TW201732424A - Photosensitive resin composition for light-shielding film functioning as spacer, light-shielding film, LCD device, method for manufacturing photosensitive resin composition for light-shielding film functioning as spacer, method for manufacturing light-sh - Google Patents

Abstract

The present invention provides a photosensitive resin composition which is excellent in spacer properties such as elastic modulus, deformation amount, elastic recovery ratio and the like while maintaining light-shielding properties and insulating properties, and can obtain a fine and good spacer shape. The present invention relates to a photosensitive resin composition for light-shielding film functioning as spacer. The photosensitive resin composition of the present invention comprises the followings as essential components: (A) a polymerizable unsaturated group-containing alkali-soluble resin which is obtained by reacting a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols and an unsaturated group-containing monocarboxylic acid, with (a) a tetracarboxylic acid or its acid dianhydride and (b) a dicarboxylic acid or a tricarboxylic acid or its anhydride; (B) a photopolymerizable monomer having at least one ethylenically unsaturated bond; (C) a photopolymerization initiator; (D) one or more light-shielding component selected from the group consisting of black organic pigments, mixed organic pigments and light-shielding materials; (E) a solvent.

Description

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

The present invention relates to a photosensitive resin composition for a light-shielding film having a spacer function and a light-shielding film having a spacer function after curing, and more particularly to a photosensitive resin composition and a cured film thereof. A black columnar spacer having a spacer function and a black matrix function in a liquid crystal display device can be formed by photolithography. The present invention is further directed to a liquid crystal display device using the black columnar spacer obtained by the above hardening. The present invention further relates to the above-described photosensitive resin composition, a light shielding film, and a method of producing a liquid crystal display device.

In recent years, color liquid crystal display devices (LCDs) have been used in all fields such as liquid crystal televisions, liquid crystal screens, and color liquid crystal mobile phones. Among them, in order to improve the performance of the LCD, improvement in the characteristics of improving the viewing angle, contrast, and response speed is actively progressing, and most of the thin film transistors (TFT)-LCDs currently used have been developed. Panel structure. The TFT-LCD is mainly manufactured by separately manufacturing an array substrate on which a TFT is formed and a color filter substrate, and bonding the two substrates in a state of being kept at a certain interval by a spacer, but is also being developed to be low. A cost-effective, high-yield ratio LCD manufacturing process. For example, a manufacturing process has been developed in which a color filter is directly formed on a TFT of an array substrate and bonded to a glass substrate as a counter substrate. The structure thus formed is referred to as a color filter on TFT (COT) or the like on the TFT. In the COT, it is also considered to have a black matrix (the black matrix is the boundary of each pixel such as red (R), green (G), and blue (B) which is a color filter layer formed on the TFT) in RGB. A method of forming before formation, a method of forming after formation of RGB pixels, a method of forming on a glass substrate opposite thereto, and the like, and various LCD panel structures.

For the spacer having a certain function of achieving a liquid crystal layer belonging to one of the factors affecting the performance of the LCD (if the previous method is the interval between the array substrate and the color filter substrate), the spacer has always been sandwiched A method of spherical spacers of particle size. However, in this method, there is a problem that the amount of penetration of light per pixel is not constant due to the uneven dispersion state of the spherical spacer. For this problem, use A method of forming a columnar spacer by photolithography. However, the columnar spacer formed by photolithography is often transparent, and in such a columnar spacer, there is a problem in that the light incident from the oblique direction affects the electrical characteristics of the TFT and deteriorates the display quality. In view of such a problem, there is proposed an LCD panel structure using a light-shielding column spacer which is a light-shielding film having a spacer function formed by photolithography (Patent Document 1). In the COT, a method of forming a so-called black columnar spacer (BCS) by forming a columnar spacer with the same material as the black matrix is also discussed (for example, Patent Document 2).

In order to exhibit the function as a spacer, the light-shielding columnar spacer must have a film thickness of about 2 to 7 μm. Further, the light-shielding columnar spacer which is different in height from the other places where the TFT is formed must be formed at the same time. In addition, the light-shielding columnar spacer is also required to have an elastic modulus, a deformation amount, an elastic recovery rate, and the like as a spacer function in an appropriate range (Patent Document 3). Further, the light-shielding columnar spacer is also required to be improved by the reduction of the curable component caused by the addition of the light-shielding component (colorant) to the separator, and the influence of impurities such as the colorant. Loss of electrical characteristics, etc. (Patent Document 4).

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Laid-Open Patent Publication No. 08-234212

Patent Document 2: US Patent Application Publication No. 2009/0303407

Patent Document 3: Japanese Laid-Open Patent Publication No. 2009-031778

Patent Document 4: International Publication 2013/062011

In Patent Document 4, although a color mixed organic pigment is used, the optical density of the light-blocking column spacer is not disclosed. The mixed color organic pigment is effectively low in dielectric constant compared to an inorganic pigment such as carbon black, but the light blocking property is often low. Further, since the spacers must simultaneously form spacers having different heights, mechanical properties such as elastic modulus, deformation amount, and elastic recovery ratio are further required for the light-blocking column spacer. Since the shape and mechanical properties of the spacer are greatly affected by the light-shielding component, the design of the photosensitive resin composition for the light-shielding film is difficult. Therefore, the shape and mechanical properties of a separator using carbon black or a mixed color organic pigment or the like are still not sufficient, and further improvement is necessary.

Further, as described above, the light-blocking columnar spacer is manufactured to have a film thickness of about 2 to 7 μm. With the recent miniaturization of the liquid crystal display element, it is desirable that the light-shielding columnar spacer can have a fine spacer shape even when the film thickness is about 2 to 7 μm.

In view of the above-described problems, the present invention provides a light-shielding resin composition for a light-shielding film having a spacer function and having excellent light-shielding property and insulating property, and more excellent in elastic modulus, deformation amount, and elastic recovery rate. And a light-shielding film having a spacer function formed using the same, and a liquid crystal display device having the light-shielding film as a constituent element.

The present inventors have solved the problem of the light shielding film as described above. As a result of reviewing the problem of the photosensitive resin composition, it was found that a specific coloring agent is suitable as a light-shielding component of the photosensitive resin composition for the intended light-shielding film, and the present invention has been completed.

(1) The present invention is a photosensitive resin composition for a light-shielding film having a separator function, which comprises the following components (A) to (E) as essential components: (A) has a derivative derived from a bisphenol a reaction product of two epoxy propyl ether group epoxy compounds and an unsaturated group-containing monocarboxylic acid, and (a) a tetracarboxylic acid or an acid dianhydride thereof, and (b) a dicarboxylic acid or a tricarboxylic acid An alkali-soluble resin containing a polymerizable unsaturated group obtained by reacting an acid or an anhydride thereof; (B) a photopolymerizable monomer having at least one ethylenically unsaturated bond; (C) a photopolymerization initiator; (D) One or more kinds of light-shielding components in a group of black organic pigments, mixed color organic pigments, and light-shielding materials are selected; and (E) a solvent.

(2) The photosensitive resin composition according to (1), which contains titanium black as the (D) light-shielding component.

(3) The photosensitive resin composition according to (2), wherein the titanium black has an average secondary particle diameter of 100 to 300 nm.

(4) The photosensitive resin composition according to any one of (1) to (3), which comprises a black organic pigment and/or a mixed color organic pigment as (D) a light-shielding component, and the aforementioned black The average secondary particle diameter of the organic pigment and/or the mixed color organic pigment is from 20 to 500 nm.

(5) The photosensitive resin composition according to any one of (1) to (4), wherein the component (B) is contained in an amount of 5 to 400 parts by mass based on 100 parts by mass of the component (A). 100 parts by mass of the total of (A) component and (B) component, containing 0.1 to 30 parts by mass of the component (C); when it is included in the light hard When the component (B) is added as a solid component and the component of the component (E) is removed as a solid component, the component (D) is contained in an amount of 5 to 80% by mass based on the total amount of the solid component.

(6) The photosensitive resin composition according to any one of (1) to (5), which is capable of forming a light-shielding film having an optical density OD of 0.5/μm or more and 3/μm or less, and the light-shielding The volume resistivity at a voltage of 10 V applied to the film was 1 × 10 ⁹ Ω ‧ cm or more, and the dielectric constant was 2 to 10.

(7) The photosensitive resin composition according to any one of (1) to (6) which can be formed in a load-unloading test applied by a micro hardness tester, which satisfies the following ( The light-shielding film of at least one of i) to (iii): (i) the breaking strength is 200 mN or more, (ii) the elastic recovery rate is 30% or more, and (iii) the compression ratio is 40% or less.

(8) The present invention is a light-shielding film having a function of a spacer, which is formed by curing the photosensitive resin composition according to any one of (1) to (7).

(9) The present invention is also a liquid crystal display device comprising the light-shielding film of (8) as a black columnar spacer (BCS).

(10) The liquid crystal display device according to (9), further comprising a thin film transistor (TFT).

(11) The present invention is also a method for producing a photosensitive resin composition for a light-shielding film having a separator function, which is obtained by dispersing a dispersion obtained by dispersing (D) a light-shielding component in (E) a solvent. Further, the (A) alkali-soluble resin, (B) a photopolymerizable monomer having at least one ethylenically unsaturated bond, (C) a photopolymerization initiator, and (E) a solvent are further added to and mixed with the dispersion. ; Wherein the (A) alkali-soluble resin is a reaction product of an epoxy compound having two epoxypropyl ether groups derived from a bisphenol and a monocarboxylic acid containing an unsaturated group, and (a) An alkali-soluble resin obtained by reacting a tetracarboxylic acid or an acid dianhydride thereof and (b) a dicarboxylic acid or a tricarboxylic acid or an anhydride thereof; (D) a light-shielding component selected from the group consisting of a black organic pigment, a mixed color organic pigment, and a light-shielding material. One or more components in a group.

(12) The method of (11), wherein the (D) light-shielding component comprises titanium black.

(13) The method according to (12), wherein, in the dispersion, the titanium dioxide has an average secondary particle diameter of 100 to 300 nm.

The method of any one of (11) to (13), wherein the (D) light-shielding component comprises a black organic pigment and/or a mixed color organic pigment, and in the dispersion, the black color The average secondary particle diameter of the organic pigment and/or the mixed color organic pigment is from 20 to 500 nm.

(15) The method of producing a light-shielding film according to any one of (1) to (7), wherein the photosensitive resin is coated by light irradiation. The composition is hardened to form a light-shielding film on the substrate.

(16) The present invention is also a method for producing a light-shielding film, which is a method for producing a light-shielding film according to (15), and at the same time, when H2 is 2 to 7 μm, ΔH=H2-H1 is 0.1 to 2.9. In the light-shielding film of the film thickness H1 and the film thickness H2, the film thickness H1 is a film thickness for making the optical density of the light-shielding film 0.5/μm or more and less than 3/μm, and the film thickness H2 is a spacer function. The film thickness of the light shielding film.

(17) The present invention is also a method for producing a liquid crystal display device, which comprises the light-shielding film produced in the method of (16) as a black columnar spacer.

(18) The manufacturing method according to (17), wherein the liquid crystal display device has a thin film transistor (TFT).

Since the photosensitive resin composition for a light-shielding film according to the present invention contains a specific coloring agent, it is possible to maintain the light-shielding property and the insulating property, and the elastic modulus and the deformation amount as compared with the conventional photosensitive resin composition. A hardened material with excellent elastic recovery rate. Further, the photosensitive resin composition for a light-shielding film according to the present invention can form a fine spacer shape even when the film thickness is about 2 to 7 μm.

Hereinafter, the present invention will be described in detail.

The alkali-soluble resin containing a polymerizable unsaturated group of the component (A) is an epoxy compound having two epoxypropyl ether groups derived from a bisphenol, and is preferably represented by the formula (I). a hydroxyl group-containing compound (c) containing a polymerizable unsaturated group and an (a) tetracarboxylic acid obtained by reacting an epoxy compound with (meth)acrylic acid (this is meaning "acrylic acid and/or methacrylic acid") An alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule obtained by reacting the acid dianhydride or (b) a dicarboxylic acid or a tricarboxylic acid or an anhydride thereof. In the component (A), the polymerizable unsaturated double bond and the carboxyl group are combined, and the photocurable property, the excellent developability, and the patterning property of the photosensitive resin composition can be imparted to obtain the physical properties of the light-shielding film. Upgrade.

However, in the formula (I), R ₁ , R ₂ , R ₃ and R ₄ are independently represented by 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-, or 茀-9,9-diyl Or a single bond, the average value of m is from 0 to 10, preferably from 0 to 3.

Examples of the bisphenol which imparts the epoxy compound of the formula (I) include bis(4-hydroxyphenyl) ketone, bis(4-hydroxy-3,5-dimethylphenyl) ketone, and bis(4- Hydroxy-3,5-dichlorophenyl)one, bis(4-hydroxyphenyl)anthracene, bis(4-hydroxy-3,5-dimethylphenyl)anthracene, bis(4-hydroxy-3,5 -dichlorophenyl)indole, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy-3,5- Dichlorophenyl) hexafluoropropane, bis(4-hydroxyphenyl)dimethyl decane, bis(4-hydroxy-3,5-dimethylphenyl)dimethyl decane, bis(4-hydroxy-3) ,5-dichlorophenyl)dimethyl decane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy-3,5- Dibromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-dual (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) Indole, 9,9-bis(4-hydroxy-3-chlorophenyl)indole, 9,9-bis(4-hydroxy-3-bromophenyl)anthracene, 9,9-bis(4-hydroxy-3- Fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)anthracene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)anthracene, 9, 9-bis(4-hydroxy-3,5-dichlorophenyl)anthracene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)anthracene, 4,4'-bisphenol, 3, 3'-bisphenol, etc. These bisphenols may be used alone or in combination of plural kinds. Among them, it is particularly preferred to use a bisphenol of the formula (I) wherein X is a -9,9-diyl group.

The compound of the formula (I) for deriving the (A) alkali-soluble resin is an epoxy compound having two epoxypropyl ether groups obtained by reacting the above bisphenols with epichlorohydrin. In the case of this reaction, generally, with the oligomerization of the diglycidyl ether compound, m is an integer of 0 to 10 in each molecule, and a molecule having a plurality of values is usually mixed, so the average value is 0 to 10. (not limited to an integer), the average value of m is preferably 0 to 3. When the average value of m exceeds the upper limit, when the alkali-soluble resin synthesized using the epoxy compound is used as a photosensitive resin composition, the viscosity of the composition becomes too large to be applied smoothly, or alkali solubility cannot be sufficiently provided. The alkali developability becomes extremely poor.

Next, a hydroxyl group-containing compound containing a polymerizable unsaturated group obtained by reacting an epoxy compound with (meth)acrylic acid and an acid component are reacted to obtain a base having a carboxyl group and a polymerizable unsaturated group in one molecule. Soluble resin. As the acid component, a tetracarboxylic acid or an acid dianhydride (a) which can react with a compound containing a hydroxyl group, and a dicarboxylic acid or a tricarboxylic acid or an acid anhydride (b) thereof are preferably used. The carboxylic acid residue of this acid component may have one of a saturated hydrocarbon or an unsaturated hydrocarbon. Further, -O-, -S-, or a carbonyl group may be contained in the carboxylic acid residues. Such as a bond containing a hetero element.

Specific examples of the acid component are shown below, but the dianhydride and monoanhydride of the exemplified polycarboxylic acid can also be used.

First, as the (a) tetracarboxylic acid, a chain hydrocarbon tetracarboxylic acid, an alicyclic tetracarboxylic acid or an aromatic polycarboxylic acid can be mentioned. Here, as the chain hydrocarbon tetracarboxylic acid, for example, butane tetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, or the like, or a tetracarboxylic acid to which an arbitrary substituent is introduced may be used. Further, as the alicyclic tetracarboxylic acid, for example, cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid, etc. It may be a tetracarboxylic acid to which 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 may be any of the substituents introduced therein. carboxylic acid. These (a) tetracarboxylic acid type may be used alone or in combination of plural kinds.

Further, as the (b) dicarboxylic acid or tricarboxylic acid, a chain hydrocarbon dicarboxylic acid or a tricarboxylic acid, an alicyclic dicarboxylic acid or a tricarboxylic acid, an aromatic dicarboxylic acid or a tricarboxylic acid can be used. Here, as a chain hydrocarbon dicarboxylic acid or a tricarboxylic acid, for example, succinic acid, acetyl succinic acid, maleic acid, adipic acid, itaconic acid, sebacic acid, methyl malic acid, malonic acid , glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, etc., and may also be a dicarboxylic acid or a tricarboxylic acid into which an arbitrary substituent is introduced. . Further, as an alicyclic dicarboxylic acid or a tricarboxylic acid, for example, a cyclobutane dicarboxylic acid, a cyclopentane dicarboxylic acid, a hexahydrophthalic acid, a tetrahydrophthalic acid, a norbornane dicarboxylic acid Further, it may be a dicarboxylic acid or a tricarboxylic acid to which an arbitrary substituent is introduced. In addition, Examples of the aromatic dicarboxylic acid or tricarboxylic acid include phthalic acid, isophthalic acid, trimellitic acid, and the like, and may be a dicarboxylic acid or a tricarboxylic acid into which an arbitrary substituent is introduced. These (b) dicarboxylic acid or tricarboxylic acid type may be used alone or in combination of plural kinds.

The molar ratio (b)/(a) of (a) a tetracarboxylic acid or an acid dianhydride thereof and (b) a dicarboxylic acid or a tricarboxylic acid or an anhydride thereof used in the (A) alkali-soluble resin is 0.01 To 0.5, preferably 0.02 or more and less than 0.1. When the molar ratio (b)/(a) is out of the above range, the optimum molecular weight of the photosensitive resin composition having high light-shielding and high electric resistance as the present invention is not obtained, which is not preferable. In addition, the smaller the molar ratio (b) / (a), the greater the alkali solubility and the higher the molecular weight.

The ratio of the reaction of the hydroxyl group-containing compound (c) containing the polymerizable unsaturated group to the acid components (b) and (a) is preferably such that the terminal of the compound becomes a carboxyl group and the components are used. The molar ratio is quantitatively reacted in the manner of (c): (b): (a) = 1: 0.2 to 1.0: 0.01 to 1.0. In this case, it is preferred that the molar ratio (c) / [(b) / 2+ (a)] = 0.5 to the total amount of the hydroxyl group-containing compound (c) containing a polymerizable unsaturated group relative to the acid component is The quantitative reaction was carried out in a 1.0 manner. When the molar ratio is less than 0.5, the end of the alkali-soluble resin becomes an acid anhydride, and the content of the unreacted acid dianhydride increases, and the stability of the alkali-soluble resin composition is lowered. On the other hand, when the molar ratio exceeds 1.0, the content of the unreacted hydroxyl group-containing compound containing a polymerizable unsaturated group increases, and the stability of the alkali-soluble resin composition is lowered. The molar ratio of each component of (a), (b), and (c) can be adjusted by adjusting the acid value and molecular weight of the alkali-soluble resin. However, it is arbitrarily changed in the above range.

(A) The alkali-soluble resin can be produced according to the method described above, and can be produced by a method described in, for example, JP-A-H08-278629 or JP-A-2008-9401. First, as a method of reacting the epoxy compound of the formula (I) with (meth)acrylic acid, for example, a molar (meth)acrylic acid such as an epoxy group of an epoxy compound is added to a solvent, A method of heating, stirring, and reacting at 90 to 120 ° C while blowing air in the presence of a medium (triethylbenzylammonium chloride, 2,6-diisobutylphenol, etc.). Next, as a method of reacting a hydroxyl group of an epoxy acrylate compound of a reaction product with an acid anhydride, a predetermined amount of an epoxy acrylate compound, an acid dianhydride, and an acid monoanhydride are added to a solvent, and a catalyst (bromination) A method of heating, stirring, and reacting at 90 to 140 ° C in the presence of tetraethylammonium, triphenylphosphine, or the like.

The (A) alkali-soluble resin produced in this manner has, for example, a structure represented by the formula (II).

In the formula, R ₁ , R ₂ , R ₃ and R ₄ are each independently represented by 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-, or 茀-9,9 a di- or direct bond, Y represents a 4-membered carboxylic acid residue, and Z is each independently represented as a hydrogen atom or -OC-W-(COOH) ₁ (only, W represents a 2- or 3-membered carboxylic acid residue, 1 Indicates the number from 1 to 2), and n represents the number from 1 to 20.

(A) The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the alkali-soluble resin, usually from 1,000 to 100,000, preferably from 2,000 to 20,000. When the weight average molecular weight is less than 1,000, there is a concern that the pattern adhesion at the time of alkali development is lowered, and when the weight average molecular weight exceeds 100,000, the developability is remarkably lowered.

Further, the acid value of the (A) alkali-soluble resin is preferably in the range of 80 to 120 mgKOH/g. When the value is less than 80 mgKOH/g, the residue tends to remain during alkali development. When the amount exceeds 120 mgKOH/g, the immersion of the alkaline developing solution is early, and peeling development occurs, and neither of them is poor. Further, (A) the alkali-soluble resin containing a polymerizable unsaturated group may be used singly or in combination of two or more kinds.

In the present invention, the weight average molecular weight of (A) is determined by dissolving the sampled solution in tetrahydrofuran and measuring the molecular weight distribution by HLC-8220GPC manufactured by TOSOH Co., Ltd., and calculating the weight average molecular weight in terms of standard polystyrene. value. The acid value of the component A is used to dissolve the sampled solution in the second The value of the acid value in terms of the solid content of the sample solution calculated from the equivalent point was determined by neutralization titration with an aqueous solution of 0.1 equivalent of potassium hydroxide in the alkane.

Next, as (B) a photopolymerizable monomer having at least one ethylenically unsaturated bond, for example, (meth)acrylic acid 2-hydroxyl group a (meth) acrylate having a hydroxyl group such as ethyl ester, 2-hydroxypropyl (meth) acrylate or 2-hydroxyhexyl (meth) acrylate; ethylene glycol di(meth) acrylate, diethylene glycol Alcohol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, trimethylol Propane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, neopentyl Alcohol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, glyceryl (meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta (methyl) Acrylate, or neopentyltetraol hexa(meth) acrylate, sorbitol hexa(meth) acrylate, phosphazene alkylene oxide modified hexa(meth) acrylate, (meth)acrylates such as ester-modified dipentaerythritol hexa(meth)acrylate; polyhydric alcohols such as pentaerythritol and dipentaerythritol; and polyphenols such as phenol novolak Vinyl benzyl Ether compounds; divinylbenzene divinyl compound based addition polymer. These (B) photopolymerizable monomers having at least one ethylenically unsaturated bond may be used alone or in combination of plural kinds. Further, (B) the photopolymerizable single system having at least one ethylenically unsaturated bond does not have a free carboxyl group.

The compounding ratio of the component (B) may be 5 to 400 parts by mass, preferably 10 to 150 parts by mass, based on 100 parts by mass of the component (A). When the blending ratio of the component (B) is more than 400 parts by mass based on 100 parts by mass of the component (A), the cured product after photocuring becomes brittle, and the acid value of the coating film in the unexposed portion becomes low, so The solubility of the alkaline developing solution is lowered, and the problem that the edge of the pattern becomes jagged becomes unclear. On the other hand, relative to (A) When the blending ratio of the component (B) is less than 5 parts by mass, the proportion of the photoreactive functional group in the resin is small, and the formation of the crosslinked structure is insufficient, and the acid value in the resin component is insufficient. When the solubility in the exposed portion is high for the alkaline developing solution, there is a concern that the formed pattern becomes thinner than the target line width, or the pattern is easily formed.

Further, examples of the photopolymerization initiator of the component (C) include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, and p-dimethylamino group. Acetophenones such as propiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone; benzophenone, 2-chlorobenzophenone, p,p'-bisdimethyl Benzophenones such as carbamide benzophenone; benzil, 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-di(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-4,5-di a biimidazole-based compound such as phenylbiimidazole, 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole or 2,4,5-triarylbiimidazole; 2-trichloromethyl- 5-styryl-1,3,4- Diazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4- Diazole, 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4- Halogenated methyldiazole compounds such as oxadiazole; 2,4,6-tris(trichloromethyl)-1,3,5-three 2-methyl-4,6-bis(trichloromethyl)-1,3,5-three 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-three , 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-three , 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-three , 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-three , 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-three 2-(4-Methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-three Isohalogenated methyl Compounds; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzamide), 1-(4-phenylthiophenyl) Butane-1,2-dione-2-indole-O-benzoate, 1-(4-methylthiophenyl)butane-1,2-dione-2-indole-O-B Acid ester, 1-(4-methylthiophenyl)butan-1-one oxime-O-acetate, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzamide) -9H-carbazol-3-yl]-, 1-(O-acetamidine), ketone, (9-ethyl-6-nitro-9H-carbazol-3-yl)[4- (2-methoxy-1-methylethoxy)-2-methylphenyl]-, O-acetamidine, ketone, (2-methylphenyl) (7-nitro-9, 9-dipropyl-9H-indol-2-yl)-, acetamidine, ethyl ketone, 1-[7-(2-methylbenzhydryl)-9,9-dipropyl-9H-indole -2-yl]-, 1-(O-acetamidine), ethyl ketone, 1-(-9,9-dibutyl-7-nitro-9H-indol-2-yl)-, 1-O - O-mercapto lanthanide compounds such as acetamidine; benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethyl thioxanthone, 2-methyl thioxanthene a sulfur compound such as a ketone or 2-isopropylthioxanthone; an anthracene such as 2-ethylhydrazine, octamethylguanidine, 1,2-benzopyrene or 2,3-diphenylanthracene; Azobisisobutyronitrile, benzammonium peroxide, cumene peroxide, etc. Thereof; 2- mercaptobenzimidazole, 2-mercaptobenzimidazole a thiol compound such as azole or 2-mercaptobenzothiazole. Among them, from the viewpoint of easily obtaining a photosensitive resin composition for a light-shielding film having high sensitivity, an O-fluorenyl compound is preferably used. These (C) photopolymerization initiators may be used alone or in combination of plural kinds. Further, the photopolymerization initiator in the present invention is used in the meaning of containing a sensitizer.

These photopolymerization initiators or sensitizers may be used alone or in combination of two or more. Moreover, it is also possible to add a function which does not exert a photopolymerization initiator or a sensitizer by itself, but by a group A compound which can increase the ability of a photopolymerization initiator or a sensitizer is used in combination. As such a compound, for example, a tertiary amine such as triethanolamine or triethylamine which is effective in combination with benzophenone can be mentioned.

The amount of the photopolymerization initiator to be used in the component (C) may be 0.1 to 30 parts by mass, preferably 1 to 25 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). When the proportion of the component (C) is less than 0.1 part by mass, the rate of photopolymerization is slow and the sensitivity is lowered. On the other hand, when it exceeds 30 parts by mass, the sensitivity is too strong, and the pattern line width is relative to the pattern mask. The state is thicker, and it is impossible to reproduce the doubt that the mask has a faithful line width, or that the edge of the pattern is jagged and cannot be sharpened.

The component (D) is a light-shielding component selected from the group consisting of a black organic pigment, a mixed color organic pigment, and a light-shielding material, and is a component excellent in insulation, heat resistance, light resistance, and solvent resistance. Here, examples of the black organic pigment include black, aniline black, cyanine black, and indoleamine black. As a color-mixing organic pigment, two or more types of pigments selected from red, blue, green, purple, yellow, cyanine, and magenta are mixed and simulated black. Examples of the light shielding material include carbon black, chromium oxide, iron oxide, and titanium black. These (D) light-shielding components may be used alone or in combination of plural kinds.

As a light-shielding material, titanium black is preferable from the viewpoint of good light-shielding property, elastic modulus, deformation amount, and elastic recovery rate. When titanium black is used, black organic pigments and/or color mixed organic pigments may be used in combination for the purpose of further improving the insulating properties. Thus, when an inorganic light-shielding material is used together with an organic pigment, [light-shielding material/(black organic pigment and/or color mixture is The mixing ratio of the organic pigment) can be 90/10 to 10/90, preferably 70/30 to 30/70 in terms of mass ratio. By such a combination of the light-shielding material and the organic pigment, and the blending ratios thereof, a light-shielding film having a spacer function having desired properties such as light-shielding property and insulating property can be obtained. For the purpose of controlling the chromaticity of the light-shielding film such as achromatic color, etc., the organic pigment other than black is not only mixed for color mixing but also black, and may be added as a single color.

The titanium black used in the present invention is a titanium-containing black inorganic pigment typified by low-order titanium oxide, titanium oxynitride or the like, and among them, those having high insulating properties can be preferably used. As a method of producing such a titanium black, a method of heating and reducing a mixture of titanium dioxide and titanium metal in a reducing environment is disclosed (JP-A-49-5432), and a high temperature of titanium tetrachloride is used. A method of reducing ultrafine titanium dioxide obtained by hydrolysis in a reducing environment containing hydrogen (JP-A-57-205322), and a method of reducing titanium dioxide or titanium hydroxide in the presence of ammonia at a high temperature (Japanese special open method) Japanese Laid-Open Patent Publication No. Sho 61-201610, etc., a method in which a vanadium compound is adhered to titanium dioxide or titanium hydroxide, and a high-temperature reduction is carried out in the presence of ammonia (JP-A-61-201610). However, it is not limited by these.

Further, the titanium-containing black inorganic pigment may be one in which an inorganic compound or an inorganic compound is coated on the surface of the inorganic particles. Examples of the organic compound to be coated include a polyol, an alcohol amine or a derivative thereof, an organic hydrazine compound (polysiloxane, a decane coupling agent, etc.), a higher fatty acid or a metal salt thereof, and an organometallic compound ( Titanium coupler, aluminum couple Mixture, etc.). On the other hand, examples of the inorganic compound to be coated include an aluminum compound, a ruthenium compound, a zirconium compound, a tin compound, a titanium compound, and a ruthenium compound. As a method of covering the surface of the titanium-containing particles, a method described in JP-A-2006-206891 or the like can be used.

Examples of commercially available products of titanium black include Titanium Black 12S, 13M-T, 13M-C, and UF8 manufactured by Mitsubishi Materials; and Tilack D ("Tilack D" is a registered trademark of the company). Wait.

The organic pigment to be used in the present invention is not particularly limited, and a known compound can be used, and it is preferred that the specific surface area by the BET method of the microparticulation processing is 50 m ² /g or more. Specific examples thereof include azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoporphyrin pigments, and a pigment, a threne pigment, an anthraquinone pigment, a picone pigment, a quinophthalone pigment, a diketopyrrolopyrrole pigment, a thioindigo pigment, etc., specifically, a CI name as described below The compounds are not limited by these.

CI 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.; CI Pigment Orange 5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81, etc.; CI 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.; CI pigment green 7, 36, 58, etc.; CI pigment blue 15, 15: 1, 15: 2, 15: 3, 15:4, 15:6, 16, 60, 80, etc.; CI Pigment Violet 19, 23, 37, etc.

Further, examples of the solvent of the component (E) include methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, and ethylene glycol monobutylene. Alcohols, alcohols such as 3-hydroxy-2-butanone and diacetone; terpenes such as α-terpineol or β-terpineol; acetone, methyl ethyl ketone, cyclohexanone, N-A Ketones such as phenyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; celecoxime, methyl acesulfame, ethyl acesulfame, carbitol, and methyl carbene Alcohol, 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. Alcohol ethers; ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, celecoxib acetate, ethyl cyanohydrin Acid ester, butyl cyproterone acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Esters and the like, etc., by using these solvents The solution is dissolved and mixed to form a uniform solution-like composition. These solvents may be used in combination of two or more kinds in order to have the necessary properties such as coating properties.

Further, these light-shielding components are preferably dispersed in a solvent together with the (F) dispersant to form a light-shielding dispersion liquid, and then formulated into a photosensitive resin composition for a light-shielding film. Here, since the solvent to be dispersed is a part of the component (E), it can be used as long as it is listed in the above component (E). For example, propylene glycol monomethyl ether acetate or acetic acid 3- can be preferably used. Methoxybutyl ester and the like. The blending ratio of the (D) light-shielding component to form the light-shielding dispersion liquid may be 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. Further, the above-mentioned solid portion means a component which removes the component (E) in the composition. In the above solid portion, the component (B) which becomes a solid component after photocuring is also included. If it is less than 5% by mass, it cannot be set to a desired light blocking property. When the content is more than 80% by mass, the content of the photosensitive resin which is originally a binder is reduced, which causes a problem of impairing the development characteristics and impairing the film forming ability.

The average particle diameter (hereinafter referred to as "average secondary particle diameter") measured by a laser diffraction/scattering particle size distribution device in the light-shielding dispersion liquid is preferably as follows. get on. The average secondary particle diameter of titanium black when using titanium black may be 100 to 300 nm; when black organic pigment and/or mixed color organic pigment, and/or monochromatic organic pigment is used, the average secondary particle diameter of the dispersed particles may be 20 to 500 nm. Further, even in the photosensitive resin composition for a light-shielding film prepared by disposing these light-shielding dispersions, the light-shielding components preferably have the same average secondary particle diameter.

In the light-shielding dispersion, a (F) dispersant is used in order to stably disperse the light-shielding component, and a known dispersant such as various polymer dispersants can be used for the purpose. As an example of a dispersant, there is no A known compound (a compound which is commercially available under the names of a dispersing agent, a dispersing wetting agent, a dispersing accelerator, etc.) used for the dispersion of the pigments can be used, and examples thereof include a cationic polymer dispersing agent and an anionic property. A polymer dispersant, a nonionic polymer dispersant, a pigment derivative dispersant (dispersion aid), and the like. In particular, it is preferred to have a cationic functional group such as an imidazolyl group, a pyrrolyl group, a pyridyl group, a primary amino group, a secondary amino group or a tertiary amino group as a point of adsorption to the pigment, and an amine value of from 1 to 100 mgKOH/g, A cationic polymer-based dispersant having a number average molecular weight of from 1,000 to 100,000. The dispersing agent is formulated in an amount of from 1 to 30% by mass, preferably from 2 to 25% by mass, based on the light-shielding component.

In addition, when a light-shielding dispersion liquid is prepared, a part of the alkali-soluble resin containing a polymerizable unsaturated group of the component (A) is co-dispersed in addition to the above-mentioned dispersing agent, thereby preparing a photosensitive resin for a light-shielding film. In the case of the composition, it is possible to obtain a photosensitive resin composition which is easy to maintain the high sensitivity of the exposure sensitivity, has good adhesion during development, and is less likely to cause residue. 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. When the amount of the component (A) is less than 2% by mass, the effect of co-dispersion such as improvement in sensitivity, improvement in adhesion, and reduction in residue cannot be obtained. In addition, when the content of the light-shielding material is large, the viscosity of the light-shielding dispersion liquid is high, and it is difficult to uniformly disperse or it takes a lot of time, and it becomes difficult to obtain a uniform light-shielding component. A photosensitive resin composition of a dispersed coating film.

The light-shielding dispersion liquid thus obtained is obtained by the component (A) (the remaining component (A) is dispersed when the light-shielding dispersion liquid is prepared The component (A), the component (B), the component (C), and the remaining component (E) are mixed to form a photosensitive resin composition for a light-shielding film.

Further, in the photosensitive resin composition of the present invention, a curing accelerator, a thermal polymerization inhibitor, and an antioxidant, a plasticizer, a filler, a solvent, a leveling agent, an antifoaming agent, a coupling agent, and an interface may be blended as needed. Additives such as active agents. Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, and thiophene Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate. Examples of the filler include glass fiber, cerium oxide, and mica. Examples of the antifoaming agent or the leveling agent include an anthrone-based, fluorine-based, or acrylic-based compound. Further, examples of the surfactant include a fluorine-based surfactant and an anthrone-based surfactant. Examples of the coupling agent include 3-(glycidoxy)propyltrimethoxydecane and 3-propene oxime. A decane coupling agent such as oxypropyltrimethoxydecane, 3-isocyanatopropyltriethoxydecane or 3-ureidopropyltriethoxydecane.

In the photosensitive resin composition of the present invention, other resin components which are polymerized or cured by heat can be used in combination. As another resin component, (G) an epoxy resin or an epoxy compound having two or more epoxy groups is preferable, and 3,3',5,5'-tetramethyl-4,4'-double is mentioned. Phenolic epoxy resin, bisphenol A epoxy resin, bisphenol oxime epoxy resin, phenol novolak epoxy resin, 3,4-epoxycyclohexenylmethyl-3', 4'- Addition of 1,2-epoxy-4-(2-oxiranyl)cyclohexane of epoxycyclohexenecarboxylate and 2,2-bis(hydroxymethyl)-1-butanol , epoxy ketone resin, and the like. These additional components can be used only One type of compound may be used in combination of plural kinds.

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

The photosensitive resin composition for a light-shielding film of the present invention is excellent as, for example, a photosensitive resin composition for forming a light-shielding film having a separator function. The method of forming the light-shielding film having a spacer function is a photolithography method as described below. First, the photosensitive resin composition for a light-shielding film of the present invention is applied onto a substrate, and then the solvent is dried (prebaked), and then a light mask is placed on the film obtained as described above. The exposed portion is cured by irradiation with ultraviolet rays, and development by elution of the unexposed portion using an alkaline aqueous solution is carried out to form a pattern, and further, a method of post-drying and baking (thermal baking) is performed.

The substrate may be a transparent substrate, or may be formed on a transparent film such as an alignment film formed on a pixel or a flattening film on a pixel or a flat film on a pixel after forming a pixel such as RGB. The substrate. The formation of a light-shielding film having a spacer function on which substrate differs depending on the design of the liquid crystal display device.

As a transparent substrate to which a photosensitive resin composition is applied, in addition to a glass substrate, vapor deposition or patterning on a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether oxime, etc.) may be exemplified. A substrate having a transparent electrode such as ITO or gold. Coating photosensitivity on a transparent substrate The method of the solution of the resin composition may be any method such as a roll coater, a land coater, a slit coater or a rotary machine, in addition to a known solution dipping method or a spray method. After coating to a desired thickness by these methods, the solvent is removed (prebaked) to form a film. The prebaking can be carried out by heating using an oven, a hot plate or the like. The heating temperature and heating time of the prebaking can be appropriately selected depending on the solvent to be used, for example, at a temperature of 60 to 110 ° C for 1 to 3 minutes.

The exposure performed after the prebaking is performed by an ultraviolet exposure apparatus, and exposure is performed through a light mask, whereby only a portion of the resist corresponding to the pattern is exposed. The exposure apparatus and the exposure and irradiation conditions thereof are appropriately selected, and exposure is performed using a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, or a far ultraviolet lamp to photoharden the photosensitive resin composition in the coating film.

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

After the development, heat treatment (post-baking) is preferably carried out at a temperature of from 180 to 250 ° C and for 20 to 60 minutes. This post-baking is performed for the purpose of improving the adhesion between the patterned light-shielding film and the substrate. This is carried out by heating using an oven, a hot plate or the like in the same manner as the prebaking. The patterned light-shielding film of the present invention is formed by the above various steps by photolithography.

According to the above method, a light-shielding film having an optical density of 0.5/μm to 3/μm, preferably 1.5/μm to 2.5/μm can be formed. Further, according to the above method, 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. Further, according to the above method, a light-shielding film having a dielectric constant of 2 to 10, preferably 2 to 8, more preferably 3 to 6 can be formed. Further, according to the above method, it is possible to form a light-shielding film having a breaking strength of 200 mN or more, and/or an elastic recovery ratio of 30% or more, and/or a compression ratio of 40% or less in the mechanical property test. The light-shielding film formed by the above method can be used as a columnar spacer of a liquid crystal display device, and is preferably used as a black columnar spacer.

In addition, when the film thickness H1 which is an optical density of the light-shielding film is 0.5/μm or more and less than 3/μm, and the film thickness H2 of the light-shielding film which functions as a spacer, H2 is 2 to 7 μm. ΔH=H2-H1 is 0.1 to 2.9, and a light-shielding film having a film thickness H1 and a light-shielding film having a film thickness H2 can be simultaneously formed. The cured film formed by the above method can be used as a columnar spacer of a liquid crystal display device, and is preferably used as a black columnar spacer. According to the cured film in which the above ΔH is in the above range, since the black columnar spacer having the height difference can be formed at one time from the same material, the liquid crystal display device can be manufactured more efficiently. At this time, for example, the cured film having the film thickness H2 functions as a spacer, and the cured film having the film thickness H1 functions as a black matrix. In addition, △H becomes For the reason, if the film of the black matrix function is set to have the same film thickness as the film of the spacer function, the liquid crystal layer is differentiated one by one in each pixel unit, and the liquid crystal layer is prevented from flowing freely. There is a concern that the yield ratio at the time of filling the liquid crystal layer into a liquid crystal display device is lowered.

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

The liquid crystal display device having the above-mentioned light-shielding film or cured film has high light-shielding property and insulating property, and has a spacer function which is excellent in elastic modulus, deformation amount, and elastic recovery rate, and can be formed fine even when the film thickness is about 2 to 7 μm. Spacer shape.

[Examples]

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

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

[solid concentration]

1 g of the resin solution obtained in the synthesis example was impregnated into a glass filter [weight: W ₀ (g)] and weighed [W ₁ (g)], and the weight after heating at 160 ° C for 2 hr [W ₂ (g) ] is obtained by the following formula.

Solid concentration (% by weight) = 100 × (W _{2 -} W ₀ ) / (W _{1 -} W ₀ ).

[acid price]

Making the resin solution in two The alkane was dissolved and titrated by a 1/10 N-KOH aqueous solution using a potentiometric titration apparatus [manufactured by Hiranuma Sangyo Co., Ltd., trade name: COM-1600].

[molecular weight]

By gel permeation chromatography (GPC) [trade name HLC-8220GPC, manufactured by TOSOH Co., Ltd., solvent: tetrahydrofuran, column: TSKgel SuperH-2000 (2) + TSKgel SuperH-3000 (1) + TSKgel SuperH-4000 (1 ) +TSKgel Super-H5000 (1) [manufactured by TOSOH Co., Ltd.], temperature: 40 ° C, speed: 0.6 ml/min], and was measured as standard polystyrene [PS- oligomer reagent manufactured by TOSOH Co., Ltd.) The weight average molecular weight (Mw) of the box was converted.

[Average secondary particle size measurement]

In the light-shielding dispersion liquid, a solvent (in the present example, PGMEA) is diluted to a solution having a light-shielding component concentration of about 0.1% by mass, and a laser diffraction/scattering particle size distribution meter (made by Nikkiso Co., Ltd., Micro track MT-3000), the average secondary particle size was determined.

Further, the abbreviations used in the synthesis examples and comparative synthesis examples are as follows.

BPFE: a reaction of 9,9-bis(4-hydroxyphenyl)anthracene with chloromethyloxirane. In the compound of the formula (I), X is a compound of -9,9-diyl, and R ₁ and R ₂ are hydrogen.

BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride

BTDA: 3,3',4,4'-benzophenone tetracarboxylic dianhydride

THPA: 1,2,3,6-tetrahydrophthalic anhydride

TPP: triphenylphosphine

PGMEA: propylene glycol monomethyl ether acetate

[Synthesis Example 1]

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 were added to a 1 L four-necked flask equipped with a reflux condenser, and stirred under heating at 100 to 105 ° C for 12 hr. Reaction product.

Next, 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 the mixture was stirred under heating at 115 to 120 ° C for 6 hr to obtain an alkali-soluble resin solution containing a polymerizable unsaturated group. (A)-1. The solid content concentration of the obtained resin solution was 56.5 wt%, the acid value (in terms of solid content) was 102 mgKOH/g, and the Mw analyzed by GPC was 3,600.

[Synthesis Example 2]

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 were added to a 1 L four-necked flask equipped with a reflux condenser, and stirred under heating at 100 to 105 ° C for 12 hr. Reaction product.

Next, BTDA 37.1 g (0.12 mol) and THPA 17.5 g (0.12 mol) were added to the obtained reaction product at 115 to 120 ° C. The mixture was stirred under heating for 6 hr to obtain an alkali-soluble resin solution (A)-2 containing a polymerizable unsaturated group. The solid content concentration of the obtained resin solution was 56.6 wt%, the acid value (in terms of solid content) was 102 mgKOH/g, and the Mw analyzed by GPC was 3,700.

[Comparative Synthesis Example 1]

51.65 g (0.60 mol) of methacrylic acid, 38.44 g (0.38 mol) of methyl methacrylate, 38.77 g (0.22 mol) of benzyl methacrylate, and even in a 1000 ml four-necked flask equipped with a nitrogen inlet tube and a reflux tube. 5.91 g of nitrogen bisisobutyronitrile and 370 g of diethylene glycol dimethyl ether were polymerized by stirring at 80 to 85 ° C for 8 hr under a nitrogen stream. Further, 39.23 g (0.28 mol) of glycidyl methacrylate, 1.42 g of TPP, and 0.055 g of 2,6-di-t-butyl-p-cresol were added to the flask, and stirred at 80 to 85 ° C for 16 hr to obtain alkali solubility. Resin solution (A)-3. 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 analyzed by GPC was 18,100.

(alkali-soluble resin containing a polymerizable unsaturated group)

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

(A)-2 component: the alkali-soluble resin solution obtained in the above Synthesis Example 2

(A)-3 component: the alkali-soluble resin solution obtained in the above Comparative Synthesis Example 1

(photopolymerizable monomer)

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

(photopolymerization initiator)

(C): Ethylketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-acetyl) (Japan) BASF company, product name Irgacure OXE02)

(light-shielding disperse pigment)

(D)-1: PGMEA dispersion of titanium black (manufactured by Mitsubishi Materials Co., Ltd., product name 13M-C) at a concentration of 20.0% by mass and a dispersant concentration of 5.0% by mass (solid content 25.0%, average secondary particle of titanium black) Trail 188nm)

(D)-2: PGMEA dispersion of 15.0% by mass of black pigment (neuroguanamine black, Irgaphor S100CF manufactured by BASF Corporation) and 4.5% by mass of polymer dispersant (19.5% solid content, average secondary particle diameter 241 nm of black pigment)

(D)-3: 7.0% by mass of CI Pigment Orange 64 (manufactured by BASF Corporation), 3.0% by mass of CI Pigment Violet 23 (manufactured by CLARIANT Co., Ltd.), and 7.0% by mass of CI Pigment Blue 15:6 (manufactured by CLARIANT Co., Ltd.), polymer dispersion A PMEEA dispersion having a concentration of 4.0% by mass, 2.0% by mass of a sulfonated azo dispersing aid, and 2.0% by mass of a benzyl methacrylate/methacrylic acid copolymer (solid content 25.0%)

(D)-4: PGMEA dispersion of carbon black 20.0% by mass and polymer dispersant concentration 5.0% by mass (solid content 25.0%, average secondary particle diameter of carbon black) 162nm)

(solvent)

(E)-1: PGMEA

(E)-2: 3-methoxy-3-methyl-1-butyl acetate

(surfactant)

(H): PGMEA solution of BYK-330 (made by BYK Chemical Co., Ltd.) (solid content 1.0%)

The above-mentioned formulation components were blended at the ratios shown in Table 1, and the photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 2 were prepared. In addition, the numerical values in Table 1 represent the parts by mass. Further, (E)-1 in the column of the solvent is PGMEA (the same as (E)-1) in the resin solution (the alkali-soluble resin solution containing a polymerizable unsaturated group) containing no unsaturated group, and the light-shielding The amount of PGMEA (same as (E)-1) in the dispersion.

[assessment]

Using the photosensitive resin compositions for the light-shielding films of Examples 1 to 6 and Comparative Examples 1 and 2, the evaluations described below were carried out. The conclusion of the evaluation The results are shown in Table 2.

<Development characteristics>

Each of the photosensitive resin compositions obtained above was applied onto a glass substrate having a thickness of 1.2 mm so that the film thickness after the heat curing treatment was 3.0 μm, and prebaked at 90 ° C for 1 minute. Thereafter, it was adhered to a light-shielding, and a 100 WJ/cm ² ultraviolet ray was irradiated with an ultrahigh-pressure mercury lamp having an illuminance of 30 mW/cm ² at a wavelength of 365 nm using a high-pressure mercury lamp of 500 W to carry out a photohardening reaction of the photosensitive portion.

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

The thin line formation of the obtained cured film pattern was confirmed by an optical microscope and evaluated in the following three stages.

The results are shown in Table 2.

○: A pattern in which L/S is 10 μm/10 μm or more has no residue formation.

△: The pattern of L/S of 30 μm/30 μm or more has no residue formation.

×: A pattern having an L/S of less than 50 μm/50 μm or a curl or residue of a pattern is not formed.

<Optical concentration>

Each of the photosensitive resin compositions obtained above is used in a spin coater to The film thickness after the thermosetting treatment was applied to a glass substrate having a thickness of 1.2 mm so as to be 1.1 μm, and prebaked at 90 ° C for 1 minute. Thereafter, the film was subjected to a heat curing treatment 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 Penetration Concentrator, and the optical density per unit film thickness was evaluated.

<Volume resistivity>

The photosensitive resin composition obtained above was applied to a portion other than the electrode on a glass substrate having a thickness of 1.2 mm by Cr deposition so that the film thickness after the heat curing treatment was 3.5 μm by a spin coater. The heat hardening treatment was carried out at 90 ° C for 1 minute. Thereafter, the film was subjected to a heat curing treatment 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 form a substrate for volume resistivity measurement. Next, using a static electricity meter ("6517A type" manufactured by Keithley Co., Ltd.), the volume resistivity of the applied voltage from 1 V to 10 V was measured. The measurement was carried out under the conditions of a voltage of 1 V at each applied voltage for 60 seconds, and the volume resistivity when 10 V was applied is shown in Table 2.

<Dielectric constant>

The photosensitive resin composition obtained above was applied to a portion other than the electrode on a glass substrate having a thickness of 1.2 mm by Cr deposition so that the film thickness after the heat curing treatment was 3.5 μm by a spin coater. At 90 Pre-bake for 1 minute at °C. Thereafter, the film was subjected to a heat curing treatment 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 form a substrate for dielectric constant measurement. Next, using a static electricity meter ("6517A" manufactured by Keithley Co., Ltd.), a capacitance of 1 Hz to 100,000 Hz was measured, and a dielectric constant was calculated from the capacitance. The calculated dielectric constants are shown in Table 2.

<Halftone (HT) characteristics of the spacer>

Each of the photosensitive resin compositions obtained above was applied onto a glass substrate having a thickness of 1.2 mm so that the film thickness after the heat curing treatment was 3.0 μm, and prebaked at 90 ° C for 1 minute. Thereafter, it was adhered to a light mask having a dot pattern, and a high-pressure mercury lamp of 500 W was used to irradiate ultraviolet rays of ⁵ mJ/cm ² or 100 mJ/cm ^{2 with an} ultrahigh pressure mercury lamp having an illuminance of 30 mW/cm ² at a wavelength of 365 nm, and the photosensitive portion was irradiated. Photohardening reaction.

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

Halftone characteristic difference based spacer thickness of the shading film exposure amount was 5 mJ / cm ² in the (H1) and 100mJ film thickness (H2) of the spacer / cm ² of (△ H) is calculated, and It is evaluated in the following four stages. The results are shown in Table 2.

○: ΔH is 1.0 μm to 2.0 μm

△: ΔH is 0.1 μm to 2.9 μm

×: ΔH is less than 0.1 μm or more than 2.9 μm

<Compression ratio, elastic recovery rate, and breaking strength of the spacer>

Each of the photosensitive resin compositions obtained above was applied onto a glass substrate having a thickness of 1.2 mm so that the film thickness after the heat curing treatment was 3.0 μm, and prebaked at 90 ° C for 1 minute. Thereafter, it was adhered to a light mask having a dot pattern, and an ultraviolet light of 100 mJ/cm ^{2 was} irradiated with an ultrahigh pressure mercury lamp having an illuminance of 30 mW/cm ² at a wavelength of 365 nm using a high-pressure mercury lamp of 500 W to carry out a photohardening reaction of the photosensitive portion.

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

The separator characteristics of the obtained cured film pattern were evaluated using an ultra-micro hardness tester (FISCHER SCOPE HM2000XyP, manufactured by FISCHER Instruments Co., Ltd.). The flat pressure was pressed at a load speed of 5.0 mN/sec and 100 μm square, and after the load reached a load of 50 mN, the unloading speed was 5.0 mN/sec, and the displacement amount curve was created.

The compression ratio is obtained by setting the displacement amount of the load of 50 mN at the time of load to L1.

Compression ratio (%) = L1/the height of the spacer × 100

The elastic recovery rate is L1 at a load of 50 mN at the time of load, and L2 at the time of unloading, and is calculated by the following formula.

Elastic recovery rate (%) = (L1-L2) / L1 × 100

The breaking strength was evaluated using an ultra-micro hardness tester (FISCHER Instruments, FISCHER SCOPE HM2000XyP). The load was applied to a load of 300 mN at a load speed of 5.0 mN/sec and a flat pressure of 100 μm square, and the load at the time of damage of the spacer was measured, and it was evaluated in the following four stages. The results are shown in Table 2.

○: The case where the breaking strength is 300 mN or more

△: The case where the breaking strength is 200 mN or less

×: the case where the breaking strength is 100 mN or less

<Shape of spacer>

Each of the photosensitive resin compositions obtained above was applied onto a glass substrate having a thickness of 1.2 mm so that the film thickness after the heat curing treatment was 3.0 μm, and prebaked at 90 ° C for 1 minute. Thereafter, it was adhered to a light mask having a dot pattern, and an ultraviolet light of 100 mJ/cm ^{2 was} irradiated with an ultrahigh pressure mercury lamp having an illuminance of 30 mW/cm ² at a wavelength of 365 nm using a high-pressure mercury lamp of 500 W to carry out a photohardening reaction of the photosensitive portion.

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

The shape of the spacer was evaluated using a scanning electron microscope to estimate the internal angle (taper angle) of the end of the spacer. When the taper angle is 70° or more and 90° or less, the case is set to ◎, In the case of 50° or more and less than 70°, it is assumed that ○ and 50° or less are Δ, and 90° or more is set to ×.

From the results of Examples 1 to 6 and Comparative Examples 1 to 2, it can be understood that by using titanium black in the (D) light-shielding material, the volume resistivity can be maintained, and at the same time, the light-shielding property, the dielectric constant, and the elastic recovery ratio can be maintained. Equal spacer characteristics are improved. It can be understood, in particular, by using titanium black and black organic pigments together or The color-mixing organic pigment does not reduce the characteristics of the spacer such as the elastic recovery rate, and can complement the shortcomings of various light-shielding materials, and effectively has both light-shielding property, volume resistivity, and dielectric constant.

Claims (18)

A photosensitive resin composition for a light-shielding film having a spacer function, comprising the following components (A) to (E) as essential components: (A) having two epoxypropyl groups derived from bisphenols a reaction of an ether group-containing epoxy compound and an unsaturated group-containing monocarboxylic acid with (a) a tetracarboxylic acid or an acid dianhydride thereof, and (b) a dicarboxylic acid or a tricarboxylic acid or an anhydride thereof An alkali-soluble resin containing a polymerizable unsaturated group; (B) a photopolymerizable monomer having at least one ethylenically unsaturated bond; (C) a photopolymerization initiator; (D) selected from a black organic pigment, One or more kinds of light-shielding components in a group of mixed color organic pigments and light-shielding materials; and (E) a solvent. The photosensitive resin composition according to claim 1, which comprises titanium black as a (D) light-shielding component. The photosensitive resin composition according to claim 2, wherein the titanium black has an average secondary particle diameter of 100 to 300 nm. The photosensitive resin composition according to any one of claims 1 to 3, which comprises a black organic pigment and/or a mixed color organic pigment as (D) a light-shielding component, and the black organic pigment and/or color mixture. The organic pigment has an average secondary particle diameter of 20 to 500 nm. The photosensitive resin composition according to any one of claims 1 to 4, wherein the component (B) is contained in an amount of 5 to 400 parts by mass based on 100 parts by mass of the component (A); 100 parts by mass of the total of the component (A) and the component (B), the component (C) is contained in an amount of 0.1 to 30 parts by mass; when the component (B) which is a solid component after photohardening is included, and (E) is removed When the component of the component is a solid component, the component (D) is contained in an amount of from 5 to 80% by mass based on the total amount of the solid component. The photosensitive resin composition according to any one of claims 1 to 5, wherein a light-shielding film having an optical density OD of 0.5/μm or more and 3/μm or less is formed, and a voltage of 10 V is applied to the light-shielding film. 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 any one of claims 1 to 6, which can be formed in a load-unloading test performed by a micro hardness tester, which satisfies the following (i) to (iii) The light shielding film of at least one of (i) the breaking strength is 200 mN or more, (ii) the elastic recovery rate is 30% or more, and (iii) the compression ratio is 40% or less. A light-shielding film having a function of a spacer, which is formed by curing a photosensitive resin composition according to any one of claims 1 to 7. A liquid crystal display device having the light-shielding film described in claim 8 as a black column spacer (BCS). The liquid crystal display device of claim 9, further comprising a thin film transistor (TFT). A method for producing a photosensitive resin composition for a light-shielding film having a separator function, wherein the (D) light-shielding component is dispersed in (E) After the dispersion is formed in the above-mentioned dispersion, (A) an alkali-soluble resin, (B) a photopolymerizable monomer having at least one ethylenically unsaturated bond, and (C) photopolymerization are further added to the dispersion. a starting agent, and (E) a solvent; wherein the (A) alkali-soluble resin is an epoxy compound having two epoxypropyl ether groups derived from a bisphenol and a monocarboxylic acid containing an unsaturated group; a reactant, which is obtained by reacting (a) a tetracarboxylic acid or an acid dianhydride thereof, and (b) a dicarboxylic acid or a tricarboxylic acid or an anhydride thereof; (D) a light-shielding component selected from the group consisting of black organic One or more components selected from the group consisting of pigments, mixed color organic pigments, and light-shielding materials. The manufacturing method according to claim 11, wherein the (D) light shielding component contains titanium black. The production method according to claim 12, wherein in the dispersion, the titanium dioxide has an average secondary particle diameter of 100 to 300 nm. The manufacturing method according to any one of claims 11 to 13, wherein the (D) light-shielding component comprises a black organic pigment and/or a mixed color organic pigment, and in the dispersion, the black organic pigment and/or The average secondary particle diameter of the color mixed organic pigment is 20 to 500 nm. A method for producing a light-shielding film formed on a substrate, which is characterized in that the photosensitive resin composition according to any one of claims 1 to 7 is coated on a substrate, and the photosensitive resin is composed by light irradiation. Hardening of matter. A method for producing a light-shielding film, which is a method for producing a light-shielding film according to claim 15 in which a film thickness H1 of ΔH=H2-H1 is 0.1 to 2.9 when H2 is 2 to 7 μm. a light-shielding film having a film thickness H2, wherein the film thickness H1 is used to make the light as a light-shielding film The film thickness is 0.5/μm or more and less than 3/μm, and the film thickness H2 is the film thickness of the light-shielding film which functions as a spacer. A method for producing a liquid crystal display device, which is a black columnar spacer, which is manufactured by the manufacturing method described in claim 16 of the patent application. The manufacturing method according to claim 17, wherein the liquid crystal display device has a thin film transistor (TFT).