KR20180111661A - Photosensitive resin composition, light-shielding film thereof, and manufacturing process of lcd with that film - Google Patents

Abstract

The present invention provides a photosensitive resin composition capable of producing a spacer which has excellent spacer characteristics such as compression ratio, elastic recovery, breakdown strength, and the like, while maintaining light-blocking properties and insulating properties; is capable of forming a step of ΔH; and has an excellent pattern profile. The present invention relates to a photosensitive resin composition. The photosensitive resin composition of the present invention is a photosensitive resin composition for a light-blocking film having a spacer function, which comprises the following components (A) to (E) as essential components: (A) an alkali-soluble resin having a polymerizable unsaturated group; (B) a photopolymerizable monomer having at least three ethylenically unsaturated bonds; (C) a photopolymerization initiator; (D) a light-blocking component containing insulating carbon black in which a resistivity of the surface of a film formed to have an optical density of 4/μm is 1*10^8 Ω/□ or more; and (E) a solvent, wherein a pencil hardness of a cured material of the composition excluding the component (D) is HB or greater.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, a light-shielding film, a liquid crystal display, and a method of manufacturing a liquid crystal display device,

The present invention relates to a photosensitive resin composition and a light-shielding film obtained by curing the same. More specifically, the present invention relates to a photosensitive resin composition which is capable of forming a black column spacer having a spacer function and a black matrix function in a liquid crystal display device by photolithography A resin composition and a cured film thereof. The present invention also relates to a liquid crystal display device using the black column spacer obtained by the above curing. The present invention also relates to a method of manufacturing the liquid crystal display device.

In recent years, color liquid crystal displays (LCDs) have been used in all fields, such as liquid crystal televisions, liquid crystal monitors, and color liquid crystal cellular phones. Among them, improvements aimed at improving characteristics such as a viewing angle, a contrast, and a response speed have been vigorously carried out in order to improve the performance of an LCD, and various panel structures (thin film transistor Is being developed. With regard to the TFT-LCD, a method of manufacturing an array substrate on which a conventional TFT is formed and a color filter substrate are manufactured, and both substrates are pasted with a spacer maintained at regular intervals.

Conventionally, for a spacer functioning to keep the thickness of the liquid crystal layer (the spacing between the array substrate and the color filter (CF) substrate in the conventional method) constant, which is one factor affecting the performance of the LCD, A method of sandwiching a ball spacer was taken. However, in this method, there is a problem that the dispersion state of the ball spacer becomes non-uniform, whereby the light transmission amount per pixel becomes uneven. To solve this problem, a method of forming a column spacer by photolithography is employed. However, the column spacers formed by the photolithography method are often transparent. In such a column spacer, light incident in the oblique direction affects the electric characteristics of the TFT, thereby deteriorating the display quality. To solve 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 photolithography, has been proposed (Patent Document 1).

This light-shielding column spacer requires a film thickness of about 1 to 7 mu m in order to function as a spacer. It is also necessary that the light-shielding column spacers having different heights at the points where the TFTs are formed and other points can be formed at the same time. It is also required that the light-shielding column spacer has a suitable range of elasticity, deformation, elastic recovery, etc. as a spacer function (Patent Document 3). It is also desired to improve the light-shielding column spacer to reduce the curing component by adding a light-shielding component (coloring agent) to the spacer, and to reduce the loss of electrical characteristics due to the influence of impurities in the coloring agent 4).

Japanese Patent Application Laid-Open No. 08-234212 U.S. Patent Application Publication No. 2009/0303407 Japanese Laid-Open Patent Publication No. 2009-031778 International Publication No. 2013/062011

In Patent Document 4, although a mixed color organic pigment is used, the optical density of the light-shielding column spacer is not disclosed. The color mixture organic pigments are effective for lowering the dielectric constant as compared with inorganic pigments such as carbon black, but often have low light shielding properties. Further, since it is necessary to form spacers having different heights at the same time, the light-shielding column spacers are also required to have mechanical properties such as compressibility, elastic recovery rate and breaking strength. Since the shape and mechanical characteristics of the spacer are greatly affected by the light shielding component, it is difficult to design the photosensitive resin composition for the light shielding film. Therefore, the shape and mechanical properties of the spacer using carbon black, a mixed color organic pigment or the like can not be said to be still sufficient, and a new modification is required.

In addition, as described above, the light-shielding column spacer is made to have a film thickness of about 1 to 7 mu m. With the recent miniaturization of liquid crystal display elements, it is desired that a light-shielding column spacer can form a fine spacer shape even if the film thickness is about 1 to 7 mu m. In addition, after the function of the black matrix and the spacer is provided, two kinds of heights of the light-shielding spacers are to be formed in order to precisely adhere the two substrates sandwiching the liquid crystal layer with each other, that is, There is a great demand for patterning characteristics such as forming a light-shielding spacer which is as vertical as possible from a glass substrate, and it is difficult to satisfy all the required characteristics.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-described problems, and it is an object of the present invention to provide a light-shielding film having a high light-shielding property and insulating property and a spacer function excellent in compression ratio, elastic recovery rate and breaking strength, A photosensitive resin composition capable of forming a pattern shape, a light-shielding film having a spacer function formed using the same, and a liquid crystal display device using the light-shielding film as a component.

The inventors of the present invention have conducted studies to solve the problems in the photosensitive resin composition for a light-shielding film as described above. As a result, they found that a specific coloring agent is preferable as a light-shielding component of a photosensitive resin composition for a light- .

(1) The present invention provides a photosensitive resin composition for a light-shielding film having a spacer function, which comprises the following components (A) to (E) as essential components: (A) a polymerizable unsaturated group- , (B) a photopolymerizable monomer having at least three ethylenically unsaturated bonds, (C) a photopolymerization initiator, (D) a film having an optical density of 4 / 탆 and having a surface resistivity of 1 × 10 ⁸ Ω / Or more, and the cured product of the composition excluding the (E) solvent and the (D) component has a pencil hardness of not less than HB.

(2) The present invention is further characterized in that the component (B) is used in an amount of 5 to 400 parts by mass based on 100 parts by mass of the component (A), 0.1 to 0.1 part by mass of the component (C) (D) is contained in an amount of 5 to 60% by mass of the total amount of solids, and the content of the component (B) (1). ≪ / RTI >

(3) The present invention is also the photosensitive resin composition characterized by using as the component (A) an alkali-soluble resin containing a polymerizable unsaturated group represented by the general formula (II).

[Chemical Formula 1]

Wherein 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, -CO-, -SO ₂ -, -C (CF ₃ ) ₂ -, -Si (CH ₃ ) ₂ -, -CH ₂ -, -C (CH ₃ ) ₂ -, -O-, Y represents a tetravalent carboxylic acid residue, and each Z independently represents a hydrogen atom or -OC-W- (COOH) ₁ (wherein W represents a divalent or trivalent carboxylic acid And l represents a number of 1 to 2), and n represents a number of 1 to 20.

(4) The present invention also provides a light-shielding film having an optical density OD of 0.5 / 탆 or more and 4 / 탆 or less as a light-shielding film having a volume resistivity of 1 × 10 ⁹ Ω · cm or more at a voltage of 10 V and a dielectric constant of 2 to 10 The photosensitive resin composition according to any one of (1) to (3),

(5) The present invention also provides a light-shielding film which is capable of forming a light-shielding film satisfying at least one of the following (i) to (iii) in a load-unloading test using a micro- Sensitive resin composition according to any one of claims 1 to 4. (i) the compression rate is 40% or less, (ii) the elastic recovery rate is 30% or more, and (iii) the breaking strength is 200 mN or more.

(6) The present invention is also a light-shielding film having a spacer function, which is formed by curing the photosensitive resin composition according to any one of (1) to (5).

(7) The present invention is also a liquid crystal display device characterized by having the light-shielding film described in (6) as a black column spacer (BCS).

(8) The present invention is also the liquid crystal display device described in (7), further comprising a thin film transistor (TFT).

(9) The present invention also provides a method for producing a light-shielding film formed on a substrate, which comprises applying the photosensitive resin composition according to any one of (1) to (5) to a substrate and curing the photosensitive resin composition by light irradiation H2 = H1 - H1 when H2 is 1 to 7 占 퐉, with respect to the film thickness H1 for setting the optical density as the light shielding film to 0.5 / 占 퐉 or more and 4 / 占 퐉 or less and the film thickness H2 of the light- Shielding film having a film thickness H1 of 0.1 to 6.9 and a film thickness H2 is formed at the same time.

(10) The present invention is also a method for manufacturing a liquid crystal display device, characterized in that the light-shielding film produced by the method described in (9) is a black column spacer.

(11) The present invention is also the manufacturing method according to (10), 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 insulating carbon black as a coloring agent, a cured product excellent in compressibility, elastic recovery and fracture strength can be obtained while maintaining the light shielding property and insulating property as compared with the conventional photosensitive resin composition . Further, the photosensitive resin composition for a light-shielding film according to the present invention can form a fine spacer shape even if the film thickness is about 1 to 7 mu m.

Hereinafter, the present invention will be described in detail.

As the polymerizable unsaturated group-containing alkali-soluble resin of the component (A), a resin having in its molecule an acidic group such as a carboxyl group which contributes to polymerizable unsaturated double bonds and alkali developability contributing to the photo-curing reaction can be used without particular limitation. Among them, as a first example which is preferably used, an epoxy compound having two glycidyl ether groups derived from bisphenols, preferably an epoxy compound represented by the general formula (I), with (meth) acrylic acid (A) a tetracarboxylic acid or its acid dianhydride, and (b) a dicarboxylic acid-containing compound (c) having a polymerizable unsaturated group which is obtained by reacting a hydroxyl group- Is an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule, which is obtained by reacting a carboxylic acid or a tricarboxylic acid or an acid anhydride thereof. The component (A) combines a polymerizable unsaturated double bond and a carboxyl group, thereby giving the photosensitive resin composition excellent photo-curability, good developing property, and patterning property, thereby improving the physical properties of the light-shielding film.

(2)

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, X represents -CO-, -SO ₂ -, -C (CF ₃ ) ₂ -, -Si (CH ₃ ) ₂ -, -CH ₂ -, -C (CH ₃ ) ₂ -, -O- or a fluorene- Or an average value of m is in the range of 0 to 10, preferably 0 to 3.

Examples of the bisphenols that provide the epoxy compound of formula (I) include bis (4-hydroxyphenyl) ketone, bis (4-hydroxy- Bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis Bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, bis Bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3,5-dimethylphenyl) dimethylsilane, bis Bis (4-hydroxy-3,5-dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) methane, bis Phenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethyl Propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2- Bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl) , 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy- (4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9- (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dichloro Phenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene, 4,4'-biphenol and 3,3'-biphenol. As these bisphenols, only one kind of compound may be used, or a plurality of these compounds may be used in combination. Among them, bisphenols in which X in the general formula (I) is a fluorene-9,9-diyl group can be particularly preferably used.

The compound represented by formula (I) for introducing into the alkali-soluble resin of (A) is an epoxy compound having two glycidyl ether groups obtained by reacting the bisphenols with epichlorohydrin. In this reaction, oligomerization of a diglycidyl ether compound is generally carried out, m is an integer of 0 to 10 in each molecule, and ordinarily, since molecules having a plurality of values are mixed, 0 to 10 (it is not limited to an integer), but the average value of m is preferably 0 to 3. When the average value of m exceeds the upper limit value, when the photosensitive resin composition is used as an alkali-soluble resin synthesized by using the epoxy compound, the viscosity of the composition becomes excessively large and the coating becomes poor or the alkali- The developing property is very bad.

Next, an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule is reacted with a hydroxyl group-containing compound (c) containing a polymerizable unsaturated group obtained by the reaction of an epoxy compound and (meth) acrylic acid with an acid component Can be obtained. As the acid component, it is possible to use a tetracarboxylic acid or its acid dianhydride (a) capable of reacting with a hydroxyl group-containing compound and a dicarboxylic acid or a tricarboxylic acid or an acid anhydride (b) good. The carboxylic acid residue of the acid component may have either a saturated hydrocarbon or an unsaturated hydrocarbon. These carboxylic acid residue may contain a bond containing a hetero element such as -O-, -S-, or carbonyl group.

Specific examples of the acid component are shown below, but the dianhydrides and monohydrides of the polyvalent carboxylic acids exemplified are also usable.

First, as the tetracarboxylic acid (a), there can be mentioned a chain type hydrocarbon tetracarboxylic acid, an alicyclic tetracarboxylic acid or an aromatic polycarboxylic acid. Examples of the chain-like hydrocarbon tetracarboxylic acid include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid and the like, and further, there can be used tetracarboxylic acid do. Examples of the alicyclic tetracarboxylic acid include, for example, cyclic butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid Or a tetracarboxylic acid to which an arbitrary substituent has been introduced. Examples of the aromatic tetracarboxylic acid include pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, biphenyl ether tetracarboxylic acid, and further, arbitrary substituents Or a tetracarboxylic acid introduced with an acid. As the tetracarboxylic acid (a), only one type of compound may be used, or a plurality of tetracarboxylic acids may be used in combination.

The dicarboxylic acid or tricarboxylic acid (b) may be a chain-like hydrocarbon dicarboxylic acid or tricarboxylic acid, alicyclic dicarboxylic acid or tricarboxylic acid, aromatic dicarboxylic acid or tricarboxylic acid, Bicic acid is used. Examples of the chain type hydrocarbon dicarboxylic acid or tricarboxylic acid include 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 and the like, and further dicarboxylic acid or tricarboxylic acid into which an arbitrary substituent has been introduced. Examples of the alicyclic dicarboxylic acid or tricarboxylic acid include cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid, and the like. Or may be a dicarboxylic acid or a tricarboxylic acid to which an arbitrary substituent has been introduced. Further, examples of the aromatic dicarboxylic acid or tricarboxylic acid include phthalic acid, isophthalic acid, trimellitic acid and the like, and further dicarboxylic acid or tricarboxylic acid into which an arbitrary substituent is introduced . As the dicarboxylic acid or tricarboxylic acid (b), only one kind of compound may be used, or a plurality of them may be used in combination.

(B) / (a) of (a) the tetracarboxylic acid or its acid dianhydride and (b) the dicarboxylic acid or the tricarboxylic acid or its acid anhydride used in the alkali- 0.01 to 0.5, preferably 0.02 or more and less than 0.1. If the molar ratio (b) / (a) deviates from the above range, it is not preferable since the optimum molecular weight can not be obtained for the photosensitive resin composition having high light shielding and high resistance and good optical patterning property of the present invention. Further, the smaller the molar ratio (b) / (a), the higher the alkali solubility and the larger the molecular weight.

The ratio of reacting the hydroxyl group-containing compound (c) containing the polymerizable unsaturated group with the acid components (b) and (a) is preferably such that the mole ratio of each component is (b): (a) = 1: 0.2 to 1.0: 0.01 to 1.0. In this case, the reaction is carried out quantitatively so that the molar ratio (c) / (b) / 2 + (a) of the total amount of the acid components to the hydroxyl group-containing compound (c) containing the polymerizable unsaturated group is 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 increases, and the stability of the alkali-soluble resin composition is deteriorated over time. On the other hand, when the molar ratio exceeds 1.0, the content of the hydroxyl group-containing compound containing an unreacted polymerizable unsaturated group increases, and the stability of the alkali-soluble resin composition over time tends to deteriorate. The molar ratios of the respective components (a), (b) and (c) can be arbitrarily changed within the above-mentioned range for the purpose of adjusting the acid value and the molecular weight of the alkali-soluble resin.

The alkali-soluble resin of the component (A) can be produced by the above-described procedure by a known method, for example, a method described in Japanese Unexamined Patent Application Publication No. 8-278629 or Japanese Unexamined Patent Publication No. 2008-9401. First, as a method of reacting (meth) acrylic acid with the epoxy compound of the general formula (I), for example, a method in which a (meth) acrylic acid equivalent to an epoxy group of an epoxy compound is added in a solvent and a catalyst (triethylbenzylammonium chloride , 2,6-diisobutylphenol, and the like), heating and stirring at 90 to 120 ° C with blowing air to react. Next, as a method for reacting the acid anhydride with the hydroxyl group of the epoxy acrylate compound as the reaction product, a predetermined amount of an epoxy acrylate compound, an acid anhydride and an acid anhydride is added to a solvent, and a catalyst (tetraethylammonium bromide, Triphenylphosphine, etc.) at 90 to 140 ° C, and the mixture is allowed to react.

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

(3)

Wherein 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, -CO-, -SO ₂ -, -C (CF ₃ ) ₂ -, -Si (CH ₃ ) ₂ -, -CH ₂ -, -C (CH ₃ ) ₂ -, -O-, Y represents a tetravalent carboxylic acid residue, and each Z independently represents a hydrogen atom or -OC-W- (COOH) ₁ (wherein W represents a divalent or trivalent carboxylic acid And l represents a number of 1 to 2), and n represents a number of 1 to 20.

The group of compounds represented by the general formula (II) is an epoxy acrylate acid adduct prepared by using a bisphenol-type epoxy compound as a raw material. However, a novolac epoxy compound, An epoxide of a compound, an epoxide of a biphenol aralkyl compound, or the like may be used as a raw material. When an acid component is added to the epoxy acrylate compound, a polyol compound having two or more alcoholic hydroxyl groups is allowed to coexist, or a compound having two or more isocyanate groups is allowed to coexist, or the like to obtain an unsaturated group-containing alkali- It is also possible to design the cured product to have desired physical properties.

As a second example of the unsaturated group-containing alkali-soluble resin as the component A, an alkali-soluble resin obtained by radical polymerization of (meth) acrylic acid with various kinds of (meth) acrylic acid esters is further reacted with glycidyl Soluble unsaturated group-containing alkali-soluble resin.

Examples of the (meth) acrylic acid ester copolymerized with (meth) acrylic acid include (meth) acrylic acid ester, (meth) acrylamide, styrene and its derivatives, maleic anhydride and its derivatives, vinyl ethers and olefins .

(Meth) acrylic acid ester or amide is a group of compounds having a structure obtained by reacting (meth) acrylic acid with an alcohol (R ₆ OH) component or an amine (R ₇ R ₈ NH), and there is no particular limitation, have. Specific examples of R ₆ , R ₇ and R ₈ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a 2-cyclopentylethyl group and a cyclohexylmethyl group A monocyclic alkyl group which may be substituted with a linear, branched or alicyclic structure, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a 4-methylcyclohexyl group, an adamantyl group, an isobornyl group, a dicyclopentanyl group, Monovalent alicyclic hydrocarbon groups such as cyclopentenyl and chloropentenyl groups and monovalent aromatic hydrocarbon groups such as phenyl, tolyl, mesityl, naphthyl, anthryl, benzyl and 2-phenylethyl groups, pyridyl, A pyridyl group, a pyridyl group, an imidazolyl group, an imidazolidinyl group, a pryl group, a tetrahydrofuryl group, a thienyl group, a tetrahydrothienyl group, a morpholinyl group, a morpholino group, Saturated or unsaturated monovalent complex Rigi, and the like. In addition, a halogen atom, a hydroxyl group, a sulfanyl group, a carbonyl group, a thiocarbonyl group, a carboxyl group, a thiocarboxyl group, a dithiocarboxyl group, a formyl group, a cyano group, a nitro group, A thioester group, a dithioester group, an amide group, a thioamide group, a urethane group, a thiourethane group, an ureido group, an ester group, an ester group, A thioureido group and the like may be introduced as a substituent.

The weight average molecular weight (Mw) of the alkali-soluble resin (A) in terms of polystyrene determined by gel permeation chromatography (GPC) measurement is usually 1,000 to 50,000, preferably 2,000 to 15,000. When the weight average molecular weight is less than 1000, the adhesion of the pattern during alkali development may be deteriorated. When the weight average molecular weight exceeds 50000, the developability is lowered, There is a possibility that it becomes difficult to make the composition. In the case of the alkali-soluble resin of the formula (II), the weight average molecular weight is preferably 2000 to 10000, more preferably 3000 to 7000.

The acid value of the alkali-soluble resin (A) is preferably from 30 to 200 mgKOH / g. If this value is less than 30 mgKOH / g, the residue tends to remain at the time of alkali development, and if it exceeds 200 mgKOH / g, the penetration of the alkaline developer becomes too fast and peeling phenomenon occurs. The polymerizable unsaturated group-containing alkali-soluble resin (A) may be used alone or as a mixture of two or more thereof.

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 with HLC-8220GPC manufactured by Toso Co., Ltd. to calculate the weight average molecular weight in terms of standard polystyrene do. The acid value of component A is the value obtained by dissolving the sampled solution in dioxane, neutralizing with 0.1 N aqueous potassium hydroxide solution, and calculating the acid value in terms of solid content of the sample solution at the equivalent point.

Examples of the photopolymerizable monomer (B) having at least three ethylenic unsaturated bonds include trimethylolpropane tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, pentaerythritol tri (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (Meth) acrylates such as alkyl (meth) acrylate, sorbitol hexa (meth) acrylate, alkylene oxide modified hexa (meth) acrylate of phosphazene and caprolactone modified dipentaerythritol hexa Vinyl benzyl ether compounds such as polyhydric alcohols (pentaerythritol, dipentaerythritol, etc.) and polyhydric phenols (phenol novolac, etc.), divinylbenzene There may be mentioned the addition polymer, such as vinyl compounds. As the photopolymerizable monomer having at least three ethylenically unsaturated bonds (B), only one kind of compound may be used, or a plurality of them may be used in combination. Further, the photopolymerizable monomer (B) having at least three ethylenically unsaturated bonds does not have an liberated carboxyl group.

(B) is preferably 5 to 400 parts by mass, more preferably 10 to 150 parts by mass, per 100 parts by mass of the component (A). If the compounding 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 disappears and the acid value of the coating film in the unexposed area is low, So that the pattern edge becomes jagged and the shape of the pattern does not become sharp. On the other hand, if the blending ratio of the component (B) is less than 5 parts by mass based on 100 parts by mass of the component (A), the ratio of the photoreactive functional groups in the resin is insufficient and the formation of the crosslinking structure is insufficient. There is a possibility that the formed pattern tends to be thinner than a target line width or that a pattern is liable to be missed because the acid value in the exposed portion is high and the solubility in the alkali developing solution in the exposed portion is high.

Examples of the photopolymerization initiator of the component (C) include, for example, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone , and p-tert-butyl acetophenone, benzophenones such as benzophenone, 2-chlorobenzophenone, and p, p'-bisdimethylaminobenzophenone, benzoin, benzoin, benzoin methyl ether, benzo Benzoin isobutyl ether; benzoin ethers such as 2- (o-chlorophenyl) -4,5-phenylbimidazole, 2- (o-chlorophenyl) -4,5-di (o-methoxyphenyl) imidazole, 2- (o-fluorophenyl) -4,5-diphenylbimidazole, 2- Imidazole compounds such as 2,4,5-triarylbimidazole, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p- (Trichloromethyl) -1,3,5-triazine, 2-methyl-4-thiophene, , Trichloromethyl) -1,3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) (Trichloromethyl) -1,3,5-triazine, 2- (4-methoxyphenyl) -4,6-bis Azine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl) Trichloromethyl) -1,3,5-triazine, 2- (3,4,5-trimethoxystyryl) -4,6-bis (trichloromethyl) Halomethyl-s-triazine compounds such as 2- (4-methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2-oxime-O-benzoate, 1- (4-phenylsulfanylphenyl) butane- (4-methylsulfanylphenyl) butane-1,2-dione-2-oxime-O- Acetate, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl -, 1- (0-acetyloxime), methanone, (9-ethyl-6-nitro-9H-carbazol- -Methylphenyl] -, O-acetyl oxime, methanone, (2-methylphenyl) (7-nitro-9,9- 1- (O-acetyloxime), ethanone, 1 - (- 9,9-dibutyl- O-acyloxime compounds such as 7-nitro-9H-fluoren-2-yl) - and 1-O-acetyloxime, benzyldimethyl ketal, thioxanthone, 2-chlorothioxanthone, Sulfur compounds such as diethylthioxanthone, 2-methylthioxanthone and 2-isopropylthioxanthone, 2-ethyl anthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenyl Anthraquinones such as anthraquinone, azobisisobutylnitrile, benzoyl peroxide, cumene Organic peroxides such as oxides, thiol compounds such as 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole, and the like. Of these, from the viewpoint of easily obtaining a photosensitive resin composition for a light-shielding film having a high sensitivity, it is preferable to use O-acyloxime compounds. As the (C) photopolymerization initiator, only one type of compound may be used, or a plurality of (C) photopolymerization initiators may be used in combination. The photopolymerization initiator used in the present invention is used to mean a sensitizer.

These photopolymerization initiators and sensitizers may be used singly or in combination of two or more. In addition, they do not act as photopolymerization initiators or sensitizers in themselves, but by using them in combination, it is possible to add a compound capable of increasing the photopolymerization initiator and the ability of the sensitizer. Such compounds include, for example, 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 from 0.1 to 40 parts by mass, and more preferably from 1 to 25 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). When the blending ratio of the component (C) is less than 0.1 part by mass, the speed of photopolymerization is slowed down and the sensitivity is lowered. On the other hand, when the mixing ratio exceeds 40 parts by mass, the sensitivity becomes excessively strong, State, it is impossible to reproduce a faithful line width with respect to the mask, or the pattern edge may become chunky and not sharp.

The component (D) is a layer having a film thickness of 10 to 1.5 탆, a composition containing 5 to 20 mass% of the component (D) and 5 to 15 mass% of the component (A) 4 / 占 퐉 is not less than 1 占⁰⁸ ? / ?, which is a light shielding component containing insulating carbon black. The insulating carbon black that can be contained in such a light-shielding component needs to be subjected to an insulating treatment on the surface of the carbon black by various methods, but the method of the insulating treatment is not particularly limited. Examples of the insulating treatment method include a method of coating with a resin (for example, Japanese Patent Application Laid-Open No. 9-95625), a method of oxidizing with an oxidizing agent (for example, Japanese Unexamined Patent Application Publication No. 11-181326) , A method of grafting with a polymer having a reactive group (for example, JP-A 9-265006), a method of chemically modifying with an organic group (for example, Japanese Patent Publication No. 2008-517330) (For example, Japanese Unexamined Patent Publication (Kokai) No. 2002-249678), a method of coating with a coloring matter (for example, International Publication No. 2013/129555), and the like are known.

As the component D, two or more kinds of insulating carbon black may be used, and black organic pigments such as perylene black, aniline black, cyanine black and lactam black, and organic pigments such as red, blue, green, yellow, cyanine and magenta An organic pigment may be used in combination. The selection of a light-shielding component containing these carbon black as an essential component needs to be carried out in consideration of the insulating property, the heat resistance, the light resistance, the solvent resistance, etc. In some cases, the combination of the light-shielding components can be selected so that black can be achromatic .

Examples of the solvent for the component (E) include a solvent selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, Butanol and diacetone alcohol, terpenes such as? - or? -Terpineol, ketones such as acetone, methyl ethyl ketone, cyclohexanone and N-methyl-2-pyrrolidone , Aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, cellosolve, methylcellosolve, ethylcellosolve, carbitol, methylcarbitol, ethylcarbitol, butylcarbitol, propyleneglycol monomethylether, propylene glycol Glycol ethers such as glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether and triethylene glycol monoethyl ether, ethers such as ethyl acetate, butyl acetate, Methyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, butyl cellosolve acetate, butyl cellosolve acetate, butyl cellosolve acetate, Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and the like, and they may be dissolved and mixed to prepare a homogeneous solution-like composition. Two or more kinds of these solvents may be used in order to make them necessary characteristics such as coating properties.

The light-shielding component containing these insulating carbon black as an essential component is preferably dispersed in a solvent (F) together with a dispersing agent in advance to prepare a carbon black dispersion, and then blended as 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 component (E). For example, propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate are preferable Lt; / RTI > The blending ratio of the insulating carbon black (D) for forming the carbon black dispersion is preferably in the range of 5 to 60 mass% with respect to the total solid content of the photosensitive resin composition for a light-shielding film of the present invention. Further, the solid content means a component excluding the component (E) in the composition. The solid content also includes a component (B) which becomes a solid content after photo-curing. If it is less than 5% by mass, the desired light shielding property can not be set. When the amount exceeds 60% by mass, the content of the photosensitive resin to be an original binder is decreased, which causes an undesirable problem of deteriorating the developing property and deteriorating the film forming ability.

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

As the dispersing agent (F), known dispersing agents such as various polymer dispersing agents can be used. Examples of the dispersing agent include known compounds (dispersing agents, dispersing wetting agents, dispersion promoting agents and the like, which are commercially available under the name of dispersion accelerators, etc.) conventionally used for pigment dispersion, without any particular limitation. For example, cationic polymer dispersing agents, Anionic polymer dispersant, a nonionic polymer dispersant, and a pigment derivative dispersant (dispersion auxiliary agent). Particularly, it is preferable to use a compound having cationic functional groups such as an imidazolyl group, a pyrrolyl group, a pyridyl group, a primary, secondary or tertiary amino group, an amine value of 1 to 100 mgKOH / g, A cationic high-molecular dispersant having an average molecular weight in the range of 1,000 to 100,000 is preferable. The blending amount of the dispersant is preferably 1 to 30% by mass, and more preferably 2 to 25% by mass, based on the light-shielding component containing the insulating carbon black as an essential component.

When preparing a photosensitive resin composition for a light-shielding film by covariance a part of the alkali-soluble resin containing a polymerizable unsaturated group of the component (A) in addition to the above-mentioned dispersant in preparing a carbon black dispersion, It is possible to obtain a photosensitive resin composition which is easy to form, has good adhesion at the time of development, and does not cause a problem of residues. The blending amount of the component (A) is preferably 2 to 20% by mass, more preferably 5 to 15% by mass in the carbon black dispersion. When the content of the component (A) is less than 2% by mass, it is impossible to obtain a covalent effect such as improvement in sensitivity, improvement in adhesion, and reduction in residues. When the content of the light-shielding component containing the insulating carbon black as an essential component is large, the viscosity of the carbon black dispersion is high, and it becomes difficult to uniformly disperse it, or it takes a very long time, It becomes difficult to obtain a photosensitive resin composition for obtaining a coating film in which insulating carbon black is dispersed.

The carbon black dispersion thus obtained is obtained by mixing the component (A) (the component (A)), the component (B), the component (C) and the remainder (E) component of the photosensitive resin composition for a light-shielding film.

In the photosensitive resin composition of the present invention, additives such as a curing accelerator, a thermal polymerization inhibitor and an antioxidant, a plasticizer, a filler, a leveling agent, a defoaming agent, a coupling agent, and a surfactant may be added as necessary. As the thermal polymerization inhibitor and the antioxidant, hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butyl catechol, phenothiazine, hindered phenol compounds and the like can be mentioned. As plasticizers, dibutyl phthalate Silica, mica, and alumina. Examples of leveling agents and defoaming agents include silicone-based, fluorine-based, and acrylic-based compounds. . Examples of the coupling agent include 3- (glycidyloxy) propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltriethoxy And silane coupling agents such as silane. Examples of the surfactant include a fluorine-based surfactant and a silicon-based surfactant.

The photosensitive resin composition of the present invention may be used in combination with other resin components which are polymerized or cured by heat. As the other resin component, (G) an epoxy resin or epoxy compound having two or more epoxy groups is preferable, and 3,3 ', 5,5'-tetramethyl-4,4'-biphenol type epoxy resin, bisphenol Epoxy resin, epoxy resin, epoxy resin, epoxy resin, epoxy resin, epoxy resin, epoxy resin, epoxy resin, epoxy resin, epoxy resin, 1,2-epoxy-4- (2-oxylenyl) cyclohexane adduct of 1-butanol, and epoxy silicone resin. As these additional components, only one kind of compound may be used, or a plurality of these may be used in combination.

The photosensitive resin composition of the present invention contains the above components (A) to (E) as main components. It is preferable that the above solid components contain the components (A) to (D) in a total amount of 70 mass%, preferably 80 mass% or more. The amount of the (E) solvent varies depending on the target viscosity, but it is preferable that the amount of the (E) solvent is contained in the photosensitive resin composition in the range of 60 to 90 mass%. (Mass%) of (G) / {(A) + (B) + (G)} is preferably 5 to 30%, more preferably 10 to 20% desirable.

In the photosensitive resin composition of the present invention, the hardness of the cured film of the composition excluding the insulating carbon black (component D), which is a light shielding component, is set to a certain level or more. The film forming conditions of the cured film for measuring the hardness are the light curing condition and the heat curing condition used when a desired pattern is obtained by using the photosensitive resin composition of the present invention. For example, a composition for hardness measurement comprising the components (A) to (C) and (E) is spin-coated on a glass substrate by a spinner and heated and dried at a temperature of 60 to 110 ° C for 1 to 3 minutes, A curing film for hardness measurement is prepared by using a light exposure apparatus equipped with a mercury lamp to perform exposure of a predetermined amount without interposing a photomask and further thermally curing at 180 to 250 DEG C for 20 to 60 minutes. When the pencil hardness of the cured film is measured, it is preferable that a cured film having pencil hardness of at least HB is obtained. (A) to (C), more preferably (G) epoxy resin or an additive such as an epoxy compound or a curing accelerator so as to have a pencil hardness of H or more, so that the photosensitive resin composition of the present invention good. If the pencil hardness is less than HB, there is a possibility that troubles such as insufficient recovery of elasticity in mechanical properties as a spacer may occur. Particularly, when the content of the light-shielding component such as carbon black is small, the influence may be considerably increased.

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

In order to make the hardness of the cured film hard, it is necessary to crosslink the molecules of the polymerizable unsaturated group-containing alkali-soluble resin (component (A)) formed at the time of photo-curing and to prevent crosslinking between the component (A) and the polymerizable monomer It is necessary to design the selection of the component (A) and the selection and blending ratio of the component (B) so that the cross-linking of the component (B) becomes a certain amount or more. When the molecular weight of the component (A) becomes large and the content of the polymerizable unsaturated group in one molecule becomes small, it becomes difficult to increase the amount of crosslinking. If the molecular weight of the component (A) is too large, even if the content of the polymerizable unsaturated group in one molecule is large, there is a tendency that it is difficult to increase the amount of crosslinking between the components (A) and the components (A) and (B) There is a need to consider. In addition, it is difficult to increase the amount of crosslinking unless the number of the polymerizable unsaturated group of the component (B) is 3 or more. Since the physical properties of the cured product are influenced by the structure of the alkali-soluble resin and the structure of the polymerizable monomer, the components (A) and (B) are selected and blended together in consideration of these points.

The photosensitive resin composition for a light-shielding film in the present invention is excellent as a photosensitive resin composition for forming, for example, a light-shielding film having a spacer function. As a method of forming a light-shielding film having a spacer function, there is a photolithography method as described below. First, a photosensitive resin composition for a light-shielding film in the present invention is coated on a substrate, and then the solvent is dried (pre-baked). Then, a photomask is placed on the thus obtained coating film, Followed by development to dissolve the unexposed portion using an aqueous alkali solution to form a pattern, and further post-baking (thermo-plasticizing) as post-drying.

The substrate may be a transparent substrate or may be a substrate other than a transparent substrate such as an alignment film formed on a planarizing film or on a pixel flat film on a pixel or a pixel after forming pixels such as RGB. The formation of a light-shielding film having a spacer function on any substrate depends on the design of the liquid crystal display device.

As the transparent substrate to which the photosensitive resin composition is applied, a transparent electrode such as ITO or gold is deposited or patterned on a transparent substrate (for example, polycarbonate, polyethylene terephthalate, polyethersulfone, etc.) Can be exemplified. As a method of applying the solution of the photosensitive resin composition on the transparent substrate, any known method such as a roller coating method, a land coater method, a method using a slit coater or a spinner can be used in addition to the known solution immersion method and spraying method have. By these methods, a coating is formed by applying the coating to a desired thickness and then removing (prebaking) the solvent. Prebaking is performed by heating with an oven, a hot plate or the like. The heating temperature and the heating time in the prebaking are appropriately selected according to the solvent to be used and are, for example, carried out at a temperature of 60 to 110 ° C for 1 to 3 minutes.

Exposure performed after pre-baking is performed by an ultraviolet ray exposure apparatus, and exposure through a photomask exposes only the resist corresponding to the pattern. The exposure apparatus and its exposure conditions are appropriately selected and exposure is performed using a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp or deep ultraviolet rays to cure the photosensitive resin composition in the coating film.

The alkali development after the exposure is performed for the purpose of removing the resist of the unexposed portion, and a desired pattern is formed by this development. Examples of the developer suitable for the alkali development include an aqueous solution of a carbonate of an alkali metal or an alkaline earth metal, an aqueous solution of an alkali metal hydroxide, and the like. Particularly, a carbonate such as sodium carbonate, potassium carbonate, %, Preferably at 23 to 28 DEG C, and a fine image can be precisely formed using a commercially available developing device or an ultrasonic washing machine.

After the development, heat treatment (post-baking) is preferably performed at a temperature of 180 to 250 占 폚 and for 20 to 60 minutes. This post-baking is performed for the purpose of enhancing adhesion between the patterned light-shielding film and the substrate. This is done by heating with an oven, hot plate or the like as in the case of pre-bake. The patterned light-shielding film of the present invention is formed through each step of the above photolithography method.

According to this method, a light-shielding film having an optical density OD of 0.5 / 탆 to 4 / 탆, preferably 1.5 / 탆 to 2.5 / 탆 can be formed. According to the above method, a light-shielding film having a volume resistivity of at least 1 x 10 ⁹ ? Cm, preferably at least 1 x 10 ¹² ? Cm at a voltage of 10 V can be formed. According to the above method, a light-shielding film having a dielectric constant of 2 to 10, preferably 2 to 8 can be formed. According to the above method, in the mechanical property test, a light-shielding film having a breaking strength of 200 mN or more and / or an elastic recovery rate of 30% or more and / or a compression ratio of 40% or less can be formed. The light-shielding film formed by the above method can be used as a column spacer of a liquid crystal display device, and preferably as a black column spacer.

According to the above method, when H2 is 1 to 7 占 퐉, with respect to the film thickness H1 for making the optical density as the light-shielding film 0.5 / 占 퐉 or more and 4 / 占 퐉 or less and the film thickness H2 of the light- It is possible to simultaneously form the light-shielding film having the film thickness H1 and the light-shielding film having the film thickness H2, in which DELTA H = H2 - H1 is 0.1 to 6.9. A more preferable range is an optical density of 0.5 / 占 퐉 to 3 / 占 퐉 as a light shielding film, H2 is 2 to 5 占 퐉, and? H is 0.1 to 2.9. More preferably, the optical density as a light-shielding film is from 0.5 / 탆 to 2 / 탆, H2 is from 2 to 4 탆, and H is from 1.0 to 2.0. The cured film formed by the above method can be used as a column spacer of a liquid crystal display device, preferably as a black column spacer. According to the cured film having the above-mentioned range of DELTA H, the black column spacer having a height difference can be formed from the same material at one time, so that the manufacture of the liquid crystal display device can be performed more efficiently. At this time, for example, a cured film having a film thickness H2 may function as a spacer, and a cured film having a film thickness H1 may function as a black matrix. The height H2 of the spacer and the thickness H1 of the light shielding film are determined by appropriate designing of the two substrates sandwiching the liquid crystal layer, and the appropriate range of H1, i.e., DELTA H, is determined in accordance with the value of H2.

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

The liquid crystal display device having the light-shielding film or the cured film has a high light-shielding property and insulation property, and further has a spacer function excellent in the elastic modulus, deformation amount and elastic recovery rate, and forms a fine spacer shape even if the film thickness is about 1 to 7 탆 can do.

[Example]

Hereinafter, embodiments of the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited thereto.

First, synthesis examples of the (A) alkali-soluble resin containing a polymerizable unsaturated group of the present invention are shown. Evaluation of the resin in the synthesis example was carried out as follows.

[Solid content concentration]

1 g of the obtained resin solution in the synthesis example was impregnated into a glass filter (weight: W0 (g)), weighed, and weight [W2 (g)] after heating at 160 DEG C for 2 hours Respectively.

Solid content concentration (% by weight) = 100 x (W2 - W0) / (W1 - W0).

[Mountain]

The resin solution was dissolved in dioxane and titrated with a 1/10 N-KOH aqueous solution using a potentiometric titration apparatus (manufactured by Hiranuma Industrial Co., Ltd., trade name: COM-1600).

[Molecular Weight]

(1) + TSKgelSuperH-4000 (1) + TSKgelSuperH-2000 (2) + TSKgelSuperH-3000 (1) + gel permeation chromatography (GPC) [trade name: HLC-8220GPC, solvent: tetrahydrofuran, (Mw) in terms of standard polystyrene (PS-oligomer kit, manufactured by TOSOH CORPORATION) was measured, and the molecular weight was measured using a spectrophotometer (manufactured by Tosoh Co., Ltd., temperature: 40 占 폚, speed: 0.6 ml / Respectively.

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

BPFE: Reaction product of 9,9-bis (4-hydroxyphenyl) fluorene and chloromethyloxirane. In the compound of formula (I), X is fluorene-9,9-diyl, and R ₁ and R ₂ are hydrogen.

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

BTDA: 3,3 ', 4,4'-benzophenone tetracarboxylic acid 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 of PGMEA were charged into a 1 L four-necked flask equipped with a reflux condenser and stirred for 12 hours under heating at 100 to 105 캜, The reaction product was obtained.

Subsequently, 33.8 g (0.12 mol) of BPDA and 17.5 g (0.12 mol) of THPA were introduced into the obtained reaction product and stirred for 6 hours under heating at 115 to 120 ° C to obtain a polymerizable unsaturated group-containing alkali-soluble resin solution (A) 1. The solid 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]

(0.60 mol) of methacrylic acid, 38.44 g (0.38 mol) of methyl methacrylate, and 38.77 g (0.22 mol) of benzyl methacrylate were placed in a 1000 ml four-necked flask equipped with a reflux condenser, 5.91 g of nitrile and 370 g of diethylene glycol dimethyl ether were charged and polymerized by stirring at 80 to 85 캜 in a nitrogen stream for 8 hours. 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 charged in the flask and stirred at 80 to 85 ° C for 16 hours, An alkali-soluble resin solution (A) -2 was obtained. The solid concentration of the obtained resin solution was 32 mass%, the acid value (in terms of solid content) was 110 mgKOH / g, and the Mw by GPC analysis was 18100.

(Polymerizable unsaturated group-containing alkali-soluble resin)

(A) -1 Component: The alkali-soluble resin solution obtained in Synthesis Example 1

(A) -2 Component: The alkali-soluble resin solution obtained in Comparative Synthesis Example 1

(Photopolymerizable monomer)

(B): A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (DPHA, manufactured by Nippon Yakusho Co., Ltd.)

(Photopolymerization initiator)

(C): ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol- Cure OXE02)

(Carbon black dispersion)

(D) -1: resin-coated PGMEA dispersion (solid content 30.0%) having a carbon black concentration of 25.0 mass% and a dispersant concentration of 5.0 mass%

(D) -2: 20% by mass of carbon black, 5.0% by mass of a polymeric dispersant, 25% by mass of a PGMEA dispersion,

(solvent)

(E) -1: PGMEA

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

(Epoxy resin)

(G): 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol ("EHPE3150"

(Silane coupling agent)

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

(Surfactants)

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

[Evaluation on Components of Composition]

≪ Preparation of Composition for Evaluating Characteristic of Carbon Black &

A resin solution (component (A) -1), a carbon black dispersion (component (D) -1 component or component (D) -2 component) and a solvent (component (E) -1 component) were mixed so as to have a solid content concentration of 20% To prepare a composition for measuring carbon black. A composition capable of forming a cured film of OD = 4 / 占 퐉 was prepared by adjusting the carbon black concentration while measuring the optical density (OD). The composition used for the measurement of the surface resistivity is shown in Table 1.

<Optical Concentration>

The composition for measuring carbon black obtained above was applied on a glass substrate having a thickness of 1.2 mm so as to have a thickness of 1.1 占 퐉 after thermal curing treatment using a spin coater and prebaked at 90 占 폚 for 1 minute. Thereafter, the film was heated and cured at 230 DEG C for 30 minutes using a hot-air dryer to obtain a cured film of the composition. Next, the optical density of the obtained cured film was measured using a Macbeth permeation densitometer, and the optical density per unit film thickness was evaluated.

&Lt; Measurement of surface resistivity &

The surface resistivity of the cured film obtained by measuring the optical density was measured at a voltage of 10 V using a surface resistivity meter (Hiresta UP manufactured by Mitsubishi Chemical Corporation). The measurement results are shown in Table 1.

&Lt; Preparation of composition for evaluating properties of photo-curing component &gt;

Curable component (C) shown in Table 2 was prepared using the resin solution (component (A) -1), the photopolymerizable monomer (component (B)), the photopolymerization initiator Was prepared. &Lt; tb &gt; &lt; TABLE &gt;

&Lt; Measurement of pencil hardness &

Each of the photosensitive resin compositions obtained above was coated on a glass substrate having a thickness of 1.2 mm so as to have a film thickness of 1.2 탆 after thermal curing treatment using a spin coater and prebaked at 90 캜 for 1 minute. Thereafter, a photo-curing reaction was carried out by irradiating ultraviolet rays of 100 mJ / cm 2 with an ultrahigh-pressure mercury lamp of 30 mW / cm 2 in wavelength and 365 nm in wavelength without a photomask. Thereafter, a heat curing treatment was performed at 230 캜 for 30 minutes using a hot-air dryer to obtain a cured film of a photo-curing component.

The highest hardness of the cured film, which did not cause scratches on the coating film when a load of 500 g was applied using a pencil hardness tester in accordance with JIS-K5400 test method, was measured. The pencil used is "Mitsubishi High Uni".

The evaluation of the photosensitive resin composition having the spacer function was carried out by preparing the photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 to 3 by blending the above-mentioned blending components in the ratios shown in Table 3. The numerical values in Table 3 indicate the parts by mass. (E) -1 in the column of the solvent is the same as PGMEA ((E) -1) in the unsaturated group-containing resin solution (polymerizable unsaturated group-containing alkali-soluble resin solution) and PGMEA E) Same as -1).

[Evaluation of composition for light-shielding film]

Using the photosensitive resin compositions for the light-shielding films of Examples 1 to 5 and Comparative Examples 1 to 3, evaluation described below was carried out. The evaluation results are shown in Table 4.

<Development Characteristic>

Each of the photosensitive resin compositions obtained above was applied onto a glass substrate having a thickness of 1.2 mm using a spin coater to a thickness of 3.0 占 퐉 after the heat curing treatment (Examples 1, 2, 4 and Comparative Example 3) or 1.5 占 퐉 3 and 5 and Comparative Examples 1 and 2), and prebaked at 90 ° C for 1 minute. Thereafter, the photomask was closely contacted, and ultraviolet rays of 100 mJ / cm &lt; 2 &gt; were irradiated with an ultrahigh pressure mercury lamp of 30 mW / cm 2 in wavelength and 365 nm in wavelength to perform photo-curing reaction of the photosensitive portion.

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

Fine 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 4.

?: A pattern having an L / S of 10 占 퐉 / 10 占 퐉 or more formed without residue

?: A pattern having L / S of 30 占 퐉 / 30 占 퐉 or more was formed without residue

X: A pattern in which L / S is less than 50 占 퐉 / 50 占 퐉 is not formed, or a pattern collapse or residue is prominent

&Lt; Volume resistivity &

Each of the photosensitive resin compositions obtained above was applied to a portion of the Cr-deposited glass substrate having a thickness of 1.2 mm except for the electrodes using a spin coater so as to have a film thickness after the heat curing treatment of 3.5 占 퐉 and prebaked at 90 占 폚 for 1 minute Respectively. Thereafter, a heat curing treatment was performed at 230 캜 for 30 minutes using a hot-air dryer to obtain a cured film of the photosensitive resin composition. Thereafter, an aluminum electrode was formed on the cured film to prepare a substrate for measuring the volume resistivity. Next, the volume resistivity at an applied voltage of 1 V to 10 V was measured using an electrometer ("Model 6517A" manufactured by Kesley Co., Ltd.). The voltage was measured under the conditions of maintaining the voltage for 60 seconds at each applied voltage in 1 V step, and the volume resistivity at the time of applying 10 V is shown in Table 4.

<Permittivity>

Each of the photosensitive resin compositions obtained above was applied to a portion of the Cr-deposited glass substrate having a thickness of 1.2 mm except for the electrodes using a spin coater so as to have a film thickness of 3.5 mu m after the heat curing treatment and prebaked at 90 DEG C for 1 minute Respectively. Thereafter, a heat curing treatment was performed at 230 캜 for 30 minutes using a hot-air dryer to obtain a cured film of the photosensitive resin composition. Thereafter, an aluminum electrode was formed on the cured film to prepare a substrate for dielectric constant measurement. Next, the electric capacity at a frequency of 1 Hz to 100000 Hz was measured using an electrometer ("6517 Type A" manufactured by Keisukei Co., Ltd.), and the dielectric constant was calculated from the electric capacity. The calculated dielectric constants are shown in Table 4.

&Lt; Halftone (HT) characteristics of spacers &gt;

Each of the photosensitive resin compositions obtained above was applied onto a glass substrate having a thickness of 1.2 mm using a spin coater to a thickness of 3.0 占 퐉 after the heat curing treatment (Examples 1, 2, 4 and Comparative Example 3) or 1.5 占 퐉 3 and 5 and Comparative Examples 1 and 2), and prebaked at 90 ° C for 1 minute. Thereafter, a photomask having a dot pattern was closely contacted, and ultraviolet light of 5 mJ / cm 2 or 100 mJ / cm 2 was irradiated with an ultrahigh pressure mercury lamp of 30 mW / cm 2 in wavelength and 365 nm in wavelength, Respectively.

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

The halftone characteristic of the spacer is calculated by calculating the difference between the film thickness H1 of the light-shielding film at the exposure amount of 5 mJ / cm2 and the film thickness H2 of the spacer at 100 mJ / Respectively. The results are shown in Table 4.

?: When? H is 1.0 占 퐉 to 2.0 占 퐉

Δ: When ΔH is 0.1 μm to 2.9 μm

X: when? H is less than 0.1 占 퐉 or greater than 2.9 占 퐉

&Lt; Compressibility of spacer, elastic recovery rate, fracture strength &gt;

Each of the photosensitive resin compositions obtained above was coated on a glass substrate having a thickness of 1.2 mm so as to have a film thickness after the heat curing treatment of 3.0 占 퐉 using a spin coater and prebaked at 90 占 폚 for 1 minute. Thereafter, a photomask having a dot pattern was closely adhered, and ultraviolet light of 100 mJ / cm 2 was irradiated with an ultrahigh-pressure mercury lamp of 30 mW / cm 2 in wavelength and 365 nm in wavelength to perform photo-curing reaction of the photosensitive portion.

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

The spacer characteristics of the obtained cured film pattern were evaluated using a micro-hardness tester (Fisher Scope HM2000Xyp, manufactured by Fisher Instruments). A load of 50 mN / sec and a load of 5.0 mN / sec were applied, and a displacement curve was prepared.

The compression ratio was calculated from the following equation, assuming that the displacement at a load of 50 mN under load is L1.

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

The elastic recovery rate was calculated from the following equation, assuming that the displacement amount at load 50 mN at the time of loading is L1 and the displacement amount of the damper is L2.

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

The fracture strength was evaluated using a micro-hardness tester (Fisher Scope HM2000Xyp, manufactured by Fisher Instruments). A load was applied to a load of 300 mN under a load of 5.0 mN / sec and a load of 300 mN was applied to measure the load when the spacer was broken. The results are shown in Table 4.

○: When the breaking strength is 300 mN or more

?: When the breaking strength is less than 200 mN and less than 300 mN

X: When the breaking strength is less than 100 mN and less than 200 mN

<Shape of Spacer>

Each of the photosensitive resin compositions obtained above was coated on a glass substrate having a thickness of 1.2 mm so as to have a film thickness after the heat curing treatment of 3.0 占 퐉 using a spin coater and prebaked at 90 占 폚 for 1 minute. Thereafter, a photomask having a dot pattern was closely adhered, and ultraviolet light of 100 mJ / cm 2 was irradiated with an ultrahigh-pressure mercury lamp of 30 mW / cm 2 in wavelength and 365 nm in wavelength to perform photo-curing reaction of the photosensitive portion.

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

The shape of the spacer was evaluated by an internal angle (taper angle) of the spacer end using a scanning electron microscope. ? When the taper angle was 70 占 or more and 90 占 or less,? When the taper angle was less than 50 占 and less than 70 占,? When the taper angle was 50 占 or less and 占 when the taper angle was 90 占 or more.

It can be seen from the results of Examples 1 to 5 and Comparative Examples 1 to 3 that by setting the hardness of the cured film excluding the component (D) to HB or higher by using the insulating carbon black (D), the light shielding property, And the spacer properties such as elastic recovery rate can be improved.

Claims (11)

A photosensitive resin composition for a light-shielding film having a spacer function, which comprises the 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) a light shielding component containing an insulating carbon black having a surface resistivity of 1 x 10 &lt; ⁸ &gt; [Omega] / square or more of a film formed so as to have an optical density of 4 /
(E) a solvent,
Wherein the cured product of the composition excluding the component (D) has a pencil hardness of at least HB. The method according to claim 1,
(B) in an amount of 5 to 400 parts by mass based on 100 parts by mass of the component (A)
(C) is contained in an amount of 0.1 to 40 parts by mass based on 100 parts by mass of the total amount of the components (A) and (B), and the component (B) , &Lt; / RTI &
(D) in an amount of 5 to 60% by mass,
Respectively. 3. The method according to claim 1 or 2,
Sensitive resin composition comprising a polymerizable unsaturated group-containing alkali-soluble resin represented by the general formula (II) is used as the component (A).
[Chemical Formula 1]

Wherein 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, , -SO ₂ -, -C (CF ₃ ) ₂ -, -Si (CH ₃ ) ₂ -, -CH ₂ -, -C (CH ₃ ) ₂ -, -O-, fluorene- Y represents a tetravalent carboxylic acid residue, and each Z independently represents a hydrogen atom or -OC-W- (COOH) ₁ (wherein W represents a divalent or trivalent carboxylic acid residue And l represents a number of 1 to 2), and n represents a number of 1 to 20. 4. The method according to any one of claims 1 to 3,
Shielding film having an optical density OD of 0.5 / 탆 or more and 4 / 탆 or less can be formed as a light-shielding film having a volume resistivity of 1 × 10 ⁹ Ω · cm or more and a dielectric constant of 2 to 10 when a voltage of 10 V is applied Sensitive resin composition. 5. The method according to any one of claims 1 to 4,
Wherein a light-shielding film satisfying at least one of the following (i) - (iii) can be formed in a load-unloading test by a micro-hardness meter.
(i) the compression rate is 40% or less
(Ii) Resilience rate of 30% or more
(Iii) a fracture strength of not less than 200 mN A light-shielding film having a spacer function, which is formed by curing the photosensitive resin composition according to any one of claims 1 to 5. A liquid crystal display device having the light-shielding film according to claim 6 as a black column spacer (BCS). 8. The method of claim 7,
Further comprising a thin film transistor (TFT). A process for producing a light-shielding film formed on a substrate, which comprises applying the photosensitive resin composition according to any one of claims 1 to 5 to a substrate and curing the photosensitive resin composition by light irradiation, H2-H1 is 0.1 to 6.9 when H2 is 1 to 7 占 퐉, with respect to the film thickness H1 for setting the thickness of the light-shielding film to 0.5 / 탆 or more and 4 / 占 퐉 or less and the film thickness H2 of the light- Shielding film having a thickness H1 and a thickness H2 is formed at the same time. A method for manufacturing a liquid crystal display device, characterized in that the light-shielding film produced by the method according to claim 9 is a black column spacer. 11. The method of claim 10,
Wherein the liquid crystal display device has a thin film transistor (TFT).