TWI768022B - Photosensitive resin composition, light-shielding film, liquid crystal display device, light-shielding film, and manufacturing method of liquid crystal display device - Google Patents

Abstract

The present invention relates to a photosensitive resin composition for a light-shielding film having a spacer function, comprising components (A) to (E) 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) the surface resistivity of the film formed so that the optical density becomes 4/μm A light-shielding component containing insulating carbon black of 1×10 ⁸ Ω/□ or more; and (E) a solvent; and a hardened product of a composition excluding the (D) component has a pencil hardness of HB or more. It is possible to obtain a spacer having excellent spacer properties such as compressibility, elastic recovery, and breaking strength, while maintaining light-shielding properties and insulating properties, and having an excellent pattern shape that can form a ΔH level difference.

Description

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

The present invention relates to a photosensitive resin composition and a light-shielding film obtained by curing the same, and more specifically, to a liquid crystal display device that can be formed by a photo-development method and has both a spacer function and a black matrix function The photosensitive resin composition of the black column spacer and its cured film. The present invention further relates to a liquid crystal display device using the black column spacer obtained by hardening. The present invention further relates to a method of manufacturing the liquid crystal display device.

In recent years, color liquid crystal display devices (Liquid Crystal Display, LCD) have 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 LCD, improvement of characteristics such as viewing angle, contrast ratio and response speed is actively carried out, and thin film transistor (TFT)-LCD, which is widely used at present, is also developing various panel structures. . Regarding the TFT-LCD, a method is mainly adopted in which an array substrate and a color filter substrate on which conventional TFTs are formed are separately manufactured, and the two substrates are bonded together in a state where a constant interval is maintained by a spacer.

Regarding the spacer that has the function of keeping the thickness of the liquid crystal layer (the distance between the array substrate and the color filter (CF) substrate in the case of the conventional method) fixed, which is one of the factors affecting the performance of the LCD, previously , adopt the method of clamping the ball spacer with fixed particle size. However, in this method, the dispersion state by the ball spacers becomes non-uniform, and there is a problem that the transmission amount of light per pixel is not constant. In order to solve such a problem, a method of forming the column spacer by a photo-development method is adopted. However, many column spacers formed by a photo-development method are transparent, and such column spacers have a problem in that light incident from an oblique direction affects the electrical characteristics of the TFT and degrades 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).

The light-shielding column spacer needs to have a film thickness of about 1 μm to 7 μm in order to function as a spacer. In addition, it is necessary to be able to form light-shielding column spacers with different heights at the same time at the site where the TFT is formed and other sites. In addition, the light-shielding column spacer is also required to be in an appropriate range for the elastic modulus, deformation amount, elastic recovery rate, etc., which function as spacers (Patent Document 3). Furthermore, improvement in the reduction of curable components due to the addition of a light-shielding component (colorant) to the spacer, or the loss of electrical properties due to the influence of impurities in the colorant, etc., is also required for the light-shielding column spacer. etc. (Patent Document 4). [Prior Art Literature]

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

THE PROBLEM TO BE SOLVED BY THE INVENTION Although the color mixing organic pigment is used in patent document 4, the optical density of the light-shielding column spacer is not shown. Compared with inorganic pigments such as carbon black, color-mixing organic pigments are effective in lowering the dielectric constant, but are often low in light-shielding properties. In addition, since the spacer must be formed at the same time as spacers with different heights, mechanical properties such as compressibility, elastic recovery rate, and breaking strength are further required for the light-shielding column spacer. Since the shape and mechanical properties of the spacer are largely affected by the light-shielding component, it is difficult to design a photosensitive resin composition for a light-shielding film. Therefore, the shape and mechanical properties of spacers using carbon black, color-mixing organic pigments, or the like are still insufficient, and further improvement is required.

In addition, as described above, the light-shielding column spacer is manufactured with a film thickness of about 1 μm to 7 μm. With the miniaturization of liquid crystal display elements in recent years, it is desired that the light-shielding column spacer can be formed into a fine spacer shape even when the film thickness is about 1 μm to 7 μm. In addition, in addition to having the functions of the black matrix and the spacer, in order to accurately attach the two substrates sandwiching the liquid crystal layer, that is, to improve the alignment accuracy, it is necessary to set the heights of the two types of light-shielding spacers (forming ΔH Further, there are many requirements for patterning properties such as the formation of light-shielding spacers that are as perpendicular to the glass substrate as possible, and it is difficult to satisfy all the required properties.

The present invention has been made in view of the above-mentioned problems, and is to provide a light-shielding film having a spacer function that is high in light-shielding properties and insulating properties, and has excellent compressibility, elastic recovery rate, and breaking strength, and can form a ΔH level difference A photosensitive resin composition having an excellent pattern shape, a light-shielding film having a spacer function formed using the same, and a liquid crystal display device including the light-shielding film as a constituent element can be formed. [Technical means to solve the problem]

The present inventors have studied in order to solve the above-mentioned problems in the photosensitive resin composition for light-shielding films, and as a result, 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, characterized by comprising the following (A) components to (E) components 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) The optical density becomes 4/ A light-shielding component containing insulating carbon black having a surface resistivity of 1 × 10 ⁸ Ω/square or more, and (E) a solvent; and (D) curing of a composition excluding the component The pencil hardness of the material is HB or higher. (2) In addition, the present invention is the photosensitive resin composition according to (1), wherein the component (B) is contained in an amount of 5 to 400 parts by mass relative to 100 parts by mass of the component (A). 0.1 mass part - 40 mass parts of (C)component are contained in the total amount of (A) component and (B) component 100 mass parts, and (E) containing (B) component which becomes a solid after photohardening (D) component is contained in 5 mass % - 60 mass % in the total amount of solid content when the component except ) component is used as solid content. (3) In addition, the present invention is the photosensitive resin composition according to (1) or (2), characterized in that a polymerizable unsaturated group-containing alkali-soluble resin represented by the general formula (II) is used as ( A) Ingredients.

[hua 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-, fluorene-9,9-diyl or direct bond, Y represents a tetravalent carboxylic acid residue, Z independently represents a hydrogen atom or -OC-W-(COOH) _l (wherein, 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) In addition, the present invention is the photosensitive resin composition according to any one of (1) to (3), wherein a light-shielding film having an optical density OD (Optical Density) of 0.5/ μm or more and 4/μm or less, the volume resistivity when a voltage of 10 V is applied is 1×10 ⁹ Ω·cm or more, and the dielectric constant is 2 to 10. (5) In addition, the present invention is the photosensitive resin composition according to any one of (1) to (4), wherein in a load-unload test using a micro hardness tester, the photosensitive resin composition satisfies the following: The light-shielding film of at least one of (i) to (iii). (i) The compression ratio is less than 40%; (ii) the elastic recovery ratio is more than 30%; (iii) the breaking strength is more than 200 mN. (6) Moreover, this invention is a light-shielding film which has a spacer function characterized by hardening and forming the photosensitive resin composition as described in any one of (1)-(5). (7) In addition, the present invention is a liquid crystal display device characterized by comprising the light-shielding film according to (6) as a black column spacer (Black Column Spacer, BCS). (8) Further, the present invention is the liquid crystal display device according to (7), further comprising a thin film transistor (TFT). (9) In addition, the present invention is a method for producing a light-shielding film, wherein the photosensitive resin composition according to any one of (1) to (5) is applied on a substrate, and the photosensitive resin composition is irradiated with light. In the manufacturing method of the light-shielding film formed on the board|substrate which hardens the said photosensitive resin composition, about the film thickness H1 for setting the optical density as the light-shielding film to 0.5/micrometer or more and 4/micrometer or less, and the burden When H2 is 1 μm to 7 μm, ΔH=H2−H1 is 0.1 to 6.9 for the thickness H2 of the light shielding film of the spacer function, and the light shielding film of the film thickness H2 is simultaneously formed. (10) Further, the present invention is a method of manufacturing a liquid crystal display device, wherein the light-shielding film manufactured by the method of manufacturing a light-shielding film according to (9) is used as a black column spacer. (11) Further, the present invention is the 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 light-shielding films of the present invention contains specific insulating carbon black as a colorant, compared with conventional photosensitive resin compositions, it is possible to obtain compression while maintaining light-shielding and insulating properties. Hardened product with excellent rate, elastic recovery rate and breaking strength. Furthermore, the photosensitive resin composition for light-shielding films of the present invention can be formed into 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 and has acidic groups such as a polymerizable unsaturated double bond that contributes to photohardening reaction and a carboxyl group that contributes to alkali developability in the molecule. of resin. Among these, the first example preferably used is a hydroxyl group-containing compound containing (a) tetracarboxylic acid or its acid dianhydride and (b) dicarboxylic acid or tricarboxylic acid or its acid anhydride and a polymerizable unsaturated group. (c) An alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule obtained by reacting, wherein the hydroxyl group-containing compound (c) is obtained by making (meth)acrylic acid (which is "acrylic acid and/or "Methacrylic acid") is obtained by reacting an epoxy compound having two glycidyl ether groups derived from bisphenols, preferably an epoxy compound represented by the general formula (I). Since the component (A) has both a polymerizable unsaturated double bond and a carboxyl group, excellent photocurability, good developability, and patterning properties are imparted to the photosensitive resin composition, and the physical properties of the light-shielding film are improved.

[hua 2]

Wherein, 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-, fluorene-9,9-diyl or single bond , the average value of m is in the range of 0 to 10, preferably 0 to 3.

Bisphenols which provide the epoxy compound of general formula (I) include bis(4-hydroxyphenyl)ketone, bis(4-hydroxy-3,5-dimethylphenyl)ketone, bis(4-hydroxyphenyl)ketone -3,5-Dichlorophenyl) ketone, bis(4-hydroxyphenyl) bis(4-hydroxy-3,5-dimethylphenyl) bis(4-hydroxy-3,5-dimethylphenyl) bis(4-hydroxy-3,5- Dichlorophenyl) bismuth, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy-3,5-difluoropropane) 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-fluorophenyl)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, etc. Only one compound of these bisphenols may be used, or a combination of two or more may be used. Among them, it is particularly preferable to use bisphenols in which X in the general formula (I) is a fluorene-9,9-diyl group.

The compound of general formula (I) to be derived as the alkali-soluble resin of (A) is an epoxy compound having two glycidyl ether groups obtained by reacting the bisphenols with epichlorohydrin. During the above reaction, the oligomerization of the diglycidyl ether compound usually accompanies the oligomerization of the diglycidyl ether compound, and m is an integer of 0 to 10 in each molecule, and since it is usually mixed in molecules of a plurality of values, the average value is 0 to 10 (not limited to Integer), the average value of m is preferably 0-3. When 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 high, and smooth coating cannot be performed, or Alkali solubility was not sufficiently imparted, and the alkali developability became very poor.

Next, an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule can be obtained by reacting a polymerizable unsaturated group-containing hydroxyl group-containing compound (c) with an acid component, the hydroxyl group-containing compound (c) ) is obtained by the reaction of an epoxy compound with (meth)acrylic acid. As the acid component, tetracarboxylic acid or its acid dianhydride (a), dicarboxylic acid or tricarboxylic acid, or its acid monoanhydride (b) which can react with a hydroxyl group-containing compound are preferably used. 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 hetero-element-containing bonds such as -O-, -S-, and carbonyl groups.

Hereinafter, although specific examples of the acid component are shown, the dianhydrides and monoanhydrides of the exemplified polycarboxylic acids can also be used.

First, the (a) tetracarboxylic acid includes a chain hydrocarbon tetracarboxylic acid, an alicyclic tetracarboxylic acid, or an aromatic polyvalent carboxylic 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. In addition, the alicyclic tetracarboxylic acid includes, for example, cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid, and the like, and may be further A tetracarboxylic acid into which an arbitrary substituent is introduced. Further, the aromatic tetracarboxylic acid includes, for example, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, and the like, and further, tetracarboxylic acid into which an arbitrary substituent is introduced may be used. . Only one compound of these (a) tetracarboxylic acids may be used, or two or more types may be used in combination.

In addition, as (b) dicarboxylic acid or tricarboxylic acid, a chain hydrocarbon dicarboxylic acid or tricarboxylic acid, an alicyclic dicarboxylic acid or tricarboxylic acid, and an aromatic dicarboxylic acid or tricarboxylic acid can be used. Here, the chain hydrocarbon dicarboxylic acid or tricarboxylic acid includes, for example, succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, Glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, etc., furthermore, dicarboxylic acid or tricarboxylic acid into which arbitrary substituents are introduced may be used . In addition, alicyclic dicarboxylic acid or tricarboxylic acid includes, for example, cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornane dicarboxylic acid, and the like, 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 includes, for example, phthalic acid, isophthalic acid, trimellitic acid, and the like, and further, dicarboxylic acid or tricarboxylic acid into which an arbitrary substituent is introduced may be used. These (b) dicarboxylic acids or tricarboxylic acids may be used alone or in combination of two or more.

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

The ratio at which the polymerizable unsaturated group-containing hydroxyl-containing compound (c) and the acid components (b) and (a) are allowed to react is preferably such that the terminal of the compound becomes a carboxyl group. The quantitative reaction was performed so that the molar ratio of each component was (c):(b):(a)=1:0.2-1.0:0.01-1.0. In such a case, it is desirable that the molar ratio of the total amount of the acid component to the polymerizable unsaturated group-containing hydroxyl-containing compound (c) is (c)/[(b)/2+(a)]= Quantitative reaction was carried out in the manner of 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 and the stability over time of the alkali-soluble resin composition may decrease. On the other hand, when the molar ratio exceeds 1.0, there is a concern that the content of the unreacted polymerizable unsaturated group-containing hydroxyl group-containing compound increases and the temporal stability of the alkali-soluble resin composition decreases. The molar ratio of each component (a), (b) and (c) can be arbitrarily changed within the above-mentioned range for the purpose of adjusting the acid value and molecular weight of the alkali-soluble resin.

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

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

[hua 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 direct bond, Y represents a tetravalent carboxylic acid residue, Z independently represents a hydrogen atom or -OC-W-(COOH) _l (wherein, 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 epoxy acrylate using a bisphenol-type epoxy compound as a raw material, but a novolac-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, etc. as raw materials. In addition, when adding the acid component to the epoxy acrylate compound, it is also possible to achieve the desired effect by coexisting two or more polyol compounds having an alcoholic hydroxyl group, coexisting two or more isocyanate group-containing compounds, or the like. The physical properties are designed to harden the obtained unsaturated group-containing alkali-soluble resin.

The second example of the unsaturated group-containing alkali-soluble resin as the component (A) includes a polymerizable unsaturated group-containing alkali obtained by further reacting glycidyl (meth)acrylate and the alkali-soluble resin. Soluble resin, which is obtained by radical polymerization of (meth)acrylic acid and various (meth)acrylates. Examples of the (meth)acrylate etc. which are copolymerized with (meth)acrylic acid include (meth)acrylate, amide (meth)acrylate, styrene and its derivatives, maleic anhydride and Its derivatives, vinyl ethers, olefins, etc.

(Meth)acrylate or (meth)acrylamide is a compound group having a structure obtained by reacting (meth)acrylic acid with an alcohol (R ₆ OH) component or an amine (R ₇ R ₈ NH), Well-known ones can be used without particular limitation. Specific examples of R ₆ , R ₇ and R ₈ include methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, neopentyl, 2-cyclopentylethyl, Linear monovalent alkyl such as cyclohexylmethyl, branched monovalent alkyl or monovalent alkyl which can be substituted by alicyclic structure, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, adamantane Monovalent alicyclic hydrocarbon groups such as base, isobornyl, dicyclopentyl, dicyclopentenyl, phenyl, tolyl, mesityl, naphthyl, anthracenyl, benzyl, 2-phenylethyl Equivalent monovalent aromatic hydrocarbon groups, or pyridyl, pyridyl, N-hexahydropyridyl, pyrrolyl, pyrrolidinyl, imidazolyl, imidazolidinyl, furanyl, tetrahydrofuranyl, thienyl, tetrahydrothienyl, Saturated monovalent heterocyclic groups such as morpholino, morpholino, and quinolyl, or unsaturated monovalent heterocyclic groups, and the like. Furthermore, the introduction of a halogen atom, a hydroxyl group, a sulfonyl group, a carbonyl group, a thiocarbonyl group, a carboxyl group, a thiocarboxy group, a dithiocarboxy group, a carboxyl group, a cyano group, and a nitro group into an arbitrary position of the above-mentioned hydrocarbon group, heterocyclic group, etc. can also be mentioned. , nitro group, sulfo group, amino group, imino group, silyl group, ether group, thioether group, ester group, thioester group, dithioester group, amide group, thioamide group, aminomethyl group A structure in which an ester group, a thiourethane group, a urea group, a thiourea group, and the like are used as a substituent.

The weight average molecular weight (Mw) of the alkali-soluble resin (A) in terms of polystyrene measured by Gel Permeation Chromatography (GPC) is usually 1,000 to 50,000, preferably 2,000 to 15,000. When the weight average molecular weight is less than 1,000, there is a concern that the adhesiveness of the pattern at the time of alkali development may decrease, and when the weight average molecular weight exceeds 50,000, the developability may decrease, or hardening by light or heat may be difficult. There is a concern that a composition with desired hardness will be formed. Moreover, in the case of the alkali-soluble resin of the general formula (II), the weight average molecular weight is preferably 2,000 to 10,000, and more preferably 3,000 to 7,000.

Moreover, the preferable range of the acid value of the alkali-soluble resin of (A) is 30 mgKOH/g - 200 mgKOH/g. If the value is less than 30 mgKOH/g, residues are likely to remain at the time of alkali development, and if it exceeds 200 mgKOH/g, the penetration of the alkali developer becomes too fast to cause peeling development, which are all unfavorable. Further, (A) the polymerizable unsaturated group-containing alkali-soluble resin may be used alone, or a mixture of two or more may be used.

In the present invention, the weight average molecular weight of (A) is as follows: The sampled solution is dissolved in tetrahydrofuran, the molecular weight distribution is measured using HLC-8220GPC manufactured by Tosoh Corporation, and the weight average in terms of standard polystyrene is calculated. The value derived from the molecular weight. In addition, the acid value of the component (A) was obtained by dissolving the sampled solution in dioxane, neutralizing titration with an aqueous potassium hydroxide solution of 0.1, and calculating the solid content conversion of the sample solution from the equivalent point. The value derived from the acid value.

Next, (B) the photopolymerizable monomer which has at least three ethylenically unsaturated bonds, for example, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, for example , 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, phosphazene modified alkylene oxide hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate (meth)acrylates such as esters, polyols (pentaerythritol, dipentaerythritol, etc.), or vinylbenzyl ether compounds of polyhydric phenols (phenol novolacs, etc.), divinyl compounds such as divinylbenzene, etc. Addition polymers, etc. These (B) photopolymerizable monomers having at least three ethylenically unsaturated bonds may be used alone or in combination of two or more. Further, (B) the photopolymerizable monomer having at least three ethylenically unsaturated bonds does not have a free carboxyl group.

The mixing ratio of the (B) component is preferably 5 to 400 parts by mass, preferably 10 to 150 parts by mass, relative to 100 parts by mass of the (A) component. When the compounding ratio of (B) component exceeds 400 parts by mass with respect to 100 parts by mass of (A) component, the cured product after photocuring becomes brittle, and since the acid value of the coating film in the unexposed part is low, it is not suitable for The solubility of the alkaline developer decreases, resulting in a problem that the edges of the pattern are jagged and unclear. On the other hand, when the compounding ratio of the (B) component is less than 5 parts by mass with respect 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, since the acid value of the resin component is high, the solubility of the exposed portion to the alkali developing solution is improved, so there is a possibility that the formed pattern becomes thinner than the target line width, or the pattern is likely to fall off. .

Moreover, as a photopolymerization initiator of (C)component, for example, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dimethy Acetophenones such as chloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminodi Benzophenones such as benzophenone, benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-(o-chlorophenyl)-4,5-phenylbiimidazole , 2-(o-chlorophenyl)-4,5-bis(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-4,5-diphenylbiimidazole, 2-(o-methylphenyl) Oxyphenyl)-4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole and other biimidazole-based compounds, 2-trichloromethyl-5-styryl-1,3, 4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-methoxystyrene) base)-1,3,4-oxadiazole and other halomethyloxadiazole compounds, 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4 ,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4 -Chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl) -1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxy styryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis( Trichloromethyl)-1,3,5-triazine, 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine and other halogens Methyl-s-triazine compounds, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzyl oxime), 1-(4- Phenylsulfonylphenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylsulfonylphenyl)butane-1,2-di Keto-2-oxime-O-acetate, 1-(4-methylsulfonylphenyl)butane-1-one oxime-O-acetate, ethyl ketone, 1-[9-ethyl- 6-(2-Methylbenzyl)-9H-oxazol-3-yl]-,1-(0-acetyloxime), ketone,(9-ethyl-6-nitro-9H - Azazol-3-yl)[4-(2-methoxy-1-methylethoxy)-2-methylphenyl]-,O-acetonitrile oxime, ketone, (2-methylphenyl) phenyl) (7-nitro-9,9-dipropyl-9H-fluoren-2-yl)-, acetyl oxime, ethyl ketone, 1-[7-(2-methylbenzyl) )-9,9-dipropyl-9H-fluoren-2-yl]-,1-(O-acetyloxime), ethyl ketone,1-(-9,9-dibutyl-7-nitro -9H-Fluorene-2-yl) -,1-O-Acetyl oxime and other O-acyl oxime compounds, benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthia Sulfur compounds such as anthrone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3 -Anthraquinones such as diphenylanthraquinone, organic peroxides such as azobisisobutyronitrile, benzyl peroxide, cumene peroxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxane azoles, thiol compounds such as 2-mercaptobenzothiazole, etc. Among them, it is preferable to use O-acyl oxime-based compounds from the viewpoint of easily obtaining a photosensitive resin composition for a high-sensitivity light-shielding film. Only one compound of these (C) photopolymerization initiators may be used, and a plurality of them may be used in combination. In addition, the photopolymerization initiator in this invention is used in the meaning containing a sensitizer.

These photopolymerization initiators or sensitizers may be used alone or in combination of two or more. In addition, although it does not function as a photopolymerization initiator or a sensitizer by itself, a compound which can increase the ability of a photopolymerization initiator or a sensitizer may be added 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.

The amount of the photopolymerization initiator used as the component (C) is preferably 0.1 to 40 parts by mass, preferably 1 to 25 parts by mass, based on 100 parts by mass of the total of the (A) component and the (B) component. portion is appropriate. When the compounding ratio of (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 sensitivity is too strong. , the pattern line width becomes thicker relative to the pattern mask, the faithful line width cannot be reproduced for the mask, or the pattern edge is jagged and unclear.

(D) Component is a film thickness of 10 μm to 1.5 μm from a composition containing 5 to 20 mass % of (D) component and 5 to 15 mass % of (A) component in (E) component In addition, the surface resistivity of the film formed so that the optical density may be 4/μm or more is 1×10 ⁸ Ω/□ or more and contains a light-shielding component of insulating carbon black. The insulating carbon black that can be included in such a light-shielding component needs to be subjected to insulating treatment on the surface of the carbon black by various methods, but the method of insulating treatment is not particularly limited. Examples of methods of insulating treatment include a method of coating with resin (for example, Japanese Patent Laid-Open No. 9-95625), a method of oxidizing with an oxidizing agent (for example, Japanese Patent Laid-Open No. 11-181326), and A method of grafting a polymer compound having a reactive group (for example, Japanese Patent Laid-Open No. 9-265006), a method of chemical modification with an organic group (for example, Japanese Patent Application Laid-Open No. 2008-517330), and a combination of A method of coating with a graft reaction and resin (for example, Japanese Patent Laid-Open No. 2002-249678 ), a method of coating with a dye (for example, International Publication No. 2013/129555 ), and the like.

As the component (D), two or more insulating carbon blacks may be used, and blacks such as perylene black, aniline black, cyanine black, and lactam black may be used in combination Organic pigments or organic pigments such as red, blue, green, purple, yellow, cyan, magenta, etc. The selection of these light-shielding components including carbon black as an essential component takes into consideration insulation, heat resistance, light resistance, solvent resistance, and the like, and the light-shielding components may be selected and combined so that black can be rendered achromatic as appropriate.

Moreover, as a solvent of (E) component, methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 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, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol Alcohol, 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 and other glycol ethers, ethyl acetate ester, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-methylbutyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl solvent Cellulosic acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and other esters; By dissolving and mixing using these solvents, a uniform solution-like composition can be formed. Two or more of these solvents may be used in order to make them essential properties such as coatability.

In addition, these light-shielding components containing insulating carbon black as an essential component are preferably dispersed in a solvent together with the (F) dispersant in advance to form a carbon black dispersion liquid, and are preferably prepared as a photosensitive resin composition for light-shielding films. . Here, since the dispersed solvent becomes a part of (E) component, it can be used as long as it is listed in the above-mentioned (E) component. For example, propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate are suitably used. Wait. The mixing ratio of the insulating carbon black of (D) forming the carbon black dispersion liquid is preferably in the range of 5% by mass to 60% by mass with respect to the total solid content of the photosensitive resin composition for light-shielding films of the present invention used within. In addition, the said solid content means the component except (E) component in a composition. (B) component which becomes a solid content after photohardening is also contained in the said solid content. If it is less than 5 mass %, desired light-shielding properties cannot be set. If it exceeds 60 mass %, since content of the photosensitive resin which becomes a binder originally will decrease, not only the developing characteristic will be impaired, but also the unfavorable problem of the film forming ability will arise.

The average particle size (hereinafter referred to as "average secondary particle size") 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 is preferably 20 nm to 500 nm. Moreover, in the photosensitive resin composition for light-shielding films prepared by mixing these carbon black dispersion liquids, it is preferable that these light-shielding components have the same average secondary particle diameter.

In addition, as the (F) dispersant, known dispersants such as various polymer dispersants can be used. As examples of the dispersing agent, well-known compounds (compounds sold under the names of dispersing agents, dispersing wetting agents, dispersing accelerators, etc.) conventionally used for pigment dispersion can be used without particular limitation, and examples thereof include: cationic polymer-based dispersing agents , Anionic polymer dispersants, non-ionic polymer dispersants, pigment derivative type dispersants (dispersing aids), etc. Particularly preferred is a cationic polymer-based dispersant, which has a cationic functional group such as an imidazole group, a pyrrole group, a pyridyl group, a primary amino group, a secondary amino group, or a tertiary amino group as an adsorption point for the pigment, and an amine group is preferred. 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% by mass to 30% by mass, preferably 2% by mass to 25% by mass, with respect to the light-shielding component including insulating carbon black as an essential component.

Furthermore, when preparing a carbon black dispersion liquid, the photosensitive resin for light-shielding films is formed by co-dispersing a part of the polymerizable unsaturated group-containing alkali-soluble resin of the component (A) in addition to the above-mentioned dispersing agent. In the case of a composition, a photosensitive resin composition in which the exposure sensitivity is easily maintained at a high sensitivity, the adhesiveness at the time of development is good, and the problem of residues hardly occurs can be formed. (A) The compounding quantity of a component becomes like this. Preferably it is 2 mass % - 20 mass % in a carbon black dispersion liquid, More preferably, it is 5 mass % - 15 mass %. When the component (A) is less than 2 mass %, the effects of co-dispersion such as sensitivity improvement, adhesion improvement, and residue reduction cannot be obtained. In addition, if it is 20 mass % or more, in particular, when the content of the light-shielding component, which is an essential component of insulating carbon black, is large, the viscosity of the carbon black dispersion liquid is high, and uniform dispersion is difficult or it takes a lot of time, and it becomes difficult to obtain a suitable In order to obtain the photosensitive resin composition of the coating film in which insulating carbon black was uniformly dispersed.

The carbon black dispersion liquid obtained in this way can be obtained by mixing with the (A) component (when the (A) component is co-dispersed at the time of preparing the carbon black dispersion liquid, the remaining (A) component), (B) component , (C) component and residual (E) component are mixed, and the photosensitive resin composition for light-shielding films is formed.

In addition, in the photosensitive resin composition of the present invention, a curing accelerator, a thermal polymerization inhibitor, an antioxidant, a plasticizer, a filler, a leveling agent, an antifoaming agent, a coupling agent, and a surfactant may be prepared as necessary. and other additives. Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, and tert-butyl catechol. catechol), phenothiazine (phenothiazine), hindered phenol (hindered phenol) compounds, etc., plasticizers include: dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc., fillers Examples include glass fibers, silica, mica, alumina, and the like, and examples of leveling agents and defoaming agents include silicone-based, fluorine-based, and acrylic-based compounds. In addition, as a coupling agent, 3-(glycidoxy)propyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, Silane coupling agents such as 3-ureidopropyl triethoxysilane, and surfactants include fluorine-based surfactants, silicone-based surfactants, and the like.

The photosensitive resin composition of the present invention may use together other resin components that are polymerized or cured by heat. The other resin components are preferably (G) epoxy resins or epoxy compounds having two or more epoxy groups, and examples thereof include 3,3',5,5'-tetramethyl-4,4'-biphenol type epoxy resin, bisphenol A type epoxy resin, bisphenol fluorene type epoxy resin, phenol novolac type epoxy resin, 3,4-epoxycyclohexenylmethyl-3,4-epoxy Cyclohexene carboxylate, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, cyclohexane oxysilicone resin, etc. Only one kind of compound may be used for these additional components, and a plurality of them may be used in combination.

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

The photosensitive resin composition of the present invention is characterized in that the hardness of the cured product of the composition excluding the insulating carbon black (component (D)) as a light-shielding component is set to a fixed level or more. About the film-forming conditions of the cured film which measures the said hardness, the photocuring conditions and thermosetting conditions used when a desired pattern is obtained using the photosensitive resin composition of this invention are utilized. For example, the composition for hardness measurement containing (A) component - (C) component and (E) component is spin-coated on a glass substrate using a spinner, and heated and dried at a temperature of 60° C. to 110° C. for 1 minute to 3 minutes Then, using an exposure apparatus equipped with an ultra-high pressure mercury lamp, a predetermined amount of exposure was performed without interposing a photoresist, and the cured film for hardness measurement was produced by thermosetting at 180° C. to 250° C. for 20 minutes to 60 minutes. And when the pencil hardness of the said cured film is measured, it is preferable to obtain the cured film of the pencil hardness of HB or more. More preferably, the photosensitivity of the present invention is prepared by combining components (A) to (C) and suitable additives such as (G) epoxy resin, epoxy compound, or curing accelerator so that the pencil hardness becomes H or more. resin composition. When the pencil hardness is softer than HB, there is a possibility that the elastic recovery rate cannot be sufficiently obtained in the mechanical properties of the spacer. In particular, when the content rate of light-shielding components such as carbon black is small, its influence may be greatly expressed.

The method for obtaining the cured film of pencil hardness of HB or more is not specifically limited, For example, (A) component and (B) component can be selected in consideration of the following points.

In order to make the hardness of the cured film hard, crosslinking between molecules of the polymerizable unsaturated group-containing alkali-soluble resin (component (A)) formed at the time of photocuring, and the component (A) and the photopolymerizable monomer are required. The selection of (A) component, the selection of (B) component, and the design-mixing ratio are performed so that the crosslinking between ((B) component) becomes a fixed amount or more. When the molecular weight of the component (A) increases and the content of the polymerizable unsaturated group in one molecule decreases, it becomes difficult to increase the amount of crosslinking. When the molecular weight of the (A) component is too large, it may be difficult to increase the (A) components and between the (A) and (B) components even if the content of the polymerizable unsaturated group in one molecule is increased. The tendency of the amount of crosslink formation. Moreover, if the polymerizable unsaturated group of (B) component is not three or more, it will become difficult to increase the quantity of crosslinking. In addition, since the physical properties of the cured product are also affected by the structure of the alkali-soluble resin or the structure of the photopolymerizable monomer, these aspects are also taken into account to select the components (A) and (B) to be combined, and to design the blending ratio. .

The photosensitive resin composition for light-shielding films of the present invention is excellent as a photosensitive resin composition for forming, for example, a light-shielding film having a spacer function. The formation method of the light-shielding film which has a spacer function includes the following photodevelopment method. First, the photosensitive resin composition for light-shielding films of the present invention is applied to a base material, and the solvent is dried (pre-baking), and then a photoresist is placed on the film obtained as described above. , irradiating ultraviolet rays to harden the exposed portion, further performing development to elute the unexposed portion using an alkaline aqueous solution to form a pattern, and further performing post-baking (heating) as post-drying.

The base material may be a transparent substrate, or may be an alignment formed by forming a film on the pixels, or on the flattening film on the pixels, or on the flattening film on the pixels after forming pixels such as RGB Substrates other than transparent substrates such as films. The type of substrate on which the light-shielding film having the spacer function is formed differs depending on the design of the liquid crystal display device.

In addition to glass substrates, the transparent substrate to which the photosensitive resin composition is applied can be exemplified by vapor deposition or patterning of indium tin oxide on a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether cellulose, etc.). (indium tin oxide, ITO) or transparent electrodes such as gold, etc. As a method of applying a solution of the photosensitive resin composition on a transparent substrate, in addition to the well-known solution dipping method and spray method, a method using a roll coater, a Land coater, a slit coater, or a spinner can also be employed any method. By these methods, after coating to a desired thickness, the solvent is removed (pre-baking) to form a film. Prebaking is performed by heating with an oven, a hot plate, or the like. The heating temperature and heating time in the prebaking are appropriately selected according to the solvent to be 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 prebaking is performed by an ultraviolet exposure apparatus, and only the resist of the part corresponding to a pattern is exposed to light by exposing through a photoresist. The exposure apparatus and its exposure irradiation conditions are appropriately selected, and light sources such as ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and extreme ultraviolet lamps are used for exposure, and the photosensitive resin composition in the coating film is photocured.

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

After image development, it is preferable to perform a heat treatment (post-baking) at a temperature of 180° C. to 250° C. and a condition of 20 minutes to 60 minutes. The post-baking is performed for the purpose of improving the adhesiveness between the patterned light-shielding film and the substrate, and the like. This is performed by heating with an oven, a hot plate, or the like, as in the prebaking. The patterned light-shielding film of the present invention is formed through each step by the above-described photo-development method.

According to the method, a light-shielding film having an optical density OD of 0.5/μm to 4/μm, 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, in the mechanical property test, a light-shielding film can be formed with a breaking strength of 200 mN or more, an elastic recovery rate of 30% or more, and/or a compressibility of 40% or less. The light-shielding film formed by the method can be used as a column spacer of a liquid crystal display device, and preferably can be used as a black column spacer.

In addition, according to the above method, the 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 the film thickness H2 of the light-shielding film serving as the spacer function can be simultaneously formed. When H2 is 1 μm to 7 μm, ΔH=H2−H1 is 0.1 to 6.9 for the light-shielding film of film thickness H1 and the light-shielding film of film thickness H2. More preferably, the optical density as a light-shielding film is 0.5/μm to 3/μm, H2 is 2 μm to 5 μm, and ΔH is 0.1 to 2.9. Particularly preferable ranges are that the optical density of 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 said method can be used as a column spacer of a liquid crystal display device, Preferably it can be used as a black column spacer. According to the cured film in which the ΔH is in the above range, the black column spacers having different heights can be formed at one time from the same material, so that the liquid crystal display device can be manufactured more efficiently. In this case, for example, the cured film of the film thickness H2 may function as a spacer, and the cured film of the film thickness H1 may be made to 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 the two substrates sandwiching the liquid crystal layer to determine appropriate values, and the appropriate value of H1, ie, the range of ΔH, is determined according to the value of H2.

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

The liquid crystal display device including the light-shielding film or cured film has high light-shielding and insulating properties, further has a spacer function excellent in 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 shape. [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 is shown. The evaluation of the resin in the synthesis example was performed as follows.

[Solid Content Concentration] 1 g of the resin solution obtained in the synthesis example was impregnated in a glass filter [weight: W0 (g)], weighed [W1 (g)], and the weight after heating at 160° C. for 2 hr was calculated. [W2(g)] is obtained from the following equation. Solid content concentration (% by weight)=100×(W2-W0)/(W1-W0)

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

[Molecular weight] By colloidal permeation chromatography (GPC) [trade name HLC-8220GPC manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (two) + TSKgelSuperH-3000 (one) + TSKgelSuperH -4000 (one piece) + TSKgelSuper-H5000 (one piece) [manufactured by Tosoh Co., Ltd.], temperature: 40°C, speed: 0.6 ml/min] Measurement was performed using standard polystyrene [manufactured by Tosoh Corporation] The weight-average molecular weight (Mw) was calculated as a value in terms of PS-oligomer set].

In addition, the abbreviations used in the synthesis examples and comparative synthesis examples are as follows. BPFE: Reaction of 9,9-bis(4-hydroxyphenyl)fluorene with chloromethyl oxirane. 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'-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 put into a 1-L four-necked flask equipped with a reflux cooler. Stir for 12 hr under heating at ℃～105℃ to obtain a 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°C to 120°C for 6 hr to obtain a polymerizable unsaturated group-containing base. 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 by GPC analysis was 3600.

[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, 5.91 g of azobisisobutyronitrile, and 370 g of diethylene glycol dimethyl ether were polymerized by stirring at 80°C to 85°C for 8 hr under nitrogen flow. Furthermore, 39.23 g (0.28 mol) of glycidyl methacrylate, 1.44 g of TPP, and 0.055 g of 2,6-di-tert-butyl-p-cresol were put into the flask, and the temperature was 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 mass %, the acid value (solid content conversion) was 110 mgKOH/g, and the Mw by GPC analysis was 18100.

(Polymerizable unsaturated group-containing alkali-soluble resin) Component (A)-1: Alkali-soluble resin solution obtained in Synthesis Example 1 (A)-2 Component: Alkali obtained in 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): Ethanone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-oxazol-3-yl]-,1-(O -Acetyl oxime) (manufactured by BASF, Japan, product name Irgacure OXE02)

(Carbon black dispersion) (D)-1: PGMEA dispersion liquid (solid content 30.0%) with resin-coated carbon black concentration of 25.0 mass % and dispersant concentration of 5.0 mass % (solid content 30.0%) (D)-2: carbon black 20.0 mass %, high Molecular dispersant 5.0 mass % PGMEA dispersion (solid content 25%)

(Solvent) (E)-1: PGMEA (E)-2: 3-methoxy-3-methyl-1-butyl acetate (epoxy) (G): 2,2-bis(hydroxymethyl) )-1,2-epoxy-4-(2-oxacyclopropyl)cyclohexane adduct of )-1-butanol (“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 (solid content 1.0%) of BYK-330 (manufactured by BYK-Chemie)

[Evaluation on the constituent components of the composition] <Preparation of the composition for evaluating the properties of carbon black> The resin solution (component (A)-1) and the carbon black dispersion ((( D)-1 component or (D)-2 component) and a solvent ((E)-1 component) The composition for carbon black measurement was prepared. The carbon black density|concentration was adjusted, measuring optical density (OD), and the composition which can form the cured film of OD=4/micrometer was prepared. The composition used for surface resistivity measurement is shown in Table 1.

<Optical Density> Using a spin coater, the obtained composition for carbon black measurement was applied on a glass substrate having a thickness of 1.2 mm so that the film thickness after thermosetting treatment was 1.1 μm, and the measurement was carried out at 90° C. for 1 . minutes to pre-bake. Then, using a hot air dryer, heat curing 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 was evaluated by the optical density per unit film thickness.

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

[Table 1]

<Preparation of a composition for evaluation of properties of a photocurable component> A resin solution (component (A)-1), a photopolymerizable monomer (component (B)), a photopolymerization initiator (component (C)), and a solvent were used ((E)-1 component), the composition for property evaluation of the photocurable component shown in Table 2 was prepared.

<Measurement of Pencil Hardness> Using a spin coater, each photosensitive resin composition obtained above was applied on a glass substrate with a thickness of 1.2 mm so that the film thickness after the thermosetting treatment was 1.2 μm, at 90° C. Pre-bake for 1 minute. Then, in the absence of photoresist, ultraviolet rays of 100 mJ/cm ² were irradiated with an ultra-high pressure mercury lamp with a wavelength of 365 nm and an illuminance of 30 mW/cm ² to perform a photohardening reaction. Then, it heat-hardened at 230 degreeC for 30 minutes using a hot air dryer, and obtained the cured film of a photocurable component. With respect to the cured film, according to the Japanese Industrial Standards (JIS)-K5400 test method, a pencil hardness tester was used to apply a load of 500 g, and the highest pencil hardness that did not damage the coating film at this time was taken as the measured value. . The pencil used is "Mitsubishi Hi-uni".

[Table 2]

About the evaluation of the photosensitive resin composition which has a spacer function, the said compounding component was mix|blended in the ratio shown in Table 3, and the photosensitive resin composition of Example 1-Example 5 and Comparative Example 1-Comparative Example 3 was prepared. , and evaluate it. In addition, the numerical values in Table 3 all represent parts by mass. In addition, (E)-1 in the column of solvent does not contain PGMEA (same as (E)-1) and carbon black in the unsaturated group-containing resin solution (polymerizable unsaturated group-containing alkali-soluble resin solution) Amount of PGMEA (same as (E)-1) in dispersion.

[table 3]

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

<Development characteristics> Using a spin coater, the film thickness after thermal curing was 3.0 μm (Example 1, Example 2, Example 4 and Comparative Example 3) or 1.5 μm (Example 3, Example 5 and Comparative Example) Example 1 and Comparative Example 2), each of the obtained photosensitive resin compositions was applied on a glass substrate with a thickness of 1.2 mm, and prebaked at 90° C. for 1 minute. Then, the photoresist was brought into close contact, and ultraviolet rays of 100 mJ/cm ² were irradiated with an ultra-high pressure mercury lamp with a wavelength of 365 nm and an illuminance of 30 mW/cm ² to perform a photohardening reaction of the photosensitive portion.

Next, the glass substrate after the exposure was developed for 60 seconds at 24° C. and a pressure of 0.1 MPa using a 0.05% potassium hydroxide aqueous solution, and the unexposed portion of the coating film was removed. Then, it heat-hardened at 230 degreeC for 30 minutes using a hot air dryer, and obtained the cured film of the photosensitive resin composition. The formation of the thin line of the obtained cured film pattern was confirmed by an optical microscope, and it evaluated by the following three steps. The results are shown in Table 4. ○: Patterns with L/S of 10 μm/10 μm or more formed without residues / 50 μm pattern, or the bottom of the pattern has significant curling or residue

<Volume resistivity> Using a spin coater, each photosensitive resin composition obtained above was applied on a glass substrate having a thickness of 1.2 mm on which Cr was vapor-deposited so that the film thickness after the thermosetting treatment was 3.5 μm. Parts other than the electrodes were pre-baked at 90°C for 1 minute. Then, it heat-hardened at 230 degreeC for 30 minutes using a hot air dryer, and obtained the cured film of the photosensitive resin composition. Then, an aluminum electrode was formed on the cured film, and it was set as the board|substrate for volume resistivity measurement. Next, the volume resistivity at an applied voltage of 1 V to 10 V was measured using an electrometer (manufactured by Keithley, Inc., "Model 6517A"). Table 4 shows the volume resistivity at the time of applying 10 V, which was measured under the condition that the voltage was held for 60 seconds at each applied voltage in the 1 V step.

<Dielectric constant> Using a spin coater, each photosensitive resin composition obtained above was applied on a glass substrate having a thickness of 1.2 mm on which Cr was vapor-deposited so that the film thickness after the thermosetting treatment was 3.5 μm. Parts other than the electrodes were pre-baked at 90°C for 1 minute. Then, it heat-hardened at 230 degreeC for 30 minutes using a hot air dryer, and obtained the cured film of the photosensitive resin composition. Then, an aluminum electrode was formed on the cured film, and it was set as the board|substrate for dielectric constant measurement. Next, the capacitance at a frequency of 1 Hz to 100,000 Hz was measured using an electrometer (manufactured by Keithley, Inc., "Type 6517A"), and the dielectric constant was calculated from the capacitance. The calculated dielectric constants are shown in Table 4.

<Half tone (HT) characteristics of the spacer> Using a spin coater, the film thickness after thermal curing treatment was 3.0 μm (Example 1, Example 2, Example 4, and Comparative Example 3) or 1.5 μm (Example 3, Example 5, Comparative Example 1, Comparative Example 2), each photosensitive resin composition obtained above was applied on a glass substrate with a thickness of 1.2 mm, and prebaked at 90° C. for 1 minute. bake. Then, the photoresist with the dot pattern was brought into close contact, and ultraviolet rays of 5 mJ/cm ² or 100 mJ/cm ² were irradiated with an ultra-high pressure mercury lamp with a wavelength of 365 nm and an illuminance of 30 mW/cm ² to perform a photohardening reaction of the photosensitive portion. Next, the glass substrate after the exposure was developed for 60 seconds at 24° C. and a pressure of 0.1 MPa using a 0.05% potassium hydroxide aqueous solution, and the unexposed portion of the coating film was removed. Then, it heat-hardened at 230 degreeC for 30 minutes using a hot air dryer, and obtained the cured film of the photosensitive resin composition.

The halftone characteristic of the spacer is 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 , using the following The evaluation is carried out 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 greater than 2.9 μm

<Compression ratio, elastic recovery ratio, and breaking strength of spacer> Using a spin coater, each photosensitive resin composition obtained above was applied to a 1.2 mm thick film so that the film thickness after the thermosetting treatment was 3.0 μm. On a glass substrate, prebake at 90°C for 1 minute. Then, the photoresist having a dot pattern was brought into close contact, and ultraviolet rays of 100 mJ/cm ² were irradiated with an ultra-high pressure mercury lamp with a wavelength of 365 nm and an illuminance of 30 mW/cm ² to perform a photohardening reaction of the photosensitive portion.

Next, the glass substrate after the exposure was developed for 60 seconds at 24° C. and a pressure of 0.1 MPa using a 0.05% potassium hydroxide aqueous solution, and the unexposed portion of the coating film was removed. Then, it heat-hardened at 230 degreeC for 30 minutes using a hot air dryer, and obtained the cured film of the photosensitive resin composition. The spacer characteristics of the obtained cured film pattern were evaluated using an ultra-fine hardness tester (Fischerscope HM2000Xyp, manufactured by Fisher Instruments). A flat indenter of 100 μm square was squeezed at a loading speed of 5.0 mN/sec. After loading up to a load of 50 mN, the load was removed at a loading speed of 5.0 mN/sec to create a displacement curve. The compressibility was calculated by the following formula, using the displacement amount under a load of 50 mN at the time of loading as L1. Compression ratio (%) = L1 / height of spacer × 100

The elastic recovery rate was calculated by the following formula, assuming that the amount of displacement under a load of 50 mN at the time of loading was L1, and the amount of displacement when the load was removed was L2. Elastic recovery rate (%)=(L1-L2)/L1×100

The breaking strength was evaluated using an ultra-micro hardness tester (Fischer scope HM2000Xyp, manufactured by Fisher Instruments). A flat indenter of 100 μm square was squeezed at a loading speed of 5.0 mN/sec, and the load at the time of breaking the spacer was measured until the load was applied to 300 mN, and the evaluation was performed in the following three stages. 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 Spacer> Using a spin coater, each of the photosensitive resin compositions obtained above was applied on a glass substrate with a thickness of 1.2 mm so that the film thickness after the thermosetting treatment was 3.0 μm, at 90° C. Pre-bake for 1 minute. Then, the photoresist having a dot pattern was brought into close contact, and ultraviolet rays of 100 mJ/cm ² were irradiated with an ultra-high pressure mercury lamp with a wavelength of 365 nm and an illuminance of 30 mW/cm ² to perform a photohardening reaction of the photosensitive portion.

Next, the glass substrate after the exposure was developed for 60 seconds at 24° C. and a pressure of 0.1 MPa using a 0.05% potassium hydroxide aqueous solution, and the unexposed portion of the coating film was removed. Then, it heat-hardened at 230 degreeC for 30 minutes using a hot air dryer, and obtained the cured film of the photosensitive resin composition. The shape of the spacer was evaluated by the inner angle (taper angle) of the spacer end using a scanning electron microscope. The case where the taper angle is 70° or more and 90° or less is ⊚, 50° or more and less than 70° is ○, 50° or less is Δ, and 90° or more 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 be HB or more, the Spacer properties such as light-shielding properties, dielectric constant, and elastic recovery rate are improved while maintaining volume resistivity.

none.

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Claims (9)

A photosensitive resin composition, which is a photosensitive resin composition for a light-shielding film with a spacer function, characterized in that it contains (A) components to (E) components as essential components: (A) contains a polymerizable unsaturated group The alkali-soluble resin, wherein the polymerizable unsaturated group-containing alkali-soluble resin represented by the general formula (II) is used as the (A) component,

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 direct bond, Y represents a tetravalent carboxylic acid residue, Z independently represents a hydrogen atom or -OC-W-(COOH) _l , wherein, 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; (B) a photopolymerizable monomer having at least three ethylenically unsaturated bonds; (C) a photopolymerization initiator; (D) containing insulating carbon A black light-shielding component; and (E) a solvent containing 5 to 400 parts by mass of the (B) component with respect to 100 parts by mass of the (A) component, and with respect to the (A) component and the The total amount of the component (B) is 100 parts by mass, and the component (C) is contained in an amount of 0.1 to 40 parts by mass, and the component (E) that contains the component (B) that becomes a solid after photohardening is ) When a component other than a component is a solid content, 5 to 60 mass % of the component (D) is contained in the total amount of the solid content, and the component (D) is a cured film obtained from the composition for evaluation. A light-shielding component having a surface resistivity of 1×10 ⁸ Ω/□ or more, wherein the evaluation composition includes the (A) component, the (D) component, and the (E) component, and the evaluation The optical density of the cured film obtained by applying the composition so that the film thickness after the thermosetting treatment may be 1.1 μm and heating and curing at 230° C. for 30 minutes after prebaking is 4/μm prepared in a manner that includes the (A) component, the (B) component, the (C) component, and the (E) component, and the combination of the (A) component and the (B) component The composition of the composition with the same mixing ratio as the above-mentioned photosensitive resin composition was coated so that the film thickness after the thermosetting treatment was 1.2 μm, and the cured film obtained by heating and curing at 230° C. for 30 minutes after prebaking was obtained. The pencil hardness is HB or higher. The photosensitive resin composition according to claim 1, wherein a light-shielding film having an optical density OD of 0.5/μm or more and 4/μm or less and a volume resistivity of 1 when a voltage of 10V is applied can be formed. ×10 ⁹ Ω. cm or more, and the dielectric constant is 2~10. The photosensitive resin composition according to claim 1, wherein a light-shielding film satisfying at least one of the following (i) to (iii) can be formed in a load-unload test using a micro hardness tester, (i) the compression ratio is 40% or less; (ii) the elastic recovery ratio is 30% or more; (iii) the breaking strength is 200 mN or more. A light-shielding film having a spacer function, characterized by being formed by curing the photosensitive resin composition according to any one of Claims 1 to 3. A liquid crystal display device is characterized by comprising the light-shielding film as described in item 4 of the patent application scope as a black column spacer. The liquid crystal display device according to claim 5, further comprising a thin film transistor. A method for producing a light-shielding film, characterized in that: after applying the photosensitive resin composition according to any one of items 1 to 3 of the patent application scope on a substrate, the photosensitive resin composition is irradiated with light to make the photosensitive resin composition In the method for producing a light-shielding film formed on a substrate in which the resin composition is cured, the film thickness H1 for setting the optical density OD as the light-shielding film to be 0.5/μm or more and 4/μm or less, and the spacer function The film thickness H2 of the light-shielding film is simultaneously formed when H2 is 1 μm to 7 μm, and ΔH=H2-H1 is 0.1 to 6.9. The film thickness H1 and the light shielding film of the film thickness H2. A method of manufacturing a liquid crystal display device, characterized in that a light-shielding film manufactured by the method of manufacturing a light-shielding film according to claim 7 is used as a black column spacer. The method for manufacturing a liquid crystal display device according to claim 8, wherein the liquid crystal display device includes a thin film transistor.