KR20170113390A - Photosensitive resin composition for light-shielding film, display substrate having the light-shielding film obtained by curing the same, and manufacturing method of display substrate - Google Patents

Abstract

(PROBLEMS) A photosensitive resin composition for a light-shielding film which is suitable for forming a light-shielding film on a plastic substrate having a heat resistance of only 160 DEG C and excellent in solvent resistance and alkali resistance, a substrate for display provided with a light- And a method for producing the same.
(A) a polymerizable unsaturated group-containing alkali-soluble resin having a structure of an epoxy (meth) acrylate acid adduct, (B) a photopolymerizable monomer having at least three ethylenically unsaturated bonds, (C) A photosensitive resin composition for a light-shielding film comprising at least one light-shielding component selected from the group consisting of a polymerization initiator, (D) an azo-based polymerization initiator, and (E) a black organic pigment, A light shielding film having a predetermined pattern is formed by heating at 160 DEG C or lower through a photomask, and a display substrate obtained by the method.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition for a light-shielding film, a substrate for a display having a light-shielding film formed by curing the light-shielding film, and a method of manufacturing a substrate for a display. BACKGROUND ART METHOD OF DISPLAY SUBSTRATE}

The present invention relates to a photosensitive resin composition for a light-shielding film, a display substrate provided with a light-shielding film obtained by curing the light-shielding film, and a method of manufacturing a display substrate. More particularly, A light-shielding film, a display substrate provided with a light-shielding film as a cured film thereof, and a method of manufacturing the display substrate.

In recent years, for the purpose of making the device flexible or one-chip, a light-shielding film (light-shielding pattern) is formed directly on a plastic substrate (plastic film or resin film) such as PET (polyethylene terephthalate) or PEN (polyethylene naphthalate) Or to form a light-shielding film directly on a glass substrate or a device provided with an organic EL or an organic TFT on a silicon wafer. However, these have a low heat resistance temperature as a plastic substrate itself or a heat resistance temperature as a device, and generally have a heat resistance of only about 160 占 폚 in many cases. Therefore, when the light-shielding film is formed on a plastic substrate or a device, the film strength becomes insufficient at a temperature of 160 ° C or lower and the film strength becomes insufficient. In the subsequent post-process (for example, each RGB resist coating or alkali resistance) , Surface roughness, pattern peeling, and the like.

Thus, for example, in JP-A 2003-15288 (Patent Document 1), a photosensitive resin composition containing a thermal polymerization initiator is added to a photopolymerization initiator based on an alkali-soluble resin of an acrylic copolymer as a base, (Peel test) with respect to the residue and the substrate is ensured. However, it is also possible to provide a substrate having a pattern line width, a developing margin, a reliability (solvent resistance, alkali resistance), etc. These are not enough yet.

Japanese Patent Application Laid-Open No. 2003-15288

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object of the present invention is to provide a plastic substrate or a device having a heat resistance of only 160 캜, which is suitable for forming a light- A photosensitive resin composition for a light-shielding film which can obtain a light-shielding film excellent in alkali resistance. The present invention also provides a substrate for a display having a light-shielding film formed by curing a photosensitive resin composition for a light-shielding film, and a method of manufacturing the same.

Therefore, the inventors of the present invention have made intensive studies on a photosensitive resin composition for a light-shielding film which can obtain a light-shielding film excellent in solvent resistance and alkali resistance while obtaining good developing adhesion and linearity of pattern by thermal curing at 160 캜 or less. Containing polymerizable unsaturated group-containing alkali-soluble resin, a photopolymerizable monomer, a light-shielding component, and a solvent, and by combining two kinds of specific polymerization initiators, the present inventors have accomplished the present invention.

That is, the gist of the present invention is as follows.

(1) the following components (A) to (E)

(A) an alkali-soluble resin containing a polymerizable unsaturated group having a structure of an epoxy (meth) acrylate acid adduct,

(B) a photopolymerizable monomer having at least three ethylenically unsaturated bonds,

(C) an oxime ester-based polymerization initiator,

(D) an azo-based polymerization initiator, and

(E) at least one light-shielding component selected from the group consisting of a black organic pigment, a mixed-color organic pigment, and a light-

Is contained as an essential component in the photosensitive resin composition for a light-shielding film.

(2) The photosensitive resin composition for a light-shielding film according to (1), wherein the polymerizable unsaturated group-containing alkali-soluble resin as the component (A) is represented by the following formula (II).

Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R ₅ is a hydrogen atom or a methyl group, A is -CO -, -SO ₂ -, -C (CF ₃ ) ₂ -, -Si (CH ₃ ) ₂ -, -CH ₂ -, -C (CH ₃ ) ₂ -, -O-, represents a bond or a straight-diyl group, X represents a tetravalent carboxylic acid moiety represents a, Y ₁ and Y ₂ are each independently a hydrogen atom or a -OC-Z- (COOH) _m (end, Z is a divalent or trivalent And m represents a number of 1 or 2), and n represents an integer of 1 to 20,

(3) The positive resist composition according to item (1) or (2), wherein the mass ratio (A) / (B) of the component (A) to the component (B) is 50/50 to 90/10, (C) is 2 to 30 parts by mass, and the component (D) is 1 to 20 parts by mass with respect to 100 parts by mass of the total of 100 parts by mass of the photosensitive resin composition for a light- And the component (E) is contained in an amount of 40 to 70 mass% in the contained solid content.

(4) The photosensitive resin composition for a light-shielding film according to any one of (1) to (3), wherein the component (E) is carbon black.

(5) A substrate for a display having a light-shielding film on a substrate having a heat-resistant temperature of 160 ° C or less, wherein the light-

(A) an alkali-soluble resin containing a polymerizable unsaturated group having a structure of an epoxy (meth) acrylate acid adduct,

(B) a photopolymerizable monomer having at least three ethylenically unsaturated bonds,

(C) an oxime ester-based polymerization initiator,

(D) an azo-based polymerization initiator, and

(E) at least one light-shielding component selected from the group consisting of a black organic pigment, a mixed-color organic pigment, and a light-

Wherein the photosensitive resin composition for a light-shielding film is cured.

(6) A method for producing a display substrate having a light-shielding film on a substrate having a heat-resistant temperature of 160 DEG C or less,

The following components (A) to (E)

(A) an alkali-soluble resin containing a polymerizable unsaturated group having a structure of an epoxy (meth) acrylate acid adduct,

(B) a photopolymerizable monomer having at least three ethylenically unsaturated bonds,

(C) an oxime ester-based polymerization initiator,

(D) an azo-based polymerization initiator, and

(E) at least one light-shielding component selected from the group consisting of a black organic pigment, a mixed-color organic pigment, and a light-

A light-shielding film having a predetermined pattern is formed by heating at 160 DEG C or lower to form a light-shielding film having a predetermined pattern, Wherein the first substrate and the second substrate are bonded to each other.

(Effects of the Invention)

The photosensitive resin composition for a light-shielding film of the present invention is excellent in developing adhesion and linearity at a line width of 5 to 15 mu m, particularly 10 mu m or less, even if it does not include a step of thermosetting at a temperature exceeding 160 DEG C in the process for producing a light- And a light shielding film (light shielding pattern) having good solvent resistance can be formed. Therefore, a light-shielding film can be formed on a film made of a resin such as PET or PEN having a heat-resistant temperature of 160 ° C or lower, or on a device including an organic EL or organic TFT formed on a glass substrate or a silicon wafer, A display substrate having a light-shielding film having the same characteristics can be obtained.

That is, as in the present invention, a polymerizable unsaturated group-containing alkali-soluble resin having a specific structure, a polymerizable monomer having at least three ethylenically unsaturated groups, an oxime ester-based polymerization initiator, an azo-based polymerization initiator, By using the resin composition, a desired light-shielding film can be formed on a substrate having a low heat resistance such that the heat-resistant temperature is not higher than 160 DEG C, and a display substrate having various functions can be obtained.

Hereinafter, the present invention will be described in detail.

Each component of the photosensitive resin composition for a light-shielding film of the present invention will be described first.

The polymerizable unsaturated group-containing alkali-soluble resin as the component (A) in the present invention has a structure of an epoxy (meth) acrylate acid adduct, specifically, a compound having two or more epoxy groups and (meth) acrylic acid Acrylic acid and / or methacrylic acid ") is further reacted with a polyvalent carboxylic acid or its anhydride. (A) a dicarboxylic acid or a tricarboxylic acid or an acid anhydride thereof, which is obtained by reacting an epoxy compound represented by the following general formula (I) with a (meth) acrylic acid to give a compound having a hydroxy group, (B) an epoxy (meth) acrylate acid adduct obtained by reacting a tetracarboxylic acid or its acid dianhydride. The epoxy compound represented by the general formula (I) means an epoxy compound obtained by reacting a bisphenol and an epihalohydrin or an equivalent thereof. Since the component (A) has both a polymerizable unsaturated double bond and a carboxyl group, the photosensitive resin composition gives excellent photo-curability, good developability and patterning property, thereby improving the properties of the light-shielding film.

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, A is -CO-, -SO ₂ -, -C (CF ₃ ) ₂ -, -Si (CH ₃ ) ₂ -, -CH ₂ -, -C (CH ₃ ) ₂ -, -O-, fluorene- And l is an average value of 0 to 10.

Examples of the bisphenols for imparting the epoxy compound of the general formula (I) include bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dichlorophenyl) sulfone, bis Bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3,5-dimethylphenyl) dimethylsilane, bis Bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dibromophenyl) Propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2- (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane, (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl) ether, 9,9- (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9- Fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9,9- 3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene, 9,9- -Dibromophenyl) fluorene, 4,4'-biphenol, 3,3'-biphenol and the like. Among them, bisphenols to which an epoxy compound in which A in the general formula (1) is a fluorene-9,9-diyl group are particularly preferably used.

(I) for deriving the epoxy resin (A) as an alkali-soluble resin is an epoxy compound having two glycidyl ether groups obtained by reacting the bisphenols with epichlorohydrin. In this reaction, an oligomerization of a diglycidyl ether compound is generally carried out, and 1 usually has a mean value of 0 to 10 (which may not be an integer) because a plurality of values are mixed, 0 to 3. When the average value of I exceeds the upper limit value, when the photosensitive resin composition is used as an alkali-soluble resin synthesized using the above-mentioned epoxy compound, the viscosity of the composition becomes excessively large and the application is not performed well or the alkali solubility can not be sufficiently given, The sex is very bad.

The (a) dicarboxylic acid or tricarboxylic acid or an acid anhydride thereof used in the epoxy (meth) acrylate acid adduct may be a chain hydrocarbon dicarboxylic acid or a tricarboxylic acid or an acid anhydride thereof or an alicyclic dicarboxylic acid An acid or a tricarboxylic acid or an acid anhydride thereof, an aromatic dicarboxylic acid or a tricarboxylic acid or an acid anhydride thereof. Examples of the chain hydrocarbon dicarboxylic acid or tricarboxylic acid or acid anhydride thereof include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citrameric acid, malonic acid, glutaric acid There may be mentioned compounds such as acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid and the like or an acid anhydride thereof, and also dicarboxylic acid or tricarboxylic acid Or an acid anhydride thereof. Examples of the alicyclic dicarboxylic acid or tricarboxylic acid or its acid anhydride include cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid, etc. Or an acid anhydride thereof, and may be a dicarboxylic acid or a tricarboxylic acid or an acid anhydride to which an arbitrary substituent has been introduced. Examples of the aromatic dicarboxylic acid or tricarboxylic acid or its acid anhydride include compounds such as phthalic acid, isophthalic acid and trimellitic acid, or acid anhydrides thereof, and also dicarboxylic acids Or a tricarboxylic acid or an acid anhydride thereof.

As the tetracarboxylic acid or its acid dianhydride (b) used in the epoxy (meth) acrylate acid adduct, a chain hydrocarbon tetracarboxylic acid or its acid dianhydride, an alicyclic tetracarboxylic acid or its acid dianhydride , Or an aromatic polycarboxylic acid or an acid dianhydride thereof is used. Here, examples of the chain hydrocarbon tetracarboxylic acid or its acid dianhydride include compounds such as butanetetracarboxylic acid, pentanetetracarboxylic acid, and hexanetetracarboxylic acid, and acid dianhydrides thereof, A tetracarboxylic acid to which a substituent is introduced or an acid anhydride thereof. Examples of the alicyclic tetracarboxylic acid or its acid dianhydride include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid, A tetracarboxylic acid or an acid anhydride thereof, or a compound such as an acid anhydride, a tetracarboxylic acid or an acid anhydride thereof. Examples of the aromatic tetracarboxylic acid and the acid dianhydride include compounds such as pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid and biphenyl ether tetracarboxylic acid, and acid anhydrides thereof And a tetracarboxylic acid or an acid dianhydride to which an arbitrary substituent has been introduced may be used.

(A) / (b) of the dicarboxylic acid or the tricarboxylic acid or an acid anhydride thereof and (b) the tetracarboxylic acid or the acid dianhydride used in the epoxy (meth) Is preferably from 0.01 to 10.0, more preferably from 0.02 to less than 3.0. If the molar ratio (a) / (b) deviates from the above range, it is not preferable because the high molecular weight light-sensitive resin of the present invention has high light resistance and good optical patterning property. Further, the smaller the molar ratio (a) / (b), the larger the molecular weight and the lower the alkali solubility.

The epoxy (meth) acrylate acid adduct can be produced by the above-described process by a known method, for example, a method described in JP-A-8-278629 or JP-A-2008-9401. First, as a method for reacting (meth) acrylic acid with the epoxy compound of the general formula (I), for example, a method in which (meth) acrylic acid equivalent to the epoxy group of the epoxy compound is added in a solvent and a catalyst (triethylbenzylammonium chloride, , 6-diisobutylphenol, etc.), and the mixture is reacted by heating and stirring at 90 to 120 ° C while blowing air. Next, as a method of 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 dianhydride and an acid anhydride is added to a solvent and a catalyst (tetraethylammonium bromide, Pin or the like) at 90 to 130 캜.

The weight average molecular weight (Mw) of the polymerizable unsaturated group-containing alkali-soluble resin (A) is preferably in the range of 2,000 to 10,000, more preferably 3,000 to 7,000. If the weight average molecular weight (Mw) is not 2000, the pattern adhesion during development of the photosensitive resin composition using (A) can not be maintained and pattern peeling occurs. When the weight average molecular weight (Mw) exceeds 10,000, The remaining film of unexposed portion becomes easy to leave. The acid value of (A) is preferably in the range of 80 to 120 mg KOH / g. If this value is less than 80 mgKOH / g, the residue tends to remain in the alkali developing of the photosensitive resin composition using (A), and when it exceeds 120 mgKOH / g, the alkali developer So that the peeling phenomenon occurs, which is not preferable. The alkali-soluble resin containing a polymerizable unsaturated group in (A) may be used alone or as a mixture of two or more thereof.

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) , Pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, glycerol tri (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (Meth) acrylates such as alkyl (meth) acrylate, sorbitol hexa (meth) acrylate, alkylene oxide modified hexa (meth) acrylate of capphalan and caprolactone modified dipentaerythritol hexa Type polyfunctional acrylates, hyperbranched polyfunctional acrylates, and the like can be presented. One kind of or two or more may be used. Further, the photopolymerizable monomer (B) having at least three ethylenically unsaturated bonds does not have an liberated carboxyl group. In the present invention, a photopolymerizable monomer having three or more functional groups is used in order to obtain a sufficient crosslinking density even by heat treatment at 160 DEG C or less.

The mixing ratio of the component (A) and the component (B) is preferably 50/50 to 90/10 in the mass ratio (A) / (B), and more preferably 60/40 to 80/20. When the mixing ratio of the component (A) is less than 50/50 in the case of (A) / (B), the cured product after photocuring is decomposed and the acid value of the coating film in the unexposed portion is low, (A) / (B) is more than 90/10, the ratio of the photoreactive functional groups to the resin is so small that the formation of the crosslinked structure is not sufficient and the resin The acid value of the coating film of the exposed portion due to the component is too high and the solubility in the alkali developing solution in the exposed portion is high, so that the formed pattern becomes thinner than the target line width or a problem that the pattern tends to be lost have.

Examples of the oxime ester polymerization initiator of component (C) include 1,2-octanedione, 1- [4- (phenylthio) phenyl] -, 2- (O-benzoyloxime) 2-oxime-O-benzoate, 1- (4- (methylsulfanyl) phenyl) butane-1,2-dione- -Acetate, 1- [9-ethyl-6- (2-methylbenzoyl) carbazol-3-yl] ethanone = O-acetyloxime, (9-ethyl-6-nitrocarbazol-3-yl) [4- (2-methoxy- 1 -methylethoxy) Phenyl] methyl} -11- (2-ethylhexyl) -11H-benzo [a] carv oxyl ester was obtained in the same manner as in Example 1, except for using 8 - {[(acetyloxy) imino] [2- (2,2,3,3-tetrafluoropropoxy) (2-methylphenyl) (7-nitro-9,9-dipropyl-9H-fluoren-2-yl) -, acetyl oxime, Ethane, 1 - (- 9 (2-methylbenzoyl) -9,9-dipropyl-9H- , 9-dibutyl-7-nitro-9H-fluoren-2-yl) - , 1-O-acetyl oxime, and the like. Two or more of these oxime ester-based polymerization initiators may be used.

The main function of the oxime ester-based polymerization initiator of the component (C) is to initiate photo-radical polymerization. The amount of the oxime ester polymerization initiator used is preferably 2 to 30 parts by mass based on 100 parts by mass of the total of the components (A) and (B) And preferably 5 to 25 parts by mass. When the compounding ratio of the component (C) is less than 2 parts by mass, the speed of photopolymerization slows down and the sensitivity is lowered. On the other hand, when the amount exceeds 30 parts by mass, the sensitivity is too strong and the pattern line width becomes thick relative to the pattern mask, There is a fear that a faithful line width can not be reproduced, or that the pattern edge is milled and not sharpened.

(10 hours half-life temperature (toluene) (hereinafter referred to as " T _1/2 ") 65 캜), 2,2'-azobis (2,4-dimethylvalonitrile _{) (T 1/2 51 ℃} ), dimethyl 2,2'-azobis _{(2-methylpropionate) (T 1/2 6 ℃} ), dimethyl 1,1'-azobis (1-cyclohexanecarboxylic (T _1/2 73 ° C), 1,1'-azobis (cyclohexane-1-carbonitrile) (T _1/2 88 ° C), 1,1'-azobis - there may be mentioned _{phenyl-ethanone) (T 1/2 61 ℃} ), dimethyl 2,2'-azobis isobutyrate (T _1/2 67 ℃) and the like.

The function of the azo-based polymerization initiator as the component (D) mainly improves the thermal radical polymerizability of the photosensitive resin composition, and particularly improves the physical properties of the cured product such as the hardness of the pattern formed by thermal polymerization during post- . Therefore, it is necessary to add an appropriate amount of a suitable half-life time (T _1/2 ) for 10 hours by postbaking conditions or the like. The preferred 10-hour half-life temperature is from 50 to 80 캜, and the amount thereof is preferably from 1 to 20 parts by mass, and preferably from 2 to 15 parts by mass, based on 100 parts by mass of the total of the components (A) and (B) .

The component (E) is a light-shielding component selected from a black organic pigment, a mixed color organic pigment or a light shielding material, and is excellent in heat resistance, light resistance and solvent resistance. Examples of the black organic pigments include perylene black, aniline black, cyanine black, and lactam black. Examples of the color-mixing organic pigments include pigments obtained by mixing two or more pigments selected from red, blue, green, purple, yellow, cyanine, magenta, and the like. Examples of the light shielding material include carbon black, chromium oxide, iron oxide, and titanium black. Two or more kinds of light-shielding components may be appropriately selected and used, but carbon black is particularly preferable in view of good light-shielding properties, surface smoothness, dispersion stability, and compatibility with resins. When carbon black to be used is coated with a dye, a resin or the like, it is suitable for use as a cured product having a high resistance.

Examples of the solvent for the component (F) include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol and propylene glycol, terpenes such as alpha or beta terpineol, Ketones such as ethyl ketone, cyclohexanone and N-methyl-2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, Propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and the like Glycol ethers, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate , Ethyl acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. These solvents may be dissolved and mixed to prepare a composition in a uniform solution state .

The light shielding component of the light shielding film (E) is preferably dispersed in the solvent (F) in advance with the dispersant (G) to form a light shielding dispersion and then mixed as a photosensitive resin composition for a light shielding film. Here, the solvent to be dispersed may be any of those listed in the above component (F), for example, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and the like are suitably used. The compounding ratio of the light-shielding component (E) for forming the light-shielding dispersion is preferably in the range of 40 to 70 mass% with respect to the total solid content of the photosensitive resin composition for a light-shielding film of the present invention, Is particularly preferable. If it is less than 40% by mass, the light shielding property becomes insufficient for high light shielding. When the amount exceeds 70% by mass, the content of the photosensitive resin as an original binder is decreased, which deteriorates the developing property and deteriorates the film forming ability. The entire solid content of the photosensitive resin composition for a light-shielding film also includes a component that becomes a solid component by photo-curing the photosensitive resin composition for a light-shielding film.

For the dispersant (G) to be used, known dispersants such as various polymer dispersants can be used. As a specific example of the dispersing agent, conventionally known compounds (such as a compound which is commercially available under the name of a dispersing agent, a dispersing wetting agent, a dispersing accelerator, etc.) conventionally used for pigment dispersion can be used without particular limitation, and examples thereof include a cationic polymer dispersant, A nonionic polymeric dispersant, a pigment-derivative dispersant (dispersion aid), and the like. Particularly, it is preferred to use a compound having a cationic functional group such as an imidazolyl group, a pyrrolyl group, a pyridyl group, a primary, secondary or tertiary amino group as an adsorption point to a pigment, an amine value of 1 to 100 mgKOH / g, A cationic polymer dispersant having a viscosity in the range of 1,000 to 100,000 is suitable. The blending amount of the dispersant is preferably from 1 to 30 mass%, more preferably from 2 to 25 mass%, based on the light shielding component.

Further, when preparing a photosensitive resin composition for a light-shielding film by covariance of a part of the polymerizable unsaturated group-containing alkali-soluble resin of the component (A) in addition to the above-mentioned dispersant in preparing the light-shielding dispersion, the sensitivity of exposure can be easily maintained at a high sensitivity , A photosensitive resin composition can be obtained which is excellent in adhesion at the time of development and hardly causes a problem of residues. The blending amount of the component (A) at this time is preferably 2 to 20% by mass, and more preferably 5 to 15% by mass in the light-shielding dispersion. When the content of the component (A) is less than 2% by mass, the covalent effect of improving the sensitivity, improving the adhesion and reducing the residue can not be obtained. If it is more than 20% by mass, it is difficult to obtain a photosensitive resin composition for obtaining a coating film having a high resistance because the light-shielding dispersion liquid has a high viscosity and is difficult to disperse uniformly or takes a very long time when the content of the light- Loses. The obtained light-shielding dispersion liquid was mixed with the component (A), the component (B), the component (C) and the component (D), and the component (F) A photosensitive resin composition may be used.

The photosensitive resin composition of the present invention may further contain additives such as a polymerization initiator, a chain transfer agent, a sensitizer, a non-photosensitive resin, a curing accelerator, an antioxidant, a plasticizer, a filler, a leveling agent, a defoaming agent, , A surfactant, a coloring pigment, and a dye. Examples of the polymerization initiators other than the oxime ester-based and azo-based polymerization initiators include acetophenones, benzophenones,? -Hydroxyalkylphenones,? -Aminoalkylphenones, benzoin ethers, biimidazole-based compounds, halomethyldiazoles Mercapto compounds, disulfide compounds and the like. Examples of the chain transfer agent and the sensitizer include sulfur-containing compounds, 1,4-butanediol compounds, 1,4-butanediol compounds, -Bis (3-mercaptobutyryloxy) butane, and the like can be preferably exemplified. Examples of the non-photosensitive resin include bisphenol type epoxy resins, novolak type epoxy resins, alicyclic epoxy resins and epoxy silicone resins. Examples of the antioxidants include hindered phenol antioxidants and phosphorus antioxidants. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate. Examples of the filler include glass fiber, silica, mica, and alumina. Examples of the defoaming agent and leveling agent include silicone, fluorine, . Examples of the surfactant include a fluorine surfactant and a silicone surfactant. Examples of the coupling agent include 3- (glycidyloxy) propyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3- And a silane coupling agent such as ethoxysilane.

The photosensitive resin composition of the present invention suitably contains the above components (A) to (F) as main components. (A) to (E) in a total amount of 80% by mass, preferably 90% by mass or more, in the solid content excluding the solvent (solid content includes monomers which become solid components after curing). (F) The amount of the solvent varies depending on the target viscosity, but it is preferable that the amount is in the range of 70 to 90% by mass in the photosensitive resin composition.

As a method of forming the light-shielding film using the photosensitive resin composition for a light-shielding film in the present invention, there is the following photolithography method. First, the photosensitive resin composition is coated on a plastic substrate or a device, and then the solvent is dried (prebaking). The thus obtained coating film is irradiated with ultraviolet rays through a photomask to cure the exposed portion, A method of forming a pattern by further performing a phenomenon of eluting the light portion, and post-baking (thermo-plasticizing) as post-curing.

As the substrate to which the photosensitive resin composition of the present invention is applied, a resin film (plastic substrate) such as PET or PEN having a heat resistance temperature of 160 占 폚 or less can be given. Here, the heat-resistant temperature is a temperature at which no problems such as deformation are caused even when the substrate is exposed in a processing process such as pattern formation of a light-shielding film on the substrate, and the resin film is also changed depending on the degree of drawing treatment. It is necessary that it does not exceed the glass transition temperature (Tg). In addition, an electrode such as ITO or gold deposited or patterned on a resin film can be exemplified as a substrate.

Another example of the substrate to which the photosensitive resin composition of the present invention is applied includes a substrate having a high heat resistance such as a glass substrate or a silicon wafer but a thin film having low heat resistance on the substrate. Specific examples include devices formed with organic EL (OLED) or organic thin film transistors (TFT) on glass or silicon wafers. The heat resistance temperature of a substrate having low heat resistance to be subjected in the present invention such as a resin film or a device varies depending on the type of resin and device, but is generally 100 to 160 占 폚.

As a method of applying the solution of the photosensitive resin composition on these substrates, any of a roller coater machine, a land coater machine, a method using a slit coater machine or a spinner machine and the like can be employed in addition to the known solution dipping method and spraying method. After coating with a desired thickness by these methods, the film is formed by removing the solvent (pre-baking). The prebaking is performed by heating with an oven, a hot plate or the like. The heating temperature and the heating time in the pre-baking are appropriately selected according to the solvent to be used and are, for example, carried out at a temperature of 60 to 110 DEG C for 1 to 3 minutes.

Exposure performed after prebaking is performed by an ultraviolet ray exposure apparatus, and exposed through a photomask to expose only the resist corresponding to the pattern. The exposure apparatus and its exposure conditions are suitably 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 a deep ultraviolet ray 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 in the unexposed portion, and a desired pattern is formed by this development. As the developer suitable for the alkali development, for example, an aqueous solution of a carbonate of an alkali metal or an alkaline earth metal, an aqueous solution of an alkali metal hydroxide or the like can be mentioned. In particular, 0.05 to 3 mass of a carbonate such as sodium carbonate, potassium carbonate, % In a weak alkaline aqueous solution at a temperature of 23 to 28 占 폚, and a fine image can be precisely formed using a commercially available developing device, an ultrasonic cleaner, or the like.

After the development, heat treatment (post baking) is preferably performed at a temperature of 100 to 160 DEG C and for 20 to 60 minutes. This post-baking is performed for the purpose of, for example, increasing the 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 prebaking. The patterned light-shielding film of the present invention is formed through each step of the above photolithography method.

As described above, the photosensitive resin composition of the present invention can be suitably used for forming a light-shielding film on the substrate up to a substrate having a low heat-resistant temperature by an operation such as exposure or alkali development. Particularly, Also suitable. More specifically, when a substrate having a low heat-resistant temperature is used, a black matrix for forming an organic EL pixel or a barrier rib material (when RGB is formed by an ink-jet method, etc.), a light-shielding film, a light- And the substrate to which these light-shielding films are attached can be made to be a display device such as a liquid crystal or an organic EL, or an object to be absent of the image pickup device (that is, to be referred to as a display substrate as a whole).

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. The evaluation of the resin in the synthesis examples was carried out as follows.

[Solid content concentration]

The following expression from: [W ₀ (g) wt] was weighed was impregnated in the [W ₁ (g)], the weight [W ₂ (g)] after 2hr heated at 160 ℃ a resin solution 1g obtained in Synthesis Example a glass filter Lt; / RTI >

Solid content concentration (% by weight) = 100 x (W ₂ -W ₀ ) / (W ₁ -W ₀ )

[Mountain]

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

[Molecular Weight]

(2) + TSKgelSuperH-3000 (1) + TSKgelSuperH-4000 (1) + TSKgelSuperH-2000 (2) + gel permeation chromatography (GPC) [trade name: HLC-8220GPC manufactured by TOSOH CORPORATION, solvent: tetrahydrofuran, column: TSKgelSuperH- And the weight average molecular weight (Mw) as a value converted into a standard polystyrene (PS-oligomer kit manufactured by TOSOH CORPORATION) was determined.

The abbreviations used in the synthesis examples are as follows.

BPFE: Reaction product of 9,9-bis (4-hydroxyphenyl) fluorene and chloromethyloxysilane.

In the compound of formula (I), A is fluorene-9,9-diyl, and R ₁ , R ₂ , R ₃ and R ₄ are hydrogen.

AA: Acrylic acid

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

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

MAA: methacrylic acid

MMA: methyl methacrylate

CHMA: cyclohexyl methacrylate

GMA: glycidyl methacrylate

TEAB: tetraethylammonium bromide

AIBN: azobisisobutyronitrile

TPP: triphenylphosphine

DTBC: 2,6-di-tert-butyl-p-cresol

PGMEA: Propylene glycol monomethyl ether acetate

DMDG: Diethylene glycol dimethyl ether

[Synthesis Example 1]

114.4 g (0.23 mol) of BPFE, 33.2 g (0.46 mol) of AA, 157 g of PGMEA and 0.48 g of TEAB were charged into a 500 ml four-necked flask equipped with a reflux condenser and reacted by heating at 100 to 105 ° C for 20 hours with stirring. Subsequently, 35.3 g (0.12 mol) of BPDA and 18.3 g (0.12 mol) of THPA were introduced into the flask, and the mixture was stirred under heating at 120 to 125 ° C for 6 hours to obtain an alkali-soluble resin (A) -1. The solid concentration of the obtained resin solution was 56.1 wt%, the acid value (in terms of solid content) was 103 mgKOH / g, and the Mw by GPC analysis was 3600.

[Synthesis Example 2]

(0.60 mole) of MAA, 38.0 g (0.38 mole) of MMA, 37.0 g (0.22 mole) of CHMA, 5.91 g of AIBN and 295 g of DMDG were charged into a 1000 ml four-necked flask equipped with a reflux condenser, And the mixture was stirred at 80 to 85 ° C for 8 hours in a nitrogen stream to effect polymerization. Further, 39.8 g (0.28 mol) of GMA, 1.44 g of TPP and 0.055 g of DTBC were poured into the flask and stirred at 80 to 85 ° C for 16 hours to obtain a polymerizable unsaturated group-containing (meth) acrylate resin (A) -2. The obtained resin solution had a solid concentration of 35.5% by mass, an acid value (in terms of solid content) of 110 mgKOH / g, and a Mw of 18080 by GPC analysis.

Next, the present invention will be specifically described with reference to examples and comparative examples relating to the production of a photosensitive resin composition for a light-shielding film and a cured product thereof, but the present invention is not limited thereto. Hereinafter, raw materials and abbreviations used in the photosensitive resin composition for a light-shielding film of the following Examples and Comparative Examples and the cured products thereof are as follows.

(Polymerizable unsaturated group-containing alkali-soluble resin)

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

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

(Photopolymerizable monomer)

(B) -1: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (TOAGOSEI CO., LTD., Trade name ARONIX M-405)

(B) -2: trimethylolpropane triacrylate (trade name: SR351S, manufactured by Sartomer Company)

(B) -3: EO adduct of bisphenol A Diacrylate (Lite acrylate BP-4EAL available from Kyoeisha Chemical Co., Ltd.)

(Oxime ester-based polymerization initiator)

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

(Other than the azo-based polymerization initiator)

(D) -1: 2,2-azobisisobutyronitrile (V-60, a product of Wako Pure Chemical Industries, Ltd.)

(D) -2: dimethyl 2,2-azobis 2-methylpropionate) (trade name V-601, manufactured by Wako Pure Chemical Industries, Ltd.)

(D) -3: 1,1'-azobis (1-acetoxy-1-phenylethane) (OTAZO-15 available from Otsuka Chemical Co., Ltd.)

(D) -4: benzoyl peroxide (NYPER BMT-K40 available from NOF CORPORATION)

(Light-shielding dispersed pigment)

(E): PGMEA dispersion (solid content: 29.75%) having a carbon black concentration of 25.0 mass% and a polymer dispersant concentration of 4.75 mass%

(solvent)

(F) -1: PGMEA

(F) -2: Cyclohexanone

(Silane coupling agent)

(H): S-510 (manufactured by JNC CORPORATION)

(Surfactants)

(I): Megafac F475 (manufactured by DIC Corporation)

The photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 4 were prepared by blending the above-mentioned blended components in the ratios shown in Table 1. In addition, the numerical values in Table 1 indicate the parts by mass. (F) -1 and (F) -2 are amounts not including the solvent in (A) -1 and (A) -2 and the solvent in (E).

[evaluation]

Using the photosensitive resin compositions for black resists of Examples 1 to 6 and Comparative Examples 1 to 4, evaluation described below was carried out. The evaluation results are shown in Tables 2 and 3.

≪ Evaluation of developing characteristics (pattern line width, pattern linearity)

Each of the photosensitive resin compositions obtained above was coated on a 125 mm x 125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking became 1.2 占 퐉 and prebaked at 90 占 폚 for 1 minute. Thereafter, the exposure gap was adjusted to 100 탆, a negative type photomask of line / space = 10 탆 / 50 탆 was placed on the dried coating film, ultraviolet rays of 50 mJ / cm 2 were irradiated with an ultrahigh pressure mercury lamp of 30 mW / And photo-curing reaction of the photosensitive part was carried out.

Subsequently, after the development of +10 second and +20 seconds from the development time (break time = BT) at which the pattern starts to appear at a shower pressure of 1 kgf / cm2 with a 0.04% potassium hydroxide aqueous solution at 25 deg. / Cm < 2 > pressure to remove the unexposed portions of the coated film to form a light-shielding film pattern on the glass substrate, followed by heat post baking at 120 DEG C for 60 minutes using a hot air drier. The line width and pattern linearity with respect to the mask width of 10 mu m lines of the obtained light-shielding film pattern were evaluated.

Pattern line width: A pattern line width of a mask width of 10 mu m was measured using a measuring microscope ("XD-20" manufactured by Nikon Corporation).

Pattern linearity: A 10 mu m mask pattern after post-baking was observed with an optical microscope, and it was found that no peeling or milling of the pattern edge portion was confirmed on the substrate, & cir & did.

The pattern line width and pattern linearity were evaluated in the case of BT + 10 seconds and BT + 20 seconds.

<Evaluation of OD / 탆>

Each of the photosensitive resin compositions obtained above was coated on a 125 mm 125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking became 1.1 占 퐉 and prebaked at 90 占 폚 for 1 minute. Thereafter, the photo-curing reaction is carried out by irradiating ultraviolet light of 80 mJ / cm 2 with an i-line illumination of an ultra-high pressure mercury lamp of 30 mW / cm 2 without applying a negative type photomask.

Subsequently, the coated board was subjected to spraying at a pressure of 5 kgf / cm 2 using a 0.05% potassium hydroxide aqueous solution at 25 ° C for 60 seconds at a shower pressure of 1 kgf / cm 2, , Baked in a heat post for 60 minutes. The OD value of this plate was evaluated using a Macbeth permeation densitometer. Further, the film thickness of the light-shielding film formed on the plate was measured, and the value obtained by dividing the OD value by the film thickness was taken as OD / 占 퐉.

&Lt; Evaluation of solvent resistance &

The evaluation of the solvent resistance of the coating film (light-shielding film) formed by using the prepared plate (glass plate with a light-shielding film) similarly to the OD evaluation. The surface state was observed by rubbing with a rag soaked in PGMEA or cyclohexanone (Anon), and the number of times of rubbing when the surface of the coating film was dissolved or softened and scratches were recorded. When the number of times when any one of the solvents was used was 20 or more, the solvent resistance was evaluated as O, and when it was less than 20, the solvent resistance was evaluated as X.

<Stability over time>

When the initial solution viscosity of the prepared photosensitive resin solution was maintained at 23 ° C at room temperature for 5 days, the solution viscosity increased 1.5 times or more than the initial solution viscosity.

When the photosensitive resin composition solution for a light-shielding film of the present invention is used, as shown in Examples 1 to 6, even when post-baking is performed at a low temperature of 120 占 폚, the linearity of the pattern is maintained and the light- And the storage stability of the photosensitive resin composition solution is sufficient.

On the other hand, when a bifunctional monomer is used as the photopolymerizable monomer as in Comparative Example 1, the crosslinking density of the cured film after post-baking is not sufficiently obtained, and the pattern linearity is poor and the solvent resistance is poor . When the peroxide-based polymerization initiator is used instead of the azo-based polymerization initiator for imparting thermal radical polymerization property as in Comparative Example 2, the storage stability of the photosensitive resin composition solution is not sufficient. When the azo-based polymerization initiator is not added as in Comparative Example 3, sufficient solvent resistance can not be obtained when the post-baking temperature is low. When the acrylic copolymer compound instead of the compound represented by the general formula (II) is used as the polymerizable unsaturated group-containing alkali-soluble resin as in Comparative Example 4, the crosslinking does not proceed sufficiently at a low post-baking temperature, It is not obtained, and there is insufficient content preparation.

The photosensitive resin composition for a light-shielding film according to the present invention can be used in a process for producing a light-shielding film, which does not include a step of thermosetting at a temperature exceeding 160 캜, but has a line width of 5 to 15 탆, Shielding film (light-shielding pattern) which is excellent in light resistance and excellent in solvent resistance can be formed. Therefore, it is possible to form a light-shielding film having the above-described characteristics for a resin film made of PET or PEN having a heat-resistant temperature of 160 ° C or lower, a device provided with an organic EL, an organic TFT, or the like on a glass substrate or a silicon wafer .

That is, in the photosensitive resin composition for a light-shielding film of the present invention, for example, a light-shielding film such as a black matrix, a barrier rib material, a column spacer having a light-shielding function or the like necessary for forming a color filter or an organic EL pixel (Bezel) portion or the like required for forming a touch panel, and the like. The substrate on which the light-shielding film is attached (that is, the substrate for display) is mounted on a display device such as liquid crystal or organic EL Or can be used in the manufacture of solid-state imaging elements such as CMOS.

Claims (6)

The following components (A) to (E)
(A) an alkali-soluble resin containing a polymerizable unsaturated group having a structure of an epoxy (meth) acrylate acid adduct,
(B) a photopolymerizable monomer having at least three ethylenically unsaturated bonds,
(C) an oxime ester-based polymerization initiator,
(D) an azo-based polymerization initiator, and
(E) at least one light-shielding component selected from the group consisting of a black organic pigment, a mixed-color organic pigment, and a light-
Is contained as an essential component in the photosensitive resin composition for a light-shielding film. The method according to claim 1,
The polymerizable unsaturated group-containing alkali-soluble resin as the component (A) is a photosensitive resin composition for a light-shielding film represented by the following general formula (II).

Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R ₅ is a hydrogen atom or a methyl group, A is -CO -, -SO ₂ -, -C (CF ₃ ) ₂ -, -Si (CH ₃ ) ₂ -, -CH ₂ -, -C (CH ₃ ) ₂ -, -O-, represents a bond or a straight-diyl group, X represents a tetravalent carboxylic acid moiety represents a, Y ₁ and Y ₂ are each independently a hydrogen atom or a -OC-Z- (COOH) _m (end, Z is a divalent or trivalent And m represents a number of 1 or 2), and n represents an integer of 1 to 20, 3. The method according to claim 1 or 2,
(C) relative to 100 parts by mass of the total of the components (A) and (B) in the mass ratio (A) / (B) of the component (A) (E) is contained in an amount of 40 to 70% by mass in a solid content containing a component which becomes a solid component by photo-curing of the photosensitive resin composition for a light-shielding film, the component (D) is 1-20 parts by mass, A photosensitive resin composition for a light-shielding film. 4. The method according to any one of claims 1 to 3,
And the component (E) is carbon black. A substrate for a display having a light-shielding film on a substrate having a heat-resistant temperature of 160 DEG C or less,
Wherein the light-shielding film comprises the following components (A) to (E)
(A) an alkali-soluble resin containing a polymerizable unsaturated group having a structure of an epoxy (meth) acrylate acid adduct,
(B) a photopolymerizable monomer having at least three ethylenically unsaturated bonds,
(C) an oxime ester-based polymerization initiator,
(D) an azo-based polymerization initiator, and
(E) at least one light-shielding component selected from the group consisting of a black organic pigment, a mixed-color organic pigment, and a light-
Wherein the photosensitive resin composition for a light-shielding film is cured. A method for producing a display substrate having a light-shielding film on a substrate having a heat-resistant temperature of 160 DEG C or less,
The following components (A) to (E)
(A) an alkali-soluble resin containing a polymerizable unsaturated group having a structure of an epoxy (meth) acrylate acid adduct,
(B) a photopolymerizable monomer having at least three ethylenically unsaturated bonds,
(C) an oxime ester-based polymerization initiator,
(D) an azo-based polymerization initiator, and
(E) at least one light-shielding component selected from the group consisting of a black organic pigment, a mixed-color organic pigment, and a light-
A light-shielding film having a predetermined pattern is formed by heating at 160 DEG C or lower to form a light-shielding film having a predetermined pattern. The light- Wherein the first substrate and the second substrate are bonded to each other.