (c ) Is obtained by reacting an epoxy compound with (meth) acrylic acid. The acid component is preferably a tetracarboxylic acid or an acid dianhydride (a) and a dicarboxylic acid or a tricarboxylic acid or an acid monoanhydride (b) thereof which can be reacted with a compound containing a hydroxyl group. The carboxylic acid residue of the acid component may have either a saturated hydrocarbon or an unsaturated hydrocarbon. In addition, these carboxylic acid residues may contain a bond containing a hetero element such as -O-, -S-, or a carbonyl group.

Although a specific example of an acid component is shown below, the dianhydride and monoanhydride of the polyvalent carboxylic acid illustrated can also be used.

First, (a) the tetracarboxylic acid includes a chain hydrocarbon tetracarboxylic acid, an alicyclic tetracarboxylic acid, or an aromatic polycarboxylic acid. Here, the chain hydrocarbon tetracarboxylic acid includes, for example, butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, and the like, and may further be a tetracarboxylic acid into which an arbitrary substituent is introduced. Examples of the alicyclic tetracarboxylic acid include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, norbornane tetracarboxylic acid, and the like. Tetracarboxylic acid having an arbitrary substituent is introduced. Further examples of the aromatic tetracarboxylic acid include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, and diphenyl ether tetracarboxylic acid, and the like may also be a tetracarboxylic acid into which an arbitrary substituent is introduced. . These (a) tetracarboxylic acids may be used alone or in combination.

As the (b) dicarboxylic acid or tricarboxylic acid, a chain hydrocarbon dicarboxylic acid or tricarboxylic acid, an alicyclic dicarboxylic acid or tricarboxylic acid, an aromatic dicarboxylic acid or a tricarboxylic acid can be used. Here, the chain hydrocarbon dicarboxylic acid or tricarboxylic acid is, for example, succinic acid, ethynyl succinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citrate, malonic acid, Glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diethylene glycol acid, etc., and may also be a dicarboxylic acid or tricarboxylic acid with an arbitrary substituent introduced . Examples of the alicyclic dicarboxylic acid or tricarboxylic acid include cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid, etc., Furthermore, it may be a dicarboxylic acid or a tricarboxylic acid into which an arbitrary substituent is introduced. Further, the aromatic dicarboxylic acid or tricarboxylic acid may be, for example, phthalic acid, isophthalic acid, trimellitic acid, or the like, and may also be a dicarboxylic acid or tricarboxylic acid into which an arbitrary substituent is introduced. These (b) dicarboxylic acids or tricarboxylic acids may be used alone or in combination.

The molar ratio of (a) tetracarboxylic acid or its dianhydride to (b) dicarboxylic acid or tricarboxylic acid or its anhydride used in (A) alkali-soluble resin is 0.01 to 0.5, preferably 0.02 or more, and preferably less than 0.1. If the molar ratio (b) / (a) is out of the range described above, the optimum molecular weight for forming the photosensitive resin composition of the present invention with high light-shielding, high resistance, and good photopatternability cannot be obtained. Poor. In addition, the smaller the molar ratio (b) / (a), the higher the alkali solubility and the larger the molecular weight.

Regarding the ratio of reacting the polymerizable unsaturated group-containing hydroxyl group-containing compound (c) with the acid components (b) and (a), it is preferable that the terminal of the compound is a carboxyl group, and it is preferable that The molar ratio of each component is (c): (b): (a) = 1: 0.2-1.0: 0.01-1.0, and a quantitative reaction is performed. In this case, it is desirable that the molar ratio of the total amount of the acid component to the hydroxyl group-containing compound (c) containing a polymerizable unsaturated group (c) / [(b) / 2 + (a)] = Quantitative reactions were performed at 0.5 to 1.0. When the molar ratio is less than 0.5, the terminal of the alkali-soluble resin becomes an acid anhydride, and the content of the unreacted acid dianhydride may increase to cause deterioration of the stability of the alkali-soluble resin composition over time. On the other hand, when the molar ratio exceeds 1.0, there is a concern that the content of unreacted polymerizable unsaturated group-containing hydroxy-containing compound increases and the stability of the alkali-soluble resin composition with time may decrease. The molar ratio of each component (a), (b), and (c) can be arbitrarily changed within the said range for the purpose of adjusting the acid value and molecular weight of an alkali-soluble resin.

The alkali-soluble resin of (A) can be produced by the above-mentioned procedure by a known method, for example, a method described in Japanese Patent Laid-Open No. 8-278629 or Japanese Patent Laid-Open No. 2008-9401. First, a method of reacting (meth) acrylic acid with an epoxy compound of the general formula (I) includes, for example, a method in which a mole (meth) acrylic acid such as an epoxy group of an epoxy compound is added to a solvent, In the presence of a catalyst (triethylbenzyl ammonium chloride, 2,6-diisobutylphenol, etc.), the reaction is carried out by heating and stirring at 90 ° C to 120 ° C while blowing air. Next, a method of reacting an acid anhydride with a hydroxyl group of an epoxy acrylate compound as a reaction product is as follows. A predetermined amount of an epoxy acrylate compound, an acid dianhydride and an acid monoanhydride are added to a solvent, and a catalyst (four In the presence of triethylammonium bromide, triphenylphosphine, etc.), the reaction is performed by heating and stirring at 90 ° C to 140 ° C.

The alkali-soluble resin (A) produced as described above has, for example, a structure represented by the general formula (II).

[Chemical 3]

In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R ₅ represents a hydrogen atom or a methyl group, and X represents -CO- _{, -SO 2 -, - C (} CF 3) 2 -, - Si (CH 3) 2 -, - CH 2 -, - C (CH 3) 2 -, - O-, fluorene-9,9-diyl Or a straight bond, Y represents a tetravalent carboxylic acid residue, and Z each independently represents a hydrogen atom or -OC-W- (COOH) _l (where W represents a divalent carboxylic acid residue or a trivalent carboxylic acid residue, l Represents a number from 1 to 2), and n represents a number from 1 to 20.

The compound group represented by the general formula (II) is an acid adduct of an epoxy acrylate based on a bisphenol-type epoxy compound, but a novolak-type epoxy compound may be used instead of the bisphenol-type epoxy compound. , Epoxides of phenol aralkyl compounds, epoxides of naphthol aralkyl compounds, epoxides of bisphenol aralkyl compounds, and the like are used as raw materials. In addition, when an acid component is added to the epoxy acrylate compound, it is also possible to coexist two or more polyol compounds having an alcoholic hydroxyl group or coexist two or more compounds having an isocyanate group, etc., as desired. The physical properties are designed to harden the obtained unsaturated group-containing alkali-soluble resin.

Regarding the second example of the unsaturated group-containing alkali-soluble resin as the component (A), a polymerizable unsaturated group-containing base obtained by further reacting glycidyl (meth) acrylate with an alkali-soluble resin can be listed. A soluble resin obtained by radically polymerizing (meth) acrylic acid with various (meth) acrylates and the like. Examples of the (meth) acrylic acid copolymerized with (meth) acrylic acid include (meth) acrylic acid esters, ammonium (meth) acrylic acid, styrene and its derivatives, maleic anhydride, and Its derivatives, vinyl ethers, olefins, etc.

The (meth) acrylate or ammonium (meth) acrylate is a group of compounds having a structure obtained by reacting (meth) acrylic acid with an alcohol (R ₆ OH) component or an amine (R ₇ R ₈ NH), A known person can be used without particular limitation. Specific examples of R ₆ , R ₇ and R ₈ include methyl, ethyl, propyl, isopropyl, butyl, third butyl, pentyl, neopentyl, 2-cyclopentylethyl, Straight-chain monovalent alkyl groups such as cyclohexylmethyl, branched monovalent alkyl groups, or monovalent alkyl groups which can be substituted by alicyclic structures, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, adamantane Monovalent alicyclic hydrocarbon groups such as methyl, isobornyl, dicyclopentyl, dicyclopentenyl, phenyl, tolyl, mesityl, naphthyl, anthryl, benzyl, 2-phenylethyl Equivalent monovalent aromatic hydrocarbon group, or pyridyl, pyridinyl, N-hexahydropyridyl, pyrrolyl, pyrrolidinyl, imidazolyl, imidazolyl, furyl, tetrahydrofuryl, thienyl, tetrahydrothienyl, Saturated monovalent heterocyclic groups such as morpholinyl, morpholinyl, and quinolinyl or unsaturated monovalent heterocyclic groups and the like. Furthermore, a halogen atom, a hydroxyl group, a sulfonyl group, a carbonyl group, a thiocarbonyl group, a carboxyl group, a thiocarboxyl group, a dithiocarboxyl group, a methylamino group, a cyano group, and a nitro group may be introduced at any positions of the hydrocarbon group and the heterocyclic group. , Nitro, sulfo, amine, imine, silane, ether, thioether, ester, thioester, dithioester, amido, thioamido, aminomethyl Structures such as an ester group, a thiocarbamate group, a ureido group, and a thiourea group as substituents.

The polystyrene-equivalent weight average molecular weight (Mw) of the alkali-soluble resin (A) measured by Gel Permeation Chromatography (GPC) is usually 1,000 to 50,000, and preferably 2,000 to 15,000. When the weight average molecular weight is less than 1,000, there is a concern that the adhesion of the pattern during alkali development may be reduced. When the weight average molecular weight exceeds 50,000, the developability may be decreased, or when it is hardened by light or heat, it may be difficult. There is a concern that a composition having a desired hardness will be formed. When the alkali-soluble resin of the general formula (II) is used, the weight-average molecular weight is preferably 2,000 to 10,000, and more preferably 3,000 to 7,000.

The acid value of the alkali-soluble resin (A) preferably ranges from 30 mgKOH / g to 200 mgKOH / g. If the value is less than 30 mgKOH / g, residues are liable to remain during alkali development, and if it exceeds 200 mgKOH / g, the penetration of the alkali developing solution becomes too fast and peeling development is caused, which are all unsatisfactory. In addition, as the alkali-soluble resin containing a polymerizable unsaturated group (A), only one kind may be used, or a mixture of two or more kinds may be used.

In the present invention, the value of the weight average molecular weight of (A) is as follows: The sampled solution is dissolved in tetrahydrofuran, the molecular weight distribution measurement is performed using HLC-8220GPC manufactured by Tosoh Corporation, and a weight average in terms of standard polystyrene is calculated. Molecular weight. In addition, the acid value of the component (A) uses the following values: the sampled solution is dissolved in dioxane, neutralization titration is performed using a 0.1 potassium hydroxide aqueous solution, and the solid content conversion of the sample solution is calculated based on the equivalent point The value of the acid value.

(B) Examples of the photopolymerizable monomer having at least three ethylenically unsaturated bonds include trimethylolpropane tri (meth) acrylate and trimethylolethane tri (meth) acrylate. , Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, alkylene oxide modified phosphazene hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate (Meth) acrylic esters such as esters, polyols (pentaerythritol, dipentaerythritol, etc.), or vinyl benzyl ether compounds of polyphenols (phenol novolac, etc.), divinyl compounds such as divinylbenzene Addition polymers and the like. These (B) photopolymerizable monomers which have at least three ethylenically unsaturated bonds may use only one type of compound, or may use multiple types together. Further, (B) the photopolymerizable monomer having at least three ethylenically unsaturated bonds does not have a free carboxyl group.

The blending ratio of the component (B) is preferably 5 to 400 parts by mass, and more preferably 10 to 150 parts by mass, with respect to 100 parts by mass of the component (A). If the blending ratio of the (B) component is more than 400 parts by mass with respect to 100 parts by mass of the component (A), the cured product after photo-hardening becomes brittle, and the acid value of the coating film in the unexposed portion is low. The solubility of the alkali developing solution is lowered, causing a problem that the pattern edges are jagged and not clear. On the other hand, if the blending ratio of the (B) component is less than 5 parts by mass relative to 100 parts by mass of the (A) component, the proportion of the photoreactive functional group in the resin is small, and the formation of the crosslinked structure is insufficient. Furthermore, because the acid value of the resin component is high, the solubility of the exposed portion to the alkali developing solution is improved. Therefore, there is a concern that the formed pattern becomes thinner than the target line, or the pattern is liable to fall off. .

Examples of the photopolymerization initiator of the (C) component include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminophenylacetone, and Acetophenones such as chloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminodiamine Benzophenones such as benzophenone, benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin ethers, 2- (o-chlorophenyl) -4,5-phenylbiimidazole , 2- (o-chlorophenyl) -4,5-bis (m-methoxyphenyl) biimidazole, 2- (o-fluorophenyl) -4,5-diphenylbiimidazole, 2- (o-methyl) (Oxyphenyl) -4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole and other biimidazole compounds, 2-trichloromethyl-5-styryl-1,3, 4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyrene) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyrene) Group) Halomethyldiazole compounds such as 1,3,4-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 -chlorine (Phenyl) -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-methoxybenzene Vinyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4,5-trimethoxystyryl) -4,6-bis (trichloro (Methyl) -1,3,5-triazine, 2- (4-methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine and other halogen methyl groups -Mestriazine-based compounds, 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzylideneoxime), 1- (4-phenyl Sulfonylphenyl) butane-1,2-dione-2-oxime-O-benzoate, 1- (4-methylsulfonylphenyl) butane-1,2-dione- 2-oxime-O-acetate, 1- (4-methylsulfonylphenyl) butane-1-oneoxime-O-acetate, ethyl ketone, 1- [9-ethyl-6- (2-methylbenzylidene) -9H-oxazol-3-yl]-, 1- (0-ethylamidooxime), ketone, (9-ethyl-6-nitro-9H-fluorene Azol-3-yl) [4- (2-methoxy-1-methylethoxy) -2-methylphenyl]-, O-acetamidooxime, ketone, (2-methylbenzene ()-(7-nitro-9,9-dipropyl-9H-fluoren-2-yl)-, acetamoxime, ethyl ketone, 1- [7- (2-methylbenzyl)- 9,9-dipropyl-9H-fluoren-2-yl]-, 1- (O-ethyl Oxime), ethyl ketone, 1-(-9,9-dibutyl-7-nitro-9H-fluoren-2-yl)-, 1-O-acetamido oxime and other O-fluorenyl oxime compounds Class, benzyldimethylketal, thiathrone, 2-chlorothiaxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthio Sulfur compounds such as heteroanthrone, anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, Organic peroxides such as benzamyl peroxide and cumene peroxide; thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole; and the like. Among these, from the viewpoint of easily obtaining a photosensitive resin composition for a light-shielding film having a high sensitivity, it is preferable to use O-fluorenyl oxime-based compounds. These (C) photopolymerization initiators may use only one kind of compound, or may use multiple types together. The photopolymerization initiator in the present invention is used in the sense that it includes a sensitizer.

These photopolymerization initiators or sensitizers may be used alone or in combination of two or more. Moreover, although it does not function as a photoinitiator or a sensitizer itself, you may add the compound which can increase the capability of a photoinitiator or a sensitizer by using it in combination. Examples of such compounds include tertiary amines such as triethanolamine and triethylamine which are effective when used in combination with benzophenone.

Based on a total of 100 parts by mass of the components (A) and (B), the amount of the photopolymerization initiator used in the component (C) is preferably 0.1 to 40 parts by mass, and more preferably 1 to 25 parts by mass Serving is better. When the blending ratio of the (C) component is less than 0.1 parts by mass, the speed of photopolymerization becomes slow and the sensitivity decreases. On the other hand, when it exceeds 40 parts by mass, there is a concern that the following problems arise: the sensitivity is too strong It becomes a state where the pattern line width becomes thicker than the pattern mask, and the faithful line width cannot be reproduced for the mask, or the pattern edges are jagged and unclear.

The (D) component is a composition having a film thickness of 10 μm to 1.5 μm from a composition containing the (D) component and the (A) component in an amount of 5% to 20% by mass in the (E) component. In addition, the film formed with a film having an optical density of 4 / μm has a surface resistivity of 1 × 10 ⁸ Ω / □ or more and a light-shielding component containing insulating carbon black. The insulating carbon black that can be contained in such a light-shielding component requires an insulating treatment on the surface of the carbon black by various methods, but the method of the insulating treatment is not particularly limited. Examples of methods for insulating treatment include a method of coating with a resin (for example, Japanese Patent Laid-Open No. 9-95625), a method of performing an oxidation treatment with an oxidizing agent (for example, Japanese Patent Laid-Open No. 11-181326), A method of grafting a polymer compound having a reactive group (for example, Japanese Patent Laid-Open No. 9-265006), a method of chemically modifying with an organic group (for example, Japanese Patent Laid-Open No. 2008-517330), A method of graft reaction and coating of a resin (for example, Japanese Patent Laid-Open No. 2002-249678), a method of coating with a pigment (for example, International Publication No. 2013/129555), and the like.

(D) The component may use two or more kinds of insulating carbon black, and may also use blacks such as perylene black, aniline black, cyanine black, and lactam black. Organic pigment or red, blue, green, purple, yellow, cyan, magenta and other organic pigments. The selection of these light-shielding components containing carbon black as an essential component needs to be performed in consideration of insulation, heat resistance, light resistance, solvent resistance, and the like. Depending on the circumstances, the combination of light-shielding components can be selected so that black can be made achromatic.

Examples of the solvent of the (E) component include methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, and 3- Alcohols such as hydroxy-2-butanone and diacetone alcohol, terpenes such as α-terpineol or β-terpineol, etc., acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2- Ketones such as pyrrolidone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, cellosolve, methylcellosolve, ethylcellosolve, carbitol, methylcarbitol, ethylcarbitol Glycol ethers such as alcohol, butylcarbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether, and ethyl acetate Ester, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-methylbutyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl solvent Fiber agent acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and the like; By using these solvents Dissolving, mixing, the composition can form a uniform solution form. These solvents may be used in combination of two or more in order to make them essential properties such as coatability.

In addition, it is preferable that these light-shielding components containing insulating carbon black as an essential component be dispersed in a solvent together with the (F) dispersant in advance to form a carbon black dispersion liquid, and then formulated as a photosensitive resin composition for a light-shielding film. . Here, since the dispersed solvent becomes a part of (E) component, if it is listed in said (E) component, it can use it, For example, a propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate are used suitably. Wait. The blending ratio of the insulating carbon black (D) forming the carbon black dispersion is preferably in a range of 5 to 60% by mass relative to the total solid content of the photosensitive resin composition for the light-shielding film of the present invention. Used within. In addition, the said solid content means a component other than (E) component in a composition. The solid content also includes a 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. When it exceeds 60 mass%, since the content of the photosensitive resin which becomes an adhesive originally decreases, it will not only impair the developing characteristic but also the film formation ability will be impaired.

The average particle diameter (hereinafter referred to as “average secondary particle diameter”) of the light-shielding component in the carbon black dispersion liquid measured by a laser diffraction × scattering particle size distribution meter is preferably as follows. Regarding the insulating carbon black and the organic pigment used in combination, the average secondary particle diameter of the dispersed particles should preferably be 20 nm to 500 nm. Moreover, in the photosensitive resin composition for light-shielding films prepared by blending these carbon black dispersion liquids, it is preferable that these light-shielding components have the same average secondary particle diameter.

As the (F) dispersant, known dispersants such as various polymer dispersants can be used. As examples of the dispersant, known compounds (compounds sold under the names of dispersant, dispersant, dispersant, and dispersant) can be used without particular limitation, and examples thereof include cationic polymer-based dispersants. , Anionic polymer dispersant, nonionic polymer dispersant, pigment derivative dispersant (dispersion aid), etc. Particularly preferred is a cationic polymer-based dispersant, which has cationic functional groups such as imidazolyl, pyrrolyl, pyridyl, primary amine, secondary amine, or tertiary amine groups as adsorption points for pigments, and amines The value is 1 mgKOH / g to 100 mgKOH / g, and the number average molecular weight is in the range of 1,000 to 100,000. The blending amount of the dispersant is 1 to 30% by mass, and preferably 2 to 25% by mass, with respect to a light-shielding component using insulating carbon black as an essential component.

Furthermore, when preparing a carbon black dispersion liquid, in addition to the dispersant, a part of the polymerizable unsaturated group-containing alkali-soluble resin of component (A) is co-dispersed to form a photosensitive resin for a light-shielding film. In the case of a composition, it is possible to form a photosensitive resin composition which is easy to maintain exposure sensitivity at a high sensitivity, has good adhesion during development, and has a problem of residues. The blending amount of the component (A) is preferably 2% by mass to 20% by mass, and more preferably 5% by mass to 15% by mass in the carbon black dispersion. If the component (A) is less than 2% by mass, co-dispersing effects such as improved sensitivity, improved adhesion, and reduced residue cannot be obtained. In addition, if the content is 20% by mass or more, particularly when the content of the light-shielding component containing insulating carbon black as an essential component is large, the carbon black dispersion liquid has a high viscosity, it is difficult to uniformly disperse it, or it takes a long time to obtain it. A photosensitive resin composition in which a coating film of insulating carbon black is uniformly dispersed is obtained.

The carbon black dispersion obtained in this way can be obtained by co-dispersing the component (A) with the component (A) when the carbon black dispersion is prepared, and the component (B) remaining. The (C) component and the remaining (E) component are mixed to form a photosensitive resin composition for a light-shielding film.

In addition, in the photosensitive resin composition of the present invention, a hardening accelerator, a thermal polymerization inhibitor and an antioxidant, a plasticizer, a filler, a leveling agent, a defoaming agent, a coupling agent, and a surfactant may be blended as necessary. And other additives. Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethylether, pyrogallol, and tert-butyl catechol), phenothiazine, hindered phenol-based compounds, etc. Plasticizers include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc., fillers Examples thereof include glass fiber, silicon dioxide, mica, and alumina. Examples of the leveling agent or defoaming agent include silicone-based, fluorine-based, and acrylic compounds. Examples of the coupling agent include 3- (glycidyloxy) propyltrimethoxysilane, 3-propenyloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, Silane coupling agents such as 3-ureidopropyltriethoxysilane, and surfactants include fluorine-based surfactants and silicone-based surfactants.

The photosensitive resin composition of the present invention may be used in combination with another resin component that is polymerized or cured by heat. The other resin component is preferably (G) an epoxy resin or an epoxy compound having two or more epoxy groups, and examples thereof include 3,3 ', 5,5'-tetramethyl-4,4'-biphenol Epoxy resin, bisphenol A epoxy resin, bisphenol fluorene epoxy resin, phenol novolac epoxy resin, 3,4-epoxycyclohexenylmethyl-3,4-epoxy Cyclohexene carboxylate, 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, ring Oxy silicone resin, etc. These additional components may be used alone or in combination.

The photosensitive resin composition of this invention contains the said (A)-(E) component as a main component. It is desirable that the solid component contains (A) to (D) components in a total amount of 70% by mass, preferably 80% by mass or more. (E) The amount of the solvent varies depending on the target viscosity, but is preferably contained in the photosensitive resin composition in a range of 60% by mass to 90% by mass. When the (G) component is used in combination, the ratio (mass%) of (G) / {(A) + (B) + (G)} is preferably 5% to 30%, and more preferably 10% to 20 %.

The photosensitive resin composition of the present invention is characterized in that the hardness of a cured product of a composition other than the insulating carbon black ((D) component) as a light-shielding component is set to a fixed level or higher. Regarding the film formation conditions of the cured film for measuring the hardness, the light curing conditions and the thermal curing conditions used when the desired pattern is obtained using the photosensitive resin composition of the present invention are used. For example, a composition for measuring hardness including the components (A) to (C) and (E) is spin-coated on a glass substrate using a spinner, and dried at a temperature of 60 ° C to 110 ° C for 1 minute to 3 minutes. Then, an exposure device equipped with an ultra-high pressure mercury lamp is used to perform a predetermined amount of exposure without blocking the photoresist, and then heat-cured at 180 ° C to 250 ° C for 20 minutes to 60 minutes, thereby producing a cured film for hardness measurement. When measuring the pencil hardness of the cured film, a cured film having a pencil hardness of HB or higher is preferably obtained. It is more preferable that the component (A) to (C) component and appropriate (G) epoxy resin, epoxy compound, or hardening accelerator and other additives be combined to make the photosensitivity of the present invention such that the pencil hardness becomes H or more. Resin composition. When the pencil hardness is softer than HB, there may be disadvantages such as insufficient elastic recovery rate in the mechanical physical properties of the spacer. In particular, when the content rate of a light-shielding component such as carbon black is small, the effect may be significantly exhibited.

The method for obtaining a cured film having a pencil hardness of HB or higher is not particularly limited, and for example, the following components can be selected to select the component (A) and the component (B).

In order to harden the hardness of the cured film, it is necessary to crosslink the molecules of the polymerizable unsaturated group-containing alkali-soluble resin ((A) component) formed during photocuring and the (A) component and the photopolymerizable monomer. The selection of (A) component, (B) component selection, and design mix ratio are performed so that crosslinking between ((B) component) may become more than a fixed amount. When the molecular weight of (A) component becomes large and the content of the polymerizable unsaturated group in one molecule becomes small, it becomes difficult to increase the amount of crosslinking. It is also necessary to consider the following cases: if the molecular weight of the component (A) is too large, even if the content of the polymerizable unsaturated group in one molecule is increased, it is difficult to increase the components of (A) and between (A) and (B) components The tendency of the amount of cross-link formation. In addition, if the polymerizable unsaturated group of the component (B) is not three or more, it is difficult to increase the amount of crosslinking. In addition, since the physical properties of the hardened material are also affected by the structure of the alkali-soluble resin or the structure of the photopolymerizable monomer, these aspects are also adopted to select the combined (A) component and (B) component, and to design a blending ratio .

The photosensitive resin composition for a light-shielding film of the present invention is excellent as a photosensitive resin composition for forming a light-shielding film having a spacer function, for example. A method of forming a light-shielding film having a spacer function is a photo developing method as described below. The method can be enumerated as follows: First, a photosensitive resin composition for a light-shielding film of the present invention is coated on a substrate, and the solvent is dried (pre-baked), and then a photoresist is placed on the film obtained in the manner described above. The exposed part is hardened by irradiating ultraviolet rays, and an alkali aqueous solution is used to develop and elute the unexposed part to form a pattern, and then post-baking (hot calcination) is performed as post-drying.

The substrate may be a transparent substrate, or an orientation formed by forming a pixel such as RGB on a pixel, or a planarizing film on a pixel, or a planarizing film on a pixel. Substrates other than transparent substrates such as films. The type of substrate on which a light-shielding film having a spacer function is formed depends on the design of the liquid crystal display device.

In addition to the glass substrate, the transparent substrate coated with the photosensitive resin composition can be exemplified by indium tin oxide vapor-deposited or patterned on a transparent film (such as polycarbonate, polyethylene terephthalate, polyether fluorene, etc.). Materials (indium tin oxide, ITO) or transparent electrodes such as gold. A method for applying a solution of a photosensitive resin composition on a transparent substrate may be a method using a roll coater, a Land coater, a slit coater, or a spinner, in addition to the known solution dipping method and spray method. Either way. By these methods, after coating to a desired thickness, the solvent is removed (pre-baking) to form a film. The pre-baking is performed by heating with an oven, a hot plate, or the like. The heating temperature and heating time in the pre-baking are appropriately selected depending on the solvent used, and for example, it is performed at a temperature of 60 ° C. to 110 ° C. for 1 minute to 3 minutes.

The exposure performed after the pre-baking is performed using an ultraviolet exposure device, and exposure is performed through a photoresist, so that only the resist corresponding to the pattern is exposed to light. The exposure device and exposure 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, and the photosensitive resin composition in the coating film is light-cured.

The alkali development after the exposure is performed for the purpose of removing the resist in the unexposed portion, and a desired pattern is formed by the development. Examples of the developing solution suitable for the alkali development include aqueous solutions of carbonates of alkali metals or alkaline earth metals, aqueous solutions of hydroxides of alkali metals, and the like, and it is particularly preferable to use sodium carbonate containing 0.05 to 3% by mass A weakly alkaline aqueous solution of carbonates such as potassium carbonate, lithium carbonate, and lithium carbonate is developed at a temperature of 23 ° C. to 28 ° C., and a commercially available developing machine or ultrasonic washing machine can be used to precisely form fine images.

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

According to the method, a light-shielding film having an optical density OD of 0.5 / μm to 4 / μm, and preferably 1.5 / μm to 2.5 / μm can be formed. In addition, according to the method, 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 can be formed. In addition, according to the method, a light-shielding film having a dielectric constant of 2 to 10, preferably 2 to 8 can be formed. In addition, according to the method, a light-shielding film having a breaking strength of 200 mN or more, an elastic recovery rate of 30% or more, and / or a compression rate of 40% or less can be formed in a mechanical property test. The light-shielding film formed by the method can be used as a column spacer of a liquid crystal display device, and is preferably used as a black column spacer.

In addition, according to the method, the film thickness H1 for setting the optical density as the light-shielding film to be 0.5 / μm or more and 4 / μm or less, and the film thickness H2 of the light-shielding film that functions as a spacer can be simultaneously formed. When H2 is 1 μm to 7 μm, ΔH = H2-H1 is a light shielding film having a film thickness H1 of 0.1 to 6.9 and a light shielding film having a film thickness H2. The more preferable ranges are 0.5 / μm to 3 / μm as the light-shielding film, H2 is 2 μm to 5 μm, and ΔH is 0.1 to 2.9. Particularly preferred ranges are that the optical density as the light-shielding film is 0.5 / μm to 2 / μm, H2 is 2 μm to 4 μm, and ΔH is 1.0 to 2.0. The cured film formed by the above method can be used as a column spacer of a liquid crystal display device, and is preferably used as a black column spacer. According to the hardened film in which the ΔH is in the range, black column spacers having different heights can be formed at the same time from the same material, so that the liquid crystal display device can be manufactured more efficiently. In this case, for example, a cured film having a film thickness H2 may function as a spacer, and a cured film having a film thickness H1 may function as a black matrix. In addition, the height H2 of the spacer and the thickness H1 of the light-shielding film are determined by designing two substrates sandwiching the liquid crystal layer to determine an appropriate value, and are determined by an appropriate value of H2, that is, a range of ΔH.

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

The liquid crystal display device including the light-shielding film or hardened film has high light-shielding property and insulation property, and further has a spacer function with excellent elastic modulus, deformation amount, and elastic recovery rate, and can be formed even with a film thickness of 1 μm to 7 μm. The left and right are also fine spacer shapes. [Example]

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

First, a synthesis example of the (A) polymerizable unsaturated group-containing alkali-soluble resin of the present invention will be described. 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 the weight was measured [W1 (g)], and the weight after heating at 160 ° C for 2 hr [W2 (g)] is determined by the following formula. Solid content concentration (% by weight) = 100 × (W2-W0) / (W1-W0)

[Acid value] The resin solution was dissolved in dioxane, and the solution was obtained by titration with a 1/10 N-KOH aqueous solution using a potential difference titration device [manufactured by Hiranuma Sangyo Co., Ltd., COM-1600].

[Molecular weight] Using colloidal permeation chromatography (GPC) [trade name HLC-8220GPC manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (two) + TSKgelSuperH-3000 (one) + TSKgelSuperH -4000 (one) + TSKgelSuper-H5000 (one) [manufactured by Tosoh Corporation], temperature: 40 ° C, speed: 0.6 ml / min] for measurement, standard polystyrene [manufactured by Tosoh Corporation] PS-oligomer set] The weight-average molecular weight (Mw) was obtained as a conversion value.

The abbreviations used in the synthesis examples and comparative synthesis examples are as follows. BPFE: reactant of 9,9-bis (4-hydroxyphenyl) fluorene and chloromethyloxane. Among the compounds of the general formula (I), X is a fluorene-9,9-diyl group, and R ₁ and R ₂ are hydrogen. BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride BTDA: 3,3', 4,4'-benzophenonetetracarboxylic dianhydride THPA: 1,2,3,6 -Tetrahydrophthalic anhydride TPP: triphenylphosphine PGMEA: propylene glycol monomethyl ether acetate

[Synthesis Example 1] A 1 L four-necked flask equipped with a reflux cooler was charged with 116.7 g (0.23 mol) of BPFE, 33.1 g (0.46 mol) of acrylic acid, 0.60 g of TPP, and 161.0 g of PGMEA. The reaction product was obtained by stirring for 12 hr at a temperature of from -10 to 105 ° C.

Then, 33.8 g (0.12 mol) of BPDA and 17.5 g (0.12 mol) of THPA were added to the obtained reaction product, and stirred under heating at 115 ° C to 120 ° C for 6 hr to obtain a base containing a polymerizable unsaturated group. Soluble resin solution (A) -1. The solid content concentration of the obtained resin solution was 56.5 wt%, the acid value (in terms of solid content) was 102 mgKOH / g, and the Mw obtained by GPC analysis was 3600.

[Comparative Synthesis Example 1] A 1000 ml four-necked flask equipped with a nitrogen introduction tube and a reflux tube was charged with 51.65 g (0.60 mol) of methacrylic acid, 38.44 g (0.38 mol) of methyl methacrylate, and 38.77 g ( 0.22 mol) of benzyl methacrylate, 5.91 g of azobisisobutyronitrile, and 370 g of diethylene glycol dimethyl ether were polymerized by stirring at 80 ° C to 85 ° C under a nitrogen stream for 8 hr. Furthermore, 39.23 g (0.28 mol) of glycidyl methacrylate, 1.44 g of TPP, and 0.055 g of 2,6-di-third-butyl-p-cresol were charged into the flask at 80 ° C to 85 ° C. After stirring for 16 hr, an alkali-soluble resin solution (A) -2 was obtained. The solid content concentration of the obtained resin solution was 32% by mass, the acid value (in terms of solid content) was 110 mgKOH / g, and the Mw obtained by GPC analysis was 18100.

(Alkali-soluble resin containing a polymerizable unsaturated group) (A) -1 component: The alkali-soluble resin solution (A) -2 obtained in the Synthesis Example 1 component: the alkali obtained in the Comparative Synthesis Example 1 Soluble resin solution

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

(Photopolymerization initiator) (C): Ethyl ketone, 1- [9-ethyl-6- (2-methylbenzylidene) -9H-oxazol-3-yl]-, 1- (O -Ethyl oxime) (manufactured by BASF, Japan, product name Irgacure OXE02)

(Carbon black dispersion) (D) -1: Resin-coated carbon black concentration 25.0% by mass and dispersant concentration 5.0% by mass PGMEA dispersion (solid content 30.0%) (D) -2: carbon black 20.0% by mass, high Molecular Dispersant 5.0% by mass PGMEA dispersion (25% solids)

(Solvent) (E) -1: PGMEA (E) -2: 3-methoxy-3-methyl-1-butyl acetate (epoxy resin) (G): 2,2-bis (hydroxymethyl) ) -1-butanol's 1,2-epoxy-4- (2-oxetanyl) cyclohexane adduct ("EHPE3150" manufactured by Daicel)

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

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

[Evaluation of constituent components of composition] <Preparation of composition for evaluating characteristics of carbon black> A resin solution ((A) -1 component) and a carbon black dispersion (( D) -1 component or (D) -2 component) and a solvent ((E) -1 component) to prepare a composition for measuring carbon black. The carbon black concentration was adjusted while measuring the optical density (OD) to prepare a composition capable of forming a cured film having an OD of 4 / μm. Table 1 shows the composition for surface resistivity measurement applications.

<Optical Density> The obtained carbon black measurement composition was coated on a glass substrate having a thickness of 1.2 mm so that the film thickness after the heat curing treatment was 1.1 μm using a spin coater, and the temperature was 1 at 90 ° C. Pre-baked in minutes. Then, using a hot-air drier, heat-hardening treatment was performed at 230 ° C for 30 minutes to obtain a cured film of the composition. Then, the optical density of the obtained cured film was measured using a Macbeth transmission densitometer, and the optical density per unit film thickness was evaluated.

<Surface Resistivity Measurement> The surface resistivity was measured at a voltage of 10 V using a surface resistivity measuring device (Hiresta UP manufactured by Mitsubishi Chemical Analytech) for a cured film having an optical density measured. . The measurement results are shown in Table 1.

[Table 1]

<Preparation of composition for evaluating characteristics of photocuring component> A resin solution ((A) -1 component), a photopolymerizable monomer ((B) component), a photopolymerization initiator ((C) component), and a solvent are used ((E) -1 component) to prepare a composition for evaluating the characteristics of the photocuring component shown in Table 2.

<Measurement of pencil hardness> Each of the obtained photosensitive resin compositions was coated on a glass substrate having a thickness of 1.2 mm using a spin coater so that the film thickness after the heat curing treatment became 1.2 μm, at 90 ° C. Pre-bake for 1 minute. Then, in a state where there is no photoresist, an ultrahigh-pressure mercury lamp with an illumination intensity of 30 mW / cm ² at a wavelength of 365 nm was irradiated with ultraviolet light of 100 mJ / cm ² to perform a photo-hardening reaction. Then, using a hot-air drier, heat-hardening treatment was performed at 230 ° C. for 30 minutes to obtain a cured film of a photo-curable component. For the cured film, a pencil hardness tester was used to apply a load of 500 g in accordance with the Japanese Industrial Standards (JIS) -K5400 test method, and the highest pencil hardness that did not damage the coating film at this time was set as the measurement value. . The pencil used is "Hi-uni".

[Table 2]

Regarding the evaluation of the photosensitive resin composition having a spacer function, the formulation components were blended at the ratios shown in Table 3 to prepare the photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 to 3. And evaluate. In addition, all the numerical values in Table 3 represent a mass part. In addition, (E) -1 in the column of the solvent is PGMEA (same as (E) -1) and carbon black in a resin solution containing an unsaturated group (an alkali-soluble resin solution containing a polymerizable unsaturated group). The amount of PGMEA (same as (E) -1) in the dispersion.

[table 3]

[Evaluation of the composition for a light-shielding film] The following evaluations were performed using the photosensitive resin composition for a light-shielding film of Examples 1 to 5 and Comparative Examples 1 to 3. These evaluation results are shown in Table 4.

<Developing characteristics> Using a spin coater, the film thickness after the thermosetting treatment was 3.0 μm (Example 1, Example 2, Example 4 and Comparative Example 3) or 1.5 μm (Example 3, Example 5 and Comparative). In the method of Example 1 and Comparative Example 2), each of the obtained photosensitive resin compositions was coated on a glass substrate having a thickness of 1.2 mm, and pre-baked at 90 ° C for 1 minute. Then, the photoresist was brought into close contact, and 100 mJ / cm ² of ultraviolet light was irradiated with an ultrahigh-pressure mercury lamp with an illumination intensity of 30 mW / cm ² at a wavelength of 365 nm to perform a photohardening reaction of the photosensitive portion.

Then, the exposed glass substrate was developed using a 0.05% potassium hydroxide aqueous solution at a pressure of 24 ° C. and 0.1 MPa for 60 seconds to remove unexposed portions of the coating film. Then, using a hot-air drier, heat-hardening treatment was performed at 230 ° C for 30 minutes to obtain a cured film of the photosensitive resin composition. The formation of thin lines of the obtained cured film pattern was confirmed with an optical microscope, and evaluation was performed in the following three stages. The results are shown in Table 4. ○: No residue and a pattern with an L / S of 10 μm / 10 μm or more △: No residue and a pattern with an L / S of 30 μm / 30 μm or more ×: No L / S less than 50 μm / 50 μm pattern, or the bottom curl or residue of the pattern is significant

<Volume resistivity> Using a spin coater, each of the obtained photosensitive resin compositions was coated on a glass substrate having a thickness of 1.2 mm in which Cr was vapor-deposited so that the film thickness after the heat curing treatment became 3.5 μm. The part except the electrode was pre-baked at 90 ° C for 1 minute. Then, a hot air dryer was used to perform heat curing treatment at 230 ° C. for 30 minutes 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, the volume resistivity at an applied voltage of 1 V to 10 V was measured using an electrometer (manufactured by Keithley, "type 6517A"). Table 4 shows the volume resistivity at the time of applying a voltage of 10 V under the conditions of holding the voltage for 60 seconds at each applied voltage.

<Dielectric Constant> Using a spin coater, each of the obtained photosensitive resin compositions was coated on a glass substrate having a thickness of 1.2 mm where Cr was vapor-deposited so that the film thickness after the heat curing treatment became 3.5 μm. The part except the electrode was pre-baked at 90 ° C for 1 minute. Then, a hot air dryer was used to perform heat curing treatment at 230 ° C. for 30 minutes to obtain a cured film of the photosensitive resin composition. Then, an aluminum electrode was formed on the cured film to form a substrate for measuring a dielectric constant. Then, an electrometer ("6517A" manufactured by Keithley) was used to measure the capacitance at a frequency of 1 Hz to 100,000 Hz, and the dielectric constant was calculated from the capacitance. Table 4 shows the calculated dielectric constants.

<Half tone (HT) characteristics of the spacer> Using a spin coater, the film thickness after heat curing treatment was 3.0 μm (Example 1, Example 2, Example 4 and Comparative Example 3) or 1.5 μm (Examples 3, 5 and Comparative Examples 1 and 2), each of the obtained photosensitive resin compositions was coated on a glass substrate having a thickness of 1.2 mm, and pre-baked at 90 ° C for 1 minute. grilled. Then, a photoresist having a dot pattern is tightly adhered, and an ultraviolet light of 5 mJ / cm ² or 100 mJ / cm ² is irradiated with an ultrahigh-pressure mercury lamp having an illuminance of 30 mW / cm ² at a wavelength of 365 nm to perform a photo-hardening reaction of the photosensitive portion. Then, the exposed glass substrate was developed using a 0.05% potassium hydroxide aqueous solution at a pressure of 24 ° C. and 0.1 MPa for 60 seconds to remove unexposed portions of the coating film. Then, using a hot-air drier, heat-hardening treatment was performed at 230 ° C for 30 minutes to obtain a cured film of the photosensitive resin composition.

The halftone characteristic of the spacer was calculated 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 . Evaluation is performed in three stages. The results are shown in Table 4. ○: 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 more than 2.9 μm

<Compression rate, elastic recovery rate, and breaking strength of the spacer> Using a spin coater, each of the obtained photosensitive resin compositions was coated onto a 1.2 mm-thick film so that the film thickness after the thermosetting treatment became 3.0 μm. The glass substrate was pre-baked at 90 ° C for 1 minute. Then, a photoresist having a dot pattern was closely adhered, and an ultrahigh-pressure mercury lamp with an illumination intensity of 30 mW / cm ² at a wavelength of 365 nm was irradiated with ultraviolet light of 100 mJ / cm ² to perform a photo-hardening reaction of the photosensitive portion.

Then, the exposed glass substrate was developed using a 0.05% potassium hydroxide aqueous solution at a pressure of 24 ° C. and 0.1 MPa for 60 seconds to remove unexposed portions of the coating film. Then, using a hot-air drier, heat-hardening treatment was performed at 230 ° C for 30 minutes to obtain a cured film of the photosensitive resin composition. The spacer characteristics of the obtained cured film pattern were evaluated using an ultra-micro hardness meter (manufactured by Fisher Instruments, Fischerscope HM2000Xyp). A 100 μm square flat indenter was squeezed in at a load speed of 5.0 mN / sec. After the load was 50 mN, the load was removed at a speed of 5.0 mN / sec to create a displacement curve. The compression ratio is calculated by the following formula by setting the displacement amount at a load of 50 mN at the load as L1. Compression ratio (%) = L1 / height of spacer × 100

The elastic recovery rate is calculated by the following formula by setting the displacement amount at a load of 50 mN at the load as L1 and the displacement amount at the time of removal of the load as L2. Elastic recovery rate (%) = (L1-L2) / L1 × 100

The breaking strength was evaluated using an ultra-micro hardness meter (manufactured by Fisher Instruments, Fischerscope HM2000Xyp). A 100 μm square flat indenter was pressed at a load speed of 5.0 mN / sec, and the load when the spacer was broken was measured at a load of 300 mN. The following three stages were used for evaluation. The results are shown in Table 4. ○: When the breaking strength is 300 mN or more △: When the breaking strength is 200 mN or more and less than 300 mN ×: When the breaking strength is 100 mN or more and less than 200 mN

<Shape of Separator> Each of the obtained photosensitive resin compositions was coated on a glass substrate having a thickness of 1.2 mm using a spin coater so that the film thickness after the thermosetting treatment became 3.0 μm at 90 ° C. Pre-bake for 1 minute. Then, a photoresist having a dot pattern was closely adhered, and an ultrahigh-pressure mercury lamp with an illumination intensity of 30 mW / cm ² at a wavelength of 365 nm was irradiated with ultraviolet light of 100 mJ / cm ² to perform a photohardening reaction of the photosensitive portion.

Then, the exposed glass substrate was developed using a 0.05% potassium hydroxide aqueous solution at a pressure of 24 ° C. and 0.1 MPa for 60 seconds to remove unexposed portions of the coating film. Then, using a hot-air drier, heat-hardening treatment was performed at 230 ° C for 30 minutes to obtain a cured film of the photosensitive resin composition. The shape of the spacer was evaluated using a scanning electron microscope with the internal angle (taper angle) of the end of the spacer. When the taper angle is 70 ° or more and 90 ° or less, ◎, when it is 50 ° or more and less than 70 °, it is ○, when it is 50 ° or less, it is △, and when it is 90 ° or more, it is ×.

[Table 4]

From the results of Examples 1 to 5 and Comparative Examples 1 to 3, it was found that by using (D) insulating carbon black and setting the hardness of the cured film excluding the (D) component to HB or more, the While maintaining the volume resistivity, spacer characteristics such as light-shielding property, dielectric constant, and elastic recovery rate are improved.

no.

no

Claims (11)

A photosensitive resin composition, which is a photosensitive resin composition for a light-shielding film having a spacer function, characterized in that it contains (A) component to (E) component as essential components: (A) containing a polymerizable unsaturated group Alkali-soluble resin; (B) a photopolymerizable monomer having at least three ethylenically unsaturated bonds; (C) a photopolymerization initiator; (D) formed into a film with an optical density of 4 / μm A light-shielding component containing an insulating carbon black having a surface resistivity of 1 × 10 ⁸ Ω / □ or more; and (E) a solvent; and a pencil hardness of a hardened material of a composition excluding the (D) component is HB or more. The photosensitive resin composition according to item 1 of the scope of patent application, wherein the (B) component is contained in an amount of 5 to 400 parts by mass based on 100 parts by mass of the (A) component, relative to the part. The component (A) and the component (B) have a total content of 100 parts by mass and contain the component (C) in an amount of 0.1 to 40 parts by mass, and the component (B) which becomes a solid component after photocuring is included. When a component other than the component (E) is a solid component, the total amount of the solid component includes the (D) component in an amount of 5 to 60% by mass. The photosensitive resin composition according to claim 1 or claim 2, wherein a polymerizable unsaturated group-containing alkali-soluble resin represented by the general formula (II) is used as the component (A), In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R ₅ represents a hydrogen atom or a methyl group, and X represents -CO- , -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, 芴 -9,9-diyl Or a straight bond, Y represents a tetravalent carboxylic acid residue, and Z each independently represents a hydrogen atom or -OC-W- (COOH) _l , where W represents a divalent carboxylic acid residue or a trivalent carboxylic acid residue, l Represents a number of 1 to 2, and n represents a number of 1 to 20. The photosensitive resin composition according to claim 1 or claim 2, wherein a light-shielding film having an optical density OD of 0.5 / μm or more and 4 / μm or less, and a voltage of 10 V when applied is formed. The volume resistivity is 1 × 10 ⁹ Ω · cm or more, and the dielectric constant is 2 to 10. The photosensitive resin composition according to claim 1 or claim 2, wherein in the load-unload test using a micro hardness tester, at least one of the following (i) to (iii) can be formed The light-shielding film has (i) a compression rate of 40% or less; (ii) an elastic recovery rate of 30% or more; (iii) a breaking strength of 200 mN or more. A light-shielding film having a spacer function, which is formed by curing the photosensitive resin composition according to any one of claims 1 to 5 of the scope of patent application. A liquid crystal display device is characterized in that it includes the light shielding film according to item 6 of the patent application scope as a black column spacer. The liquid crystal display device according to item 7 of the patent application scope, further comprising a thin film transistor. A method for manufacturing a light-shielding film, comprising: coating the photosensitive resin composition according to any one of claims 1 to 5 on a substrate; and applying light to the photosensitive resin composition. In a method for producing a light-shielding film that is cured on a substrate by curing a resin composition, the optical density OD as a light-shielding film is set to a film thickness H1 of 0.5 / μm or more and 4 / μm or less, and a spacer function The light-shielding film has a film thickness H2, and when H2 is 1 μm to 7 μm, a light-shielding film having a film thickness H1 and a film thickness H2 of ΔH = H2-H1 is 0.1-6.9. A method for manufacturing a liquid crystal display device, characterized in that a light-shielding film manufactured by using the method for manufacturing a light-shielding film according to item 9 of the scope of patent application is used as a black column spacer. The method for manufacturing a liquid crystal display device according to item 10 of the scope of patent application, wherein the liquid crystal display device includes a thin film transistor.