KR100777561B1 - Alkali-developable resins and photosensitive resin composition comprising the same - Google Patents

Abstract

The present invention provides a composition for producing an alkali-soluble resin comprising a) a diol compound having two polymerizable unsaturated groups, b) an acid dianhydride, c) a diamine compound, and d) an acid anhydride, if necessary, wherein the composition comprises alternating copolymerization. It provides an alkali-soluble resin formed through and a photosensitive resin composition comprising the same. The photosensitive resin composition according to the present invention has excellent sensitivity and chemical resistance due to the alkali-soluble resin of the present invention.

Description

Alkali-soluble resin and the photosensitive resin composition containing the same {ALKALI-DEVELOPABLE RESINS AND PHOTOSENSITIVE RESIN COMPOSITION COMPRISING THE SAME}

1 is a view observed with an optical microscope after immersing the color filter photosensitive material to which the photosensitive resin composition of Example 4 was applied for 5 minutes at 60 ℃ NMP,

2 is a view observed with an optical microscope after immersing the color filter photosensitive material to which the photosensitive resin composition of Example 5 is applied for 5 minutes at 60 ℃ NMP,

3 is a view observed with an optical microscope after immersing the color filter photosensitive material to which the photosensitive resin composition of Comparative Example 2 is applied for 5 minutes at 60 ℃ NMP,

4 is a diagram observed with an optical microscope after immersing the color filter photosensitive material to which the photosensitive resin composition of Comparative Example 3 is applied for 5 minutes at 60 ℃ NMP.

The present invention relates to an alkali-soluble resin and a photosensitive resin composition comprising the same, and more particularly, to an alkali-soluble resin and a flat panel display (FPD) including the same, which can increase the chemical resistance of the photosensitive resin composition and achieve high sensitivity. It relates to a photopolymerizable negative photosensitive resin composition which can be used for.

The photopolymerization type negative photosensitive resin composition is used in various applications such as photoresist for color filter production, overcoat photoresist, column spacer, and insulating material having light shielding properties, which are generally alkali-soluble resins, polymerizable compounds having ethylenically unsaturated bonds, Photopolymerization initiator and solvent. Such a photosensitive resin composition forms a coating film by apply | coating the photosensitive resin composition on a board | substrate, after exposing by a radiation irradiation to a specific part of this coating film using a photomask etc., a non-exposure part is removed by the development process, It can be used in a manner to form a pattern.

Recently, the use of LCD (liquid crystal display) has been expanded from the existing notebook monitors to desktop monitors, LCD TVs, etc., in order to realize high quality color, the pigment concentration in the color filter photosensitive material is increased, and the pigment is finely dispersed. The concentration of the dispersant used for pigment dispersion is increasing. Relatively high concentrations of pigments and pigment dispersants are known to cause particularly poor chemical resistance and sensitivity of color filter photosensitive materials. The photoresist with low chemical resistance may be damaged by the high temperature alignment film liquid during the alignment film coating process, and may emit a substance that contaminates the liquid crystal during the subsequent liquid crystal injection, which may adversely affect the driving of the liquid crystal, resulting in poor quality. . On the other hand, color filter photoresist with high concentration of high density, black matrix photoresist requiring high light shielding, and column space photoresist requiring thick film formation of 3 microns or more require a lot of energy irradiation due to the small amount of UV energy transmitted to the lower part of the film. In order to improve the yield per unit time of the process in the process of using the photosensitive resin composition for manufacturing a filter substrate, the high sensitivity of the photosensitive resin composition itself is required.

The most representative method for improving the chemical resistance of the photosensitive resin composition is to increase the amount of ethylenically unsaturated compounds which can increase the crosslinking density. However, when the amount of ethylenically unsaturated compound is increased, the amount of the binder polymer that can be injected is relatively reduced, resulting in deterioration of developability or physical properties of the coating film.

In order to achieve high sensitivity of the photosensitive resin composition, a method using a high sensitivity photoinitiator is most typical, but when an excessive amount of photoinitiator is used, many low molecular weights may be eluted in the polyimide solution, causing chemical resistance problems. Many photoinitiators are sublimable and may increase the oven contamination in the postbake process.

However, high chemical resistance and high sensitivity of the photosensitive resin are not separate properties, and photosensitive resins having high sensitivity are generally likely to have high chemical resistance. Therefore, a technique generally known such as JP 2003-241374 or JP 2004-219979, which introduces an unsaturated double bond group into the side chain of an alkali-soluble binder resin and makes the resulting resin film dense. However, the alkali-soluble resin provided in this document has a limit to increase the fraction of unsaturated double bond groups that can be introduced into the side chain in the manufacturing process, and cannot achieve high sensitivity and high chemical resistance to a satisfactory level.

Meanwhile, in order to sufficiently introduce unsaturated double bonds capable of participating in photocrosslinking in the binder resin, JP 1997-325494, JP 2005-77451, KR 2005-0021902, and the like have diol compounds having one or more polymerizable unsaturated groups in a molecule; The carboxyl group-containing alternating copolymer obtained by making an acid dianhydride react is provided. However, the copolymer prepared in this way can achieve high sensitivity, but does not have sufficient chemical resistance because unreacted diol compound and low molecular weight remain in the resin solution.

The present inventors have found that high sensitivity and high chemical resistance can be achieved by reacting a diol compound having two polymerizable unsaturated groups and an acid dianhydride in a molecule and additionally adding a diamine compound in preparing a carboxyl group-containing alternating copolymer obtained. .

Accordingly, an object of the present invention is to provide a composition for preparing an alkali-soluble resin using a diol compound, an acid dianhydride, a diamine compound, an acid anhydride as a monomer, and an alkali-soluble resin polymerized with the composition. do.

In addition, another object of the present invention is to provide a photosensitive resin composition, particularly a photosensitive resin composition for manufacturing an LCD color filter substrate, in which the composition is used as an essential component to achieve high sensitivity and high chemical resistance.

The present invention relates to a composition for producing an alkali-soluble resin comprising a) a diol compound having two polymerizable unsaturated groups, b) an acid dianhydride, c) a diamine compound, and d) an acid anhydride, if necessary, wherein the composition comprises alternating copolymerization. It provides an alkali-soluble resin formed through and a photosensitive resin composition comprising the same.

Hereinafter, the present invention will be described in detail.

The diol compound which has two polymerizable unsaturated groups which are a) component of this invention provides a photocrosslinkable ethylenically unsaturated group, and is a compound which provides the diol group which can be copolymerized alternately with the acid dianhydride which is b) component, Preferably Is a compound of formula 1 which is presented through a condensation reaction of a diglycidyl ether compound with (meth) acrylic acid. Here, (meth) acrylic acid means acrylic acid or methacrylic acid.

Where

R is hydrogen or methyl,

(단, Y는 직접 결합, C₁~C₆의 알킬렌, 케톤, -O-, -S-, -SO₂-, 헥사플루오로프로필, -OC₆H₄O-, -OC₆H₄C(CH₃)₂C₆H₄O-로 이루어지는 군으로부터 1종 선택된다), 9,9-비스페놀 플로레닐 및 9,9-비스(4-에톡시페닐) 플로레닐로 이루어진 군으로부터 1종 이상 선택되어진다. X is C _n H _2n ,-(CH ₂ CH ₂ O) _n CH ₂ CH _{2 -} ,-(CHCH ₃ CH ₂ ) _n OCHCH ₃ CH _2- , (where n is an integer from 1 to 10),

Wherein Y is a direct bond, C ₁ -C ₆ alkylene, ketone, -O-, -S-, -SO _2- , hexafluoropropyl, -OC ₆ H ₄ O-, -OC ₆ H ₄ One selected from the group consisting of C (CH ₃ ) ₂ C ₆ H ₄ O-), 9,9-bisphenol florenyl and 9,9-bis (4-ethoxyphenyl) florenyl Is selected.

The acid dianhydride as the component b) of the present invention is a compound that provides two anhydride groups capable of alternating copolymerization with a diol compound as a component and a diamine compound as a component, a compound having two acid anhydride groups in one molecule. to be.

Specific examples include 1,2,4,5-benzene tetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl ) Ether dianhydride, bis (3,4-dicarboxyphenyl) sulfide dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, ethylene glycol bis (4- trimellitate) dianhydride, glycerol bis (1 , 3-trimeric anhydride) -2-acetate, 1,4-bis (2,3-dicarboxyphenoxy) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy ) Diphenyl ether dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfone dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 1,1-bis (3) , 4-dicarboxyphenyl) ethane dianhydride Water, 1,2-bis (3,4-dicarboxyphenyl) ethane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis [4- (3,4 -Dicarboxyphenoxy) phenyl] propane dianhydride, 4- (2,3-dicarboxyphenoxy) -4'- (3,4-dicarboxyphenoxy) diphenyl-2,2-propane dianhydride, 2 , 2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis [4- ( 3,4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride, 4,4'-bis [2- (3,4-dicarboxyphenyl) hexafluoroisopropyl] diphenyl ether dianhydride, and the like. .

The diamine compound which is c) component of this invention is a compound which provides the diamine group which can be copolymerized alternately with the acid dianhydride compound which is b) component.

Specific examples include m-phenylene diamine, p-phenylene diamine, 1,3-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) propane, 4,4'-diamino-diphenyl Methane, 1,2-bis (4-aminophenyl) ethane, 1,1-bis (4-aminophenyl) ethane, 2,2'-diamino-diethyl sulfide, bis (4-aminophenyl) sulfide, bis (4-aminophenyl) sulfone, bis (4-aminophenyl) ether, 4,4'-diamino-benzophenone, 2,2-bis (4-aminophenyl) hexa fluoropropane, 2,2-bis [ 4- (4-aminophenoxy) phenyl] hexafluoropropane, 4,4'-bis [2- (4-aminophenoxyphenyl) hexafluoroisopropyl] diphenyl ether, 4,4 '-(1 , 4-phenylenedioxy) dianiline, 4,4 '-(1,3-phenylenedioxy) dianiline, 4,4'-(4,4'-isopropylidene diphenyl-1,1'-diyl -Dioxy) dianiline and the like.

Acid anhydride, which is a d) component of the present invention, is a compound used to control the molecular weight at the time of alternating copolymerization or to convert the amine end to the carboxy terminus after completion of the alternating copolymerization, and may be additionally included in the alkali-soluble resin composition.

Specific examples include succinic anhydride, glutaric anhydride, methyl succinic anhydride, maleic anhydride, methyl maleic anhydride, phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic acid Anhydride, hexahydrophthalic anhydride, cis-5-norbornene- (endo, exo) -2,3-dicarboxylic acid anhydride and the like.

Alkali-soluble resin of this invention is manufactured by the following method.

First, a) 50 to 150 moles of acid dianhydride, preferably 60 to 120 moles, and d) 0.1 to 20 moles of acid monoanhydride, preferably 0.5 to 10 moles per 100 moles of diol compound. Mole was added and an alcohol-free solvent was added, followed by heating at 80 ° C. to 150 ° C. for 4 to 48 hours to prepare alternate copolymers of a) and b) or a) and b) and d).

Thereafter, the reaction temperature was lowered to 10 ° C. to 70 ° C., c) 0.1 to 20 mol of the diamine compound was added to the alternating copolymer, the mixture was stirred for 4 hours to 48 hours, and d) 0.1 to 20 mol of the acid anhydride, if necessary. It is further prepared by stirring for 4 hours to 24 hours.

Alkali-soluble resin of the present invention prepared in this way can introduce a sufficient amount of ethylenically unsaturated groups in one molecule to increase the sensitivity and chemical resistance, and the amic acid group in the resin is changed to the imide group through the post-baking process Chemical resistance can be further improved.

Representative examples of the alkali-soluble resin prepared according to the present invention may be represented by the following formula (2).

Wherein m and n are integers of 1 or greater.

In addition, the present invention

1) alkali-soluble resin in which the alkali-soluble resin composition of the present invention is polymerized;

2) a polymerizable compound having an ethylenically unsaturated bond;

3) photopolymerization initiator; And

4) It provides the photosensitive resin composition containing a solvent as an essential component.

Among the constituents of the photosensitive resin composition according to the present invention, non-limiting examples of the polymerizable compound having 2) ethylenically unsaturated bonds include ethylene glycol di (meth) acrylate and polyethylene glycol di with 2 to 14 ethylene groups. (Meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 2-trisacryloyl Polyhydric alcohols such as oxymethylethylphthalic acid, propylene glycol di (meth) acrylate having 2 to 14 propylene groups, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like; Compounds obtained by esterification with an unsaturated carboxylic acid; Compounds obtained by adding (meth) acrylic acid to a compound containing glycidyl groups such as trimethylolpropane triglycidyl ether acrylic acid adduct and bisphenol A diglycidyl ether acrylic acid adduct; Ester compound of the compound which has hydroxyl group or ethylenically unsaturated bond, such as phthalic acid diester of (beta) -hydroxyethyl (meth) acrylate and toluene diisocyanate adduct of (beta) -hydroxyethyl (meth) acrylate, and polyhydric carboxylic acid Or adducts with polyisocyanates; And (meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and 9,9'-bis [4- ( 2-acryloyloxyethoxy) phenyl] fluorene, but not limited to these, those known in the art may be used. In some cases, silica dispersions may be used for these compounds, for example, Nanocryl XP series (0596, 1045, 21/1364) and Nanopox XP series (0516, 0525) manufactured by Hanse Chemie.

Since alkali-soluble resin of this invention has an ethylenically unsaturated bond, 2) the polymeric compound which has an ethylenically unsaturated bond in the photosensitive resin composition can be omitted, and this also belongs to the scope of the present invention.

Among the constituents of the photosensitive resin composition according to the present invention, non-limiting examples of the 3) photopolymerization initiator include 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4-trichloro Rhomethyl- (4'-methoxystyryl) -6-triazine, 2,4-trichloromethyl- (piflonil) -6-triazine, 2,4-trichloromethyl- (3 ', 4 Triazine compounds such as' -dimethoxyphenyl) -6-triazine and 3- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} propanoic acid; 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5 Biimidazole compounds such as 5′-tetraphenylbiimidazole; 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxy Methoxy) -phenyl (2-hydroxy) propyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenyl acetophenone, 2-methyl- (4-methylthiophenyl) -2-mol Acetophenone-based compounds (Irgacure- such as polyno-1-propane-1-one (Irgacure-907) and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one) 369); O-acyl oxime compounds such as Irgacure OXE 01 and Irgacure OXE 02 by Ciba Geigy, benzophenones such as 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone compound; Thioxanthone-based compounds such as 2,4-diethyl thioxanthone, 2-chloro thioxanthone, isopropyl thioxanthone and diisopropyl thioxanthone; 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide, bis (2,6-dichlorobenzoyl) propyl phosphine oxide Phosphine oxide compounds such as these; 3,3'-carbonylvinyl-7- (diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3-benzoyl-7- (diethylamino) coumarin, 3-benzoyl-7-methoxy-coumarin, 10,10'-carbonylbis [1,1,7,7-tetramethyl-2,3,6,7-tetra hydro-1H, 5H, 11H-Cl] Coumarin-based compounds such as -benzopyrano [6,7,8-ij] -quinolizin-11-one.

Among the constituents of the photosensitive resin composition according to the present invention, non-limiting examples of the solvent 4) methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl Ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, 2-ethoxy propanol, 2-methoxy propanol, 3-methoxy butanol, cyclohexanone, Cyclopentanone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, dipropylene glycol mono Methyl ether or mixtures of one or more thereof.

The photosensitive resin composition of the present invention may additionally include one or more additives such as alkali-soluble acrylic copolymer resins, photosensitizers, colorants, curing accelerators, thermal polymerization inhibitors, plasticizers, adhesion promoters, fillers, or surfactants. .

The alkali-soluble acrylic copolymer resin refers to a polymer in which a monomer containing an acid functional group and a monomer copolymerizable with the monomer are copolymerized with a thermal polymerization initiator.

Non-limiting examples of the monomer containing an acid group include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethyl maleic acid, isoprene sulfonic acid, styrene sulfonic acid, 5-norbornene-2 -Carboxylic acid, mono-2-((meth) acryloyloxy) ethyl phthalate, mono-2-((meth) acryloyloxy) ethyl succinate, ω-carboxy polycaprolactone mono (meth) acrylate or these And mixtures thereof.

Non-limiting examples of monomers copolymerizable with monomers containing an acid group include benzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) acrylic Rate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, ethylhexyl (meth) acrylate, 2-phenoxyethyl (meth ) Acrylate, tetrahydroperpril (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4 -Hydroxybutyl (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, glycerol (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) ) Acrylate, ethoxy Ethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, methoxy tripropylene glycol (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, phenoxydiethylene glycol (meth) Acrylate, p-nonylphenoxypolyethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, glycidyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1 , 1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, tribromophenyl (meth) Acrylate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, propyl α-hydroxymethyl acrylate, butyl α-hydroxymethyl acrylate, dicyclopentanyl (methol ) Acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl oxyethyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) unsaturated carboxylic acid esters such as acrylate; Aromatic vinyls such as styrene, α-methylstyrene, (o, m, p) -vinyl toluene, (o, m, p) -methoxy styrene, (o, m, p) -chloro styrene; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether; N-vinyl tertiary amines, such as N-vinyl pyrrolidone, N-vinyl carbazole, and N-vinyl morpholine; Unsaturated imides such as N-phenyl maleimide, N- (4-chlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide, and N-cyclohexyl maleimide; Maleic anhydrides such as maleic anhydride and methyl maleic anhydride; Unsaturated glycidyl compounds such as allyl glycidyl ether, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, or mixtures thereof.

The alkali-soluble acrylic copolymer resin may further include an ethylenically unsaturated group capable of participating in photopolymerization in the side chain, if necessary. This ethylenically unsaturated group is prepared by condensation with an ethylenically unsaturated compound containing an epoxy group capable of reacting with an acid group in the acrylic copolymer resin, and non-limiting examples of the ethylenically unsaturated compound containing an epoxy group capable of reacting with an acid group include Allyl glycidyl ether, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl 5-norbornene-2-methyl-2-carboxylate (endo, exo mixture) , 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene or mixtures thereof.

As the colorant, one or more pigments, dyes or mixtures thereof may be used. Specifically, as the black pigment, a metal oxide such as carbon black, graphite, or titanium black may be used. Examples of carbon black include cysto 5HIISAF-HS, cysto KH, cysto 3HHAF-HS, cysto NH, cysto 3M, cysto 300HAF-LS, cysto 116HMMAF-HS, cysto 116MAF, cysto FMFEF-HS , Sisto SOFEF, Sisto VGPF, Sisto SVHSRF-HS and Sisto SSRF (Donghae Carbon Co., Ltd.); Diagram Black II, Diagram Black N339, Diagram Black SH, Diagram Black H, Diagram LH, Diagram HA, Diagram SF, Diagram N550M, Diagram M, Diagram E, Diagram G, Diagram R, Diagram N760M, Diagram LR, # 2700, # 2600, # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 900, MCF88, # 52, # 50, # 47, # 45, # 45L, # 25, # CF9, # 95, # 3030, # 3050, MA7, MA77, MA8, MA11, MA100, MA40, OIL7B, OIL9B, OIL11B, OIL30B and OIL31B (Mitsubishi Chemical Corporation); PRINTEX-U, PRINTEX-V, PRINTEX-140U, PRINTEX-140V, PRINTEX-95, PRINTEX-85, PRINTEX-75, PRINTEX-55, PRINTEX-45, PRINTEX-300, PRINTEX-35, PRINTEX-25, PRINTEX- 200, PRINTEX-40, PRINTEX-30, PRINTEX-3, PRINTEX-A, SPECIAL BLACK-550, SPECIAL BLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100, and LAMP BLACK-101 (Daegu Corporation); RAVEN-1100ULTRA, RAVEN- 1080ULTRA, RAVEN-1060ULTRA, RAVEN-1040, RAVEN-1035, RAVEN-1020, RAVEN-1000, RAVEN-890H, RAVEN-890, RAVEN-880ULTRA, RAVEN-860ULTRA, RAVEN-850, RAVEN- 820, RAVEN-790ULTRA, RAVEN-780ULTRA, RAVEN-760ULTRA, RAVEN-520, RAVEN-500, RAVEN-460, RAVEN-450, RAVEN-430ULTRA, RAVEN-420, RAVEN-410, RAVEN-2500ULTRA, RAVEN-2000, RAVEN-1500, RAVEN-1255, RAVEN-1250, RAVEN-1200, RAVEN-1190ULTRA, RAVEN-1170 (Colombia Carbon, Inc.) or mixtures thereof.

In addition, examples of the colorant to be colored are carmine 6B (CI12490), phthalocyanine green (CI 74260), phthalocyanine blue (CI 74160), perylene black (BASF K0084. K0086), cyanine black, linole yellow (CI21090), Linol yellow GRO (CI 21090), benzidine yellow 4T-564D, Victoria pure blue (CI42595), CI PIGMENT RED 3, 23, 97, 108, 122, 139, 140, 141, 142, 143, 144, 149, 166, 168, 175, 177, 180, 185, 189, 190, 192, 202, 214, 215, 220, 221, 224, 230, 235, 242, 254, 255, 260, 262, 264, 272; C.I. PIGMENT GREEN 7, 36; C.I. PIGMENT blue 15: 1, 15: 3, 15: 4, 15: 6, 16, 22, 28, 36, 60, 64; C.I. PIGMENT yellow 13, 14, 35, 53, 83, 93, 95, 110, 120, 138, 139, 150, 151, 154, 175, 180, 181, 185, 194, 213; C.I. PIGMENT VIOLET 15, 19, 23, 29, 32, 37, etc. In addition, a white pigment, a fluorescent pigment, etc. can also be used.

Examples of the curing accelerator include 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mer Capto-4,6-dimethylaminopyridine, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), Pentaerythritol tris (2-mercaptoacetate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (2-mercaptoacetate), trimethyl One or more kinds selected from the group consisting of octane tris (3-mercaptopropionate) may be used, but are not limited thereto, and those known in the art may be used.

The thermal polymerization inhibitors include p-anisole, hydroquinone, pyrocatechol, t-butyl catechol, N-nitrosophenylhydroxyamine ammonium salt, N-nitrosophenylhydroxyamine One or more selected from the group consisting of aluminum salts and phenothiazines can be used, but are not limited thereto, and those known in the art can be used.

Other plasticizers, adhesion promoters, fillers, surfactants and the like can also be used for all compounds that can be included in conventional photosensitive resin compositions.

The photosensitive resin composition according to the present invention

 1) 1 to 20 parts by weight of alkali-soluble resin,

 2) 0.5 to 30 parts by weight of a polymerizable compound having an ethylenically unsaturated bond;

 3) 0.1 to 5 parts by weight of the photopolymerization initiator; And

 4) 10 to 95 parts by weight of solvent

It is preferable to include.

On the other hand, when the alkali-soluble acrylic copolymer resin is added as an additive to the component, the sum of the alkali-soluble acrylic copolymer resin and the alkali-soluble resin of the present invention does not exceed 20 parts by weight, preferably 1 to 19 parts by weight. . In addition, when the above-mentioned additives other than the alkali-soluble acrylic copolymer resin are added, the coloring agent in the additive is 0.5 to 20 parts by weight, the other additives are 0.01 to 10 parts by weight It is preferable to contain.

The composition for producing an alkali-soluble resin according to the present invention may further include a solvent, a condensation catalyst, and other additives commonly used in addition to the above components.

Hereinafter, the manufacturing method of alkali-soluble resin of this invention is demonstrated.

Alkali-soluble resins of the present invention undergo at least two stages of reaction.

The first step is a reaction in which a monomolecular compound forms a polymer, and is an alternating copolymerization reaction of a diol compound as a) and a carboxylic dianhydride compound as b) of the alkali-soluble resin composition of the present invention. The ratio of diol compound to carboxylic anhydride compound may be selected in the range of 50 to 150 moles of carboxylic acid anhydride with respect to 100 moles of diol compound, and in order to obtain a sufficient molecular weight, it is preferable to use a similar mole fraction of about 60 to 120 moles. . This reaction occurs more easily with the addition of small amounts of catalyst. As the catalyst that can be used in the present invention, a conventional catalyst known in the art as a catalyst for condensation reaction can be used, and for example, a basic catalyst such as alkylammonium salt, triphenylphosphine, triphenylantimony, dimethylaminopyridine, or the like can be used. Can be.

The reaction temperature of the condensation reaction is preferably in the range of 80 to 150 ° C, in particular 100 to 150 ° C, and the reaction time is preferably 1 to 48 hours, particularly 4 to 48 hours. In the above temperature range, since the ethylene group added through the condensation reaction may cause gelation through thermal polymerization, a thermal polymerization inhibitor suitable for the polymerization reaction may be used under an oxygen atmosphere, and a representative example of the thermal polymerization inhibitor 4-methoxyphenol (MEHQ), 2,6-di-thibutyl-4-methyl phenol.

The second step according to the present invention is a step in which the carboxylic acid anhydride terminal of the polymer formed through the first step and the diamine compound, which is the c) component of the alkali-soluble resin composition of the present invention, form an amic acid group through a condensation reaction. In this case, the formed amic acid serves to increase chemical resistance of the photosensitive material pattern formed by converting the imide group through a post-baking process. The amount of diamine compound may be selected in a range of 1: 0.5 to 1: 2, preferably 1: 0.8 to 1: 1.5, of the moles of unreacted carboxylic acid: diamine compound of the polymer formed through the first step.

The reaction temperature of the condensation reaction is preferably in the range of 10 ° C to 70 ° C, and the reaction time is preferably 1 to 48 hours. The diamine compound may develop a dark brown color through an oxidation process. In order to prevent such a phenomenon from occurring, the diamine compound may be reacted under a nitrogen atmosphere. However, since the diamine compound may still be gelled, the diamine compound is preferably reacted under an oxygen atmosphere.

Alkali-soluble resin of the present invention may be added, if necessary, the step of condensing the amine terminal with the carboxylic acid anhydride compound to convert the imide group and the reaction conditions are the same as in the second step. The amount of unreacted amine group: carboxylic acid anhydride may be selected in the range of 1: 0.8 to 1: 1.2, preferably 1: 1 to 1: 1.2 in moles.

The acid value of the alkali-soluble resin binder prepared according to this method is preferably in the range of 50 to 200 KOH mg / g. If the acid value is less than 50, the solubility in the alkaline developer is low, which may lead to a long development time and to leave residue on the substrate. When the acid value is more than 200, the pattern may be detached and the pattern may not go straight. You will see an inverse taper (or T-top) over 90 degrees.

In addition, the weight average molecular weight of the alkali-soluble resin binder is preferably in the range of 3000 to 100,000, more preferably in the range of 5,000 to 30,000. If the weight average molecular weight is less than 3000, the binding function between the components required as the binder polymer is weak, and the pattern is lost due to the physical external force during development, and the physical properties such as basic heat resistance and chemical resistance required for the photosensitive material for LCD can be satisfied. none. If the weight average molecular weight is more than 100,000, the developability of the alkaline developer is excessively low, so that the development process characteristics are deteriorated, and if it is severe, the development is impossible, and the flowability is also poor, making it difficult to control the coating thickness or secure the uniformity of the thickness. Lose.

The photosensitive resin composition of the present invention is used in a roll coater, curtain coater, spin coater, spin coater, slot die coater, various printing, deposition, and the like, and supports for metal, paper, and glass plastic substrates. Can be applied to the phase. Moreover, after apply | coating on support bodies, such as a film, it is also possible to transfer on other support bodies, The application method is not specifically limited.

As a light source for hardening the photosensitive resin composition of this invention, mercury vapor arc (arc), carbon arc, Xe arc etc. which emit light of 250-450 nm in wavelength, for example are mentioned.

The present invention will be described in more detail with reference to the following examples. However, the Examples are provided to illustrate the present invention and the scope of the present invention is not limited thereto.

[Synthesis example 1-4. Manufacture of alkali-soluble resin]

Synthesis Example  One

1) Bisphenol A Glycerate Diacrylate ( BGDA ) 69.78 g (0.144 mol), 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride ( DTDA ) 56.76 g (0.158 mol), catalyst 0.89 g of tetrabutylammonium bromide ( TBAB ), 0.39 g of p-methoxyphenol ( MEHQ ) as a thermal polymerization inhibitor, and 287 g of propylene glycol methyl ether acetate ( PGMEA ) as a solvent were placed in a 500 mL two-neck round bottom flask. Heated at 115 ° C. for 2 hours with air. Thereafter, the flask was cooled to obtain a polymer solution A obtained by condensation polymerization of BGDA and DTDA. (Mw 8,300, acid value 144, solids 30.6%)

2) 3.77 g (0.013 mol) of 4,4 '-(1,4-phenylenedioxy) dianiline ( TPEQ ) was dissolved in 25.3 g of cyclohexanone and 66.43 g of the polymer solution A (0.0023 mol of unreacted anhydride group). Drop) and stir at room temperature for 24 hours. During the stirring, air was continuously flowing to create an oxygen atmosphere. Thereafter, 2.00 g (0.013 mol) of tetrahydrophthalic anhydride ( THPA ) was added thereto, and the reaction was terminated for 5 hours to obtain Polymer Solution 1. (Mw 15,000, acid value 156, solids 26.1%)

Synthesis Example  2

1) Bisphenol A Glycerate Diacrylate (BGDA) 62.78 g (0.130 mol), Ethylene Glycol Bis (4-Trimellitate) Anhydride (TMEG) 58.48 g (0.143 mol), TBAB 0.81 g as Catalyst, Thermal Polymerization 0.19 g of MEHQ as inhibitor and 230 g of PGMEA as solvent were placed in a 500 mL two-neck round bottom flask. Heated for 11 hours at 115 ℃ flowing air. Thereafter, the flask was cooled to obtain a polymer solution B obtained by condensation polymerization of BGDA and TMEG. (Mw 5800, Acid Value 142, Solids 34.1%)

2) Dissolve 2.40 g (0.0059 mol) of 4,4 '-(4,4'-isopropylidene diphenyl-1,1'-diyl-dioxy) dianiline (BAPP) in 22.4 g of cyclohexanone Dropped to 115.66 g of polymer solution B (corresponds to 0.0042 mol of unreacted anhydride groups) and stirred at room temperature for 24 hours. During the stirring, air was continuously flowing to create an oxygen atmosphere. After that, 0.64 g (0.004 mol) of THPA was added thereto, and the reaction was terminated by stirring for 24 hours to obtain Polymer Solution 2. (Mw 10,100, acid value 153, solids 29.8%)

Synthesis Example  3

1) Bisphenol A Glycerate Diacrylate (BGDA) 98.68 g (0.204 mol), Biphenyl tetracarboxylic dianhydride (BPDA) 65.89 g (0.224 mol), TBAB 1.32 g as catalyst, MEHQ 0.65 g, as thermal polymerization inhibitor, 126 g of PGMEA was placed in a 500 mL two-neck round bottom flask. Heated at 115 ° C. for 10 hours with air. Then 69.00 g of BGDA solution (31.82 g of solid content, 0.066 mol) was added thereto, followed by 2 hours at 115 ° C., 33.00 g of BGDA solution (15.22 g of solid content of 0.031 mol), and 2 hours at 115 ° C., 28.50 g of BGDA solution (solid content 13.14). g, 0.027 mol), and further heated at 115 ° C. for 1 hour to cool the flask to obtain a polymer solution C obtained by condensation polymerization of BGDA and BPDA. (Mw 5100, acid value 122, solids 38.4%)

2) 0.54 g (0.0018 mol) of 4,4 '-(1,3-phenylenedioxy) dianiline (APB) was dissolved in 3.57 g of cyclohexanone to 107.57 g of the polymer solution C (0.0017 mol of unreacted anhydride group). Drop), stirred at room temperature for 24 hours to terminate the reaction, to obtain a polymer solution 3. During the stirring, air was continuously flowing to create an oxygen atmosphere. (Mw 6,600, acid value 117, solids 40.0%)

Synthesis Example  4

1) 55.55 g (0.120 mol) of bisphenol fluorene diglycidyl ether (BPFG), 19.06 g (0.265 mol) of acrylic acid, 1.52 g of tetrabutylammonium bromide (TBAB) as a catalyst, p-methoxyphenol as a thermal polymerization inhibitor ( MEHQ) 0.81 g and 169 g PGMEA were placed in a 500 mL two-neck round bottom flask. After heating for 12 hours at 120 ° C, confirming that no BPFG remained by TLC. After adding 23.03 g (0.078 mol) of BPDA for 8 hours, adding 1.70 g (0.0057 mol) of BPDA for 5 hours, and then BPDA 1.70 g (0.0057 mol) was added thereto, followed by additional heating for 4 hours, and the flask was cooled to obtain a polymer solution. After taking 169.10 g of this solution, the temperature was raised to 120 ° C., 3.24 g (0.011 mol) of BPDA and 71 g of PGMEA were added thereto, and the result was heated for 8 hours. After cooling, polymer solution D was obtained. (Mw 4,500, acid value 123, solids 27.7%)

2) Dissolve 1.16 g (0.0040 mol) of 4,4 '-(1,3-phenylenedioxy) dianiline (APB) in 8.00 g of PGMEA and add 169,95 g of the polymer solution D (0.0040 mol of unreacted anhydride group). Drop), stirred at room temperature for 24 hours to terminate the reaction, to obtain a polymer solution 4. During the stirring, air was continuously flowing to create an oxygen atmosphere. (Mw 5,100, acid value 117, solids 27.0%)

Comparative Examples 1-3. Alkali-soluble resin production]

Comparative Synthesis Example  One

89.3 g of benzyl methacrylate (BzMA) and 10.7 g of methyl methacrylic acid (MAA), 0.3 g of dodecylmercaptan as a chain transfer agent, and 375 g of PGMEA as a solvent were put in a reactor, and the temperature of the reaction was increased to 70 ° C. At this time, nitrogen was purged in the solution and oxygen was removed for 1 hour. After the reaction temperature reached 70 ° C. and oxygen was sufficiently removed, 2.5 g of 2,2′-azobis (isobutyronitrile) ( AIBN ) was dissolved in 25 g of PGMEA as a thermal initiator. After the polymerization for 6 hours, the temperature was raised to 80 ° C and heated for one hour to cool the reaction to obtain a polymer solution E. (Mw 22000, AV 70, SC 19.24%)

Comparative Synthesis Example  2

83.1 g of benzyl methacrylate (BzMA) and 16.9 g of methyl methacrylic acid (MAA), 1.5 g of dodecylmercaptan as a chain transfer agent, 375 g of PGMEA as a solvent were put in a reactor, and the temperature of the reactant was raised to 70 ° C. At this time, nitrogen was purged in the solution and oxygen was removed for 1 hour. After the reaction temperature reached 70 ° C. and oxygen was sufficiently removed, 2.5 g of 2,2′-azobis (isobutyronitrile) ( AIBN ) was dissolved in 25 g of PGMEA as a thermal initiator. After polymerization for 6 hours, the temperature was raised to 80 ° C., heated for one hour, and the reaction product was cooled down to obtain a polymer solution F (Mw 18000, AV 110, SC 19.42%).

Comparative Synthesis Example  3

Polymer solution G was obtained in the same manner as in the preparation of polymer solution 3 except that 4,4 ′-(1,3-phenylenedioxy) dianiline (APB) was not added in Synthesis Example 3). (Mw 5100, acid value 122, solids 38.4%)

Example 1-5. Photosensitive resin composition]

Example  One

35 g of carbon black 25% dispersion, 13.4 g of alkali-soluble resin (solid content 3.5 g) prepared in Synthesis Example 1 as alkali-soluble resin, 3.5 g of dipentaerythritol hexaacrylate as a polymerizable compound, 2.5 g of photopolymerization initiator Irgacure-369 , 1 g of 3- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} propanoic acid, 0.5 g of 4,4'-diethylaminobenzophenone, organic solvent 44.5 g of PGMEA was mixed for 3 hours to prepare a photosensitive resin composition.

Example  2

35 g of carbon black 25% dispersion, 11.7 g (solid content 3.5 g) of alkali-soluble resin prepared in Synthesis Example 2 as alkali-soluble resin, 3.5 g of dipentaerythritol hexaacrylate as a polymerizable compound, 2.5 g of photopolymerization initiator Irgacure-369 , 1 g of 3- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} propanoic acid, 0.5 g of 4,4'-diethylaminobenzophenone, organic solvent 45.8 g of PGMEA were mixed for 3 hours to prepare a photosensitive resin composition.

Example  3

35 g of 25% dispersion of carbon black, 13.0 g of alkali-soluble resin (solid content 3.5 g) prepared in Synthesis Example 4 as alkali-soluble resin, 3.5 g of dipentaerythritol hexaacrylate as a polymerizable compound, 2.5 g of photopolymerization initiator Irgacure-369 , 1 g of 3- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} propanoic acid, 0.5 g of 4,4'-diethylaminobenzophenone, organic solvent 48.75 g of PGMEA was mixed for 3 hours to prepare a photosensitive resin composition.

Example  4

Pigment C.I. 50 g of 15% dispersion of Pigment Red 254, 12.5 g of alkali-soluble resin solution prepared in Synthesis Example 3 (5.0 g of solid content), 3 g of dipentaerythritol hexaacrylate as a polymerizable compound, 2 g of photopolymerization initiator Irgacure-369, PGMEA as an organic solvent 32.5 g of the mixture was mixed for 3 hours to prepare a photosensitive resin composition.

Example  5

Pigment C.I. 50 g of 15% dispersion of Pigment Red 254, 18.5 g of alkali-soluble resin solution prepared in Synthesis Example 4 (5.0 g of solid content), 3 g of dipentaerythritol hexaacrylate as a polymerizable compound, 2 g of photopolymerization initiator Irgacure-369, PGMEA as an organic solvent 26.5 g were mixed for 3 hours to prepare a photosensitive resin composition.

Comparative Example 1-3. Photosensitive resin composition]

Comparative example  One

A photosensitive resin composition was prepared in the same manner as in Example 1, except that 13.4 g of Polymer Solution E of Comparative Synthesis Example 1 was used as the alkali-soluble resin.

Comparative example  2

A photosensitive resin composition was prepared in the same manner as in Example 4, except that 12.5 g of the polymer solution F of Comparative Synthesis Example 2 was used as the alkali-soluble resin.

Comparative example  3

A photosensitive resin composition was prepared in the same manner as in Example 5, except that 18.5 g of the polymer solution G of Comparative Synthesis Example 3 was used as the alkali-soluble resin.

Experimental Example  1. Evaluation of sensitivity and chemical resistance of photosensitive resin composition

The following method was used to test the sensitivity and chemical resistance of the photosensitive resin composition prepared according to the present invention.

The photosensitive resin composition solutions prepared by Examples 1 to 5 and Comparative Examples 1 to 3 were respectively spin coated on glass and prebakeed at about 100 ° C. for 2 minutes to form a film. Each formed film was exposed to an energy of 100 or 200 mJ / cm 2 under a high-pressure mercury lamp using a photomask, and then the pattern was subjected to time using an aqueous KOH alkali solution of pH 11.3 to 11.7. Developed and washed with deionized water. It was then postbake at 200 ° C. for about 40 minutes.

The sensitivity of each photosensitive resin composition was determined using the minimum pixel size remaining after development when exposed using a Line & space mask.

The chemical resistance of each photosensitive resin composition was immersed in 60 ° C. NMP (N-methyl pyrrolidone) for 3 minutes in the case of the black matrix photosensitive material, followed by optical microscope observation of the shape and the change in thickness. After soaking for 5 minutes, it was determined by measuring color change (ΔEab *), thickness change, and optical microscope observation.

Experimental results for the sensitivity and chemical resistance are shown in Tables 1 and 2 below.

As shown in Table 1, as a result of applying the photosensitive resin compositions of Examples 1 to 3 of the present invention to the black matrix photoresist, the minimum pixel size remaining after development was 10 to 14 µm, which is significantly higher than that of 28 µm of Comparative Example 1. Low sensitivity can be confirmed. In addition, the thickness change after immersion in NMP for 3 minutes shows 1.0 ~ 1.8%, it can be seen that the chemical resistance to chemicals is much higher than 5.4% of Comparative Example 1.

As shown in Table 2, as a result of applying the photosensitive resin compositions of Examples 4 and 5 of the present invention to the color filter photosensitive member, the minimum pixel size remaining after development was less than 10 µm, 20 µm of Comparative Examples 2 and 3 and It is remarkably lower than 14 μm, which shows excellent sensitivity characteristics. In addition, the change in thickness after 5 minutes of immersion in NMP showed 5.5 and 7.3%, indicating that the chemical resistance to chemicals was much higher than that of 16.4% and 8.2% of Comparative Examples 2 and 3, and the color filter photoresist Color change also shows a lower value, it can be confirmed that the excellent chemical resistance.

After immersing the color filter photosensitive material to which the photosensitive composition was applied for 5 minutes at 60 ° C. NMP, the result of observing with an optical microscope is shown in FIGS.

As shown in FIG. 1 and FIG. 2, the color filter photosensitive material to which the photosensitive resin compositions of Examples 4 and 5 were applied was observed with an optical microscope, and no change was observed.

On the other hand, as shown in Figure 3, the color filter photosensitive material to which the photosensitive resin composition of Comparative Example 2 is applied was confirmed that the surface is very rough and the color change is severe. In addition, as shown in Figure 4, the color filter photosensitive material to which the photosensitive resin composition of Comparative Example 3 was applied, it was confirmed that a pin hole occurred on the surface.

Therefore, it was confirmed that the photosensitive composition containing the alkali-soluble resin according to the present invention is superior in sensitivity and chemical resistance as compared with the existing photosensitive composition.

The photosensitive resin composition according to the present invention has good sensitivity and excellent chemical resistance due to the alkali-soluble resin of the present invention. Since the sensitivity is excellent, the exposure time can be shortened, which is useful for improving the manufacturing processability. The chemical resistance is excellent, and thus there is little risk of damage to the pattern due to the chemicals processed in the process.

Claims (18)

In the composition for producing alkali-soluble resin, a) diol compound having two polymerizable unsaturated groups, b) acid dianhydrides, and c) Alkali-soluble resin manufacturing composition containing a diamine compound. The composition for producing an alkali-soluble resin according to claim 1, further comprising d) acid anhydride in the alkali-soluble resin composition. The composition for producing an alkali-soluble resin according to claim 1, wherein the aol diol compound having two polymerizable unsaturated groups is represented by the following [Formula 1]. [Formula 1]

Where R is hydrogen or methyl, X is C _n H _2n ,-(CH ₂ CH ₂ O) _n CH ₂ CH ₂ -,-(CHCH ₃ CH ₂ ) _n OCHCH ₃ CH _2- , (where n is an integer from 1 to 10),

Wherein Y is a direct bond, C ₁ -C ₆ alkylene, ketone, -O-, -S-, -SO _2- , hexafluoropropyl, -OC ₆ H ₄ O-, -OC ₆ H ₄ One selected from the group consisting of C (CH ₃ ) ₂ C ₆ H ₄ O-), 9,9-bisphenol florenyl and 9,9-bis (4-ethoxyphenyl) florenyl Is selected. According to claim 1, wherein b) the acid dianhydride is a compound having two acid anhydride groups in one molecule, 1,2,4,5-benzene tetracarboxylic dianhydride, 3,3 ', 4,4'-benzo Phenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfide dianhydride, bis (3,4-dicarboxyphenyl ) Sulfone dianhydride, ethylene glycol bis (4- trimellitate) dianhydride, glycerol bis (1,3- trimellitic anhydride) -2-acetate, 1,4-bis (2,3-dicarboxyphenoxy) benzene Dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy Diphenyl dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl ether dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfone dianhydride , Bis (3,4- Carboxyphenyl) methane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2-bis (3,4-dicarboxyphenyl) ethane dianhydride, 2,2-bis (3 , 4-dicarboxyphenyl) propane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 4- (2,3-dicarboxyphenoxy) -4 ' -(3,4-dicarboxyphenoxy) diphenyl-2,2-propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-bis ( 3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride and 4,4'-bis [2 -(3,4-dicarboxyphenyl) hexafluoroisopropyl] diphenyl ether dianhydride The composition for alkali-soluble resin manufacture which is 1 or more types chosen from the group which consists of dianhydrides. The method of claim 1, wherein c) the diamine compound is m-phenylene diamine, p-phenylene diamine, 1,3-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) propane, 4,4'-diamino-diphenyl methane, 1,2-bis (4-aminophenyl) ethane, 1,1-bis (4-aminophenyl) ethane, 2,2'-diamino-diethyl sulfide, Bis (4-aminophenyl) sulfide, bis (4-aminophenyl) sulfone, bis (4-aminophenyl) ether, 4,4'-diamino-benzophenone, 2,2-bis (4-aminophenyl) hexa Fluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 4,4'-bis [2- (4-aminophenoxyphenyl) hexafluoroisopropyl] di Phenyl ether, 4,4 '-(1,4-phenylenedioxy) dianiline, 4,4'-(1,3-phenylenedioxy) dianiline, and 4,4 '-(4,4'-iso A composition for producing an alkali-soluble resin, which is at least one member selected from the group consisting of propylidene diphenyl-1,1'-diyl-dioxy) dianiline. The method of claim 2, wherein d) the acid anhydride is succinic anhydride, glutaric anhydride, methyl succinic anhydride, maleic anhydride, methyl maleic anhydride, phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, At least one member selected from the group consisting of 3,4,5,6-tetrahydrophthalic anhydride, hexahydropthalic anhydride, and cis-5-norbornene- (endo, exo) -2,3-dicarboxylic anhydride Alkali-soluble resin manufacturing composition. The method of claim 1, a) with respect to 100 mol of a diol compound having two polymerizable unsaturated groups, b) 50 to 150 moles of acid dianhydride, c) 0.1 to 20 moles of diamine compound Alkali-soluble resin manufacturing composition characterized by including. The method of claim 2, a) with respect to 100 mol of a diol compound having two polymerizable unsaturated groups, b) 50 to 150 moles of acid dianhydride, c) 0.1 to 20 moles of diamine compound, d) 0.1-20 moles of acid anhydride Alkali-soluble resin manufacturing composition characterized by including. The alkali-soluble resin formed by superposing | polymerizing in the composition for alkali-soluble resin manufacture of any one of Claims 1-8 by alternating copolymerization. The alkali-soluble resin of claim 9, wherein the acid value of the alkali-soluble resin is in the range of 50 to 200 KOH mg / g, and the weight average molecular weight is in the range of 3,000 to 100,000. The alkali-soluble resin according to claim 9, wherein a) a diol compound having two polymerizable unsaturated groups and b) an acid dianhydride are reacted to prepare an alternating copolymer, and then c) a diamine compound is added to the alternating copolymer. . The method of claim 9, wherein a) a diol compound having two polymerizable unsaturated groups, b) an acid dianhydride, and d) an acid anhydride is reacted to prepare an alternating copolymer, and then c) a diamine compound to the alternating copolymer. Alkali-soluble resin formed by adding. The alkali-soluble resin according to claim 11 or 12, which is formed by adding c) a diamine compound and then further adding an acid anhydride. In the photosensitive resin composition, 1) Alkali-soluble resin formed by superposing | polymerizing by the copolymerization of the composition for alkali-soluble resin manufacture of any one of Claims 1-8; 2) a polymerizable compound having an ethylenically unsaturated bond; 3) photopolymerization initiator; And 4) solvent Photosensitive resin composition comprising a. The method of claim 14, 1) 1 to 20 parts by weight of alkali-soluble resin, 2) 0.5 to 30 parts by weight of a polymerizable compound having an ethylenically unsaturated bond; 3) 0.1 to 5 parts by weight of the photopolymerization initiator; And 4) 10 to 95 parts by weight of solvent Photosensitive resin composition comprising a. 15. The photosensitive film according to claim 14, further comprising at least one additive selected from the group consisting of alkali-soluble acrylic copolymer resins, colorants, curing accelerators, thermal polymerization inhibitors, plasticizers, adhesion promoters, fillers and surfactants. Resin composition. The photosensitive resin composition according to claim 16, wherein the amount of the alkali-soluble acrylic copolymer resin included as an additive is less than 20 parts by weight in combination with the alkali-soluble resin. The method of claim 16, wherein the colorant is 0.5 to 20 parts by weight, the other additives are 0.01 to 10 parts by weight It contains, Photosensitive resin composition characterized by the above-mentioned.

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