TWI557510B - Photosensitive resin composition and uses thereof - Google Patents

Description

Photosensitive resin composition and application thereof

The present invention relates to a photosensitive resin composition for a black matrix and a color filter and a liquid crystal display element formed using the black matrix. In particular, a photosensitive resin composition for a black matrix having improved resolution and a taper angle, and a color filter and a liquid crystal display element formed using the black matrix are provided.

In recent years, various liquid crystal display technologies have flourished, and in order to improve the contrast and display quality of current liquid crystal displays, black is generally placed in the stripe and dot gaps of the color filters in the display. matrix. The black matrix described above can prevent problems such as a decrease in contrast due to light leakage between pixels and a decrease in color purity. Conventionally, materials used for the black matrix are mainly vapor-deposited films containing chromium or chromium oxide. However, when the vapor deposited film is used as a material of a black matrix, there are disadvantages such as complicated process and high material cost. In order to solve this problem, a technique of forming a black matrix by photolithographic use of a photosensitive resin composition has been proposed.

At present, the industry has increasingly increased the shading requirements of the black matrix, and one of the solutions is to increase the amount of black pigment used, thereby improving the shading of the black matrix. For example, Japanese Laid-Open Patent Publication No. 2006-259716 discloses a photosensitive resin composition for a black matrix comprising a high-use black pigment, an alkali-soluble resin, a photopolymerization initiator, and a difunctional group. Reactive monomer and organic solvent. Among them, a reactive monomer having a difunctional group can improve the reaction between the compounds to form a high-definition pattern. Thereby, in the photosensitive resin composition, while increasing the light-shielding property so as to increase the amount of use of the black pigment, the taper angle of the photosensitive resin composition can be maintained.

In addition, Japanese Laid-Open Patent Publication No. 2008-268854 discloses a photosensitive resin composition for a black matrix. The photosensitive resin composition contains an alkali-soluble resin having a carboxylic acid group and an unsaturated group, a photopolymerizable monomer containing an ethylenically unsaturated group, a photopolymerization initiator, and a high-usage black pigment. In the photosensitive resin composition for black matrices, the resolution of the photosensitive resin composition of the high-use black pigment is improved by using a specific alkali-soluble resin.

Although the photosensitive resin composition in which the amount of the black pigment used is increased in the prior art, the resolution and the like can be increased. However, the resolution and the taper angle of the photosensitive resin composition of each of the above-mentioned prior methods have not yet been accepted by the industry. In view of this, there is still a need to develop a photosensitive resin composition for a black matrix which can improve the resolution and the taper angle.

The present invention provides a photosensitive resin composition for a black matrix having excellent resolution and taper angle by using a component which provides a specific polyoxyalkylene polymer and a special photoinitiator.

Accordingly, the present invention provides a photosensitive resin composition comprising: a polyoxyalkylene polymer (A); a compound (B) having an ethylenically unsaturated group; a photoinitiator (C); a solvent (D); a black pigment (E); wherein: the polymerization decane monomer of the polyoxyalkylene polymer (A) comprises at least one decane monomer having the structure of the formula (I): Si(X ¹ ) _t (OX ² ) _{4- t} formula (I)

t is an integer from 1 to 3, and when t represents 2 or 3, the plurality of X ¹ are each the same or different; and when 4-t represents 2 or 3, the plurality of X ² are each the same or different; at least one X ¹ represents a substituted alkyl group of an anhydride-C ₁ to C _10, the epoxy-substituted the C ₁ to C ₁₀ alkyl group or of the epoxy-substituted alkoxy group, and the remaining X ¹ represents hydrogen, C _a C ₁ alkyl group, a C ₂ to C ₁₀ alkenyl group or a C ₆ to C ₁₅ aryl group; and X ² represents hydrogen, a C ₁ to C ₆ alkyl group, a C ₁ to C ₆ fluorenyl group or An aromatic group of C ₆ to C ₁₅ ; the photoinitiator (C) comprising the α-ketoxime ester compound (C-1) represented by the formula (II):

In the formula (II): Y ¹ represents a methylphenyl group having 1 to 5 methyl groups; Y ² represents a C ₁ to C ₁₀ alkyl group, a benzamidine group or a C ₃ to C ₆ cycloalkyl group; Y ³ represents a methyl group, an ethyl group, a propyl group or a benzamidine group; and Y ⁴ represents a -H group. , , , , Wherein a represents methyl or ethyl; and b represents -H or methyl.

The present invention also provides a black matrix formed of the aforementioned photosensitive resin composition.

The present invention further provides a color filter comprising the aforementioned black matrix.

The present invention further provides a liquid crystal display element comprising the aforementioned color filter.

Figure 1 is a graph showing the relationship between the taper angle and the resist pattern in a scanning electron microscope.

The present invention provides a photosensitive resin composition comprising: a polyoxyalkylene polymer (A); a compound (B) having an ethylenically unsaturated group; a photoinitiator (C); a solvent (D); and a black pigment (E); wherein: the polymerization decane monomer of the polyoxyalkylene polymer (A) comprises at least one decane monomer having the structure of the formula (I): Si(X ¹ ) _t (OX ² ) _4-t (I)

t is an integer from 1 to 3, and when t represents 2 or 3, the plurality of X ¹ are each the same or different; and when 4-t represents 2 or 3, the plurality of X ² are each the same or different; at least one X ¹ represents a substituted alkyl group of an anhydride-C ₁ to C _10, the epoxy-substituted the C ₁ to C ₁₀ alkyl group or of the epoxy-substituted alkoxy group, and the remaining X ¹ represents hydrogen, C _a C ₁ alkyl group, a C ₂ to C ₁₀ alkenyl group or a C ₆ to C ₁₅ aryl group; and X ² represents hydrogen, a C ₁ to C ₆ alkyl group, a C ₁ to C ₆ fluorenyl group or An aromatic group of C ₆ to C ₁₅ ; the photoinitiator (C) comprising the α-ketoxime ester compound (C-1) represented by the formula (II):

In the formula (II): Y ¹ represents a methylphenyl group having 1 to 5 methyl groups; Y ² represents a C ₁ to C ₁₀ alkyl group, a benzamidine group or a C ₃ to C ₆ cycloalkyl group; Y ³ represents a methyl group, an ethyl group, a propyl group or a benzamidine group; and Y ⁴ represents a -H group. , , , , Wherein a represents methyl or ethyl; and b represents -H or methyl.

Polyoxyalkylene polymer (A) can be selected from decane monomer and polyoxane The polymer or decane monomer is combined with the polyoxyalkylene prepolymer to form a polymerization (ie, hydrolysis and partial condensation).

The decane monomer for polymerization of the polyoxyalkylene polymer (A) according to the present invention comprises at least one decane monomer having the structure of the formula (I): Si(X ¹ ) _t (OX ² ) _4-t (I)

t is an integer from 1 to 3, and when t represents 2 or 3, the plurality of X ¹ are each the same or different; and when 4-t represents 2 or 3, the plurality of X ² are each the same or different; at least one X ¹ represents a substituted alkyl group of an anhydride-C ₁ to C _10, the epoxy-substituted the C ₁ to C ₁₀ alkyl group or of the epoxy-substituted alkoxy group, and the remaining X ¹ represents hydrogen, C _a C ₁ alkyl group, a C ₂ to C ₁₀ alkenyl group or a C ₆ to C ₁₅ aryl group; and X ² represents hydrogen, a C ₁ to C ₆ alkyl group, a C ₁ to C ₆ fluorenyl group or An aromatic group of C ₆ to C ₁₅ .

Specific examples of the acid anhydride group-substituted and C ₁ to C ₁₀ alkyl group are, for example, ethyl succinic anhydride, propyl succinic anhydride or propyl glutaric anhydride.

Specific examples of the epoxy group-substituted and C ₁ to C ₁₀ alkyl group, such as oxetanylpentyl or 2-(3,4-epoxycyclohexyl)ethyl [2-(3, 4-epoxycyclohexyl)ethyl] and the like.

Specific examples of the epoxy group-substituted oxyalkyl group are, for example, glycidoxypropyl or 2-oxetanylbutoxy.

In X ² , the aforementioned alkyl group may include, but is not limited to, methyl, ethyl, n-propyl, isopropyl or n-butyl groups and the like. The thiol group can include, but is not limited to, an ethyl group. The aryl group can include, but is not limited to, a phenyl group.

The decane monomer represented by the formula (I) may include, but is not limited to, 3-glycidoxypropyltrimethoxysilane (TMS-GAA), 3-glycidoxypropyltriethyl 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane[2-(3,4-epoxycyclohexyl)ethyl Trimethoxy silane], 2-oxetanylbutoxypropyltriphenoxysilane, 3-(triphenyloxyindenyl)propyl succinic anhydride, 3-(trimethoxyindenyl) ) propyl glutaric anhydride (TMSG), 3-(triethoxymethyl) glutaric anhydride, 3-(triphenyloxyindenyl) propyl glutaric anhydride, diisopropoxy-di ( Diisopropoxy-di(2-oxetanylbutoxypropyl)silane; DIDOS], bis(3-epoxypropenylpentyl)dimethoxydecane [di(3-oxetanylpentyl) Dimethoxy silane], (di-n-butoxycarbonyl) bis(propyl succinic anhydride), (dimethoxyindenyl) bis(ethyl succinic anhydride), 3-glycidoxy propyl 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyldimethylethoxysilane, bis(2-propylene oxide-butoxypentyl)-2 -di(2-oxetanylbutoxypentyl)-2-oxetanylpentylethoxysilane, tris(2-oxetanylpentyl)methoxysilane (phenoxy Mercapto) tris(propyl succinic anhydride), (methyl methoxy decyl) bis (ethyl succinic anhydride); manufactured by Toagosei Co., Ltd., model TMSOX-D 2-epoxypropane butoxide 2-oxetanylbutoxypropyltrimethoxysilane, 2-oxetanylbutoxypropyltriethoxysilane of the type TESOX-D, model 3-SOX-ethyl 3-ethyl- 3-{[3-(trimethoxyindenyl)propoxy]methyl} propylene oxide; 3-(trimethoxyindenyl)propyl butylate manufactured by Shin-Etsu Chemical Co., Ltd., model X-12-967 Diacid anhydride; 3-(triethoxyindenyl)propyl succinic anhydride manufactured by WACKER, model GF-20. The decane monomers represented by the above formula (I) may be used singly or in combination of plural kinds.

In another preferred embodiment of the present invention, the decane monomer for polymerization of the polyoxyalkylene polymer (A) of the present invention further comprises a decane monomer represented by the following structural formula (I-1): Si (X) ³ ) _u (OX ⁴ ) _4-u (I-1)

Wherein: X ³ represents a group selected from the group consisting of a hydrogen atom, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₀ alkenyl group, and a C ₆ to C ₁₅ aryl group, wherein the C ₁ to C ₁₀ alkyl group Does not contain a carboxylic anhydride substituent; X ⁴ is independently selected from the group consisting of a hydrogen atom, a C ₁ to C ₆ alkyl group, a C ₁ to C ₆ fluorenyl group, and a C ₆ to C ₁₅ aryl group; and u represents An integer from 1 to 3; when u represents 2 or 3, the plural X ³ may be the same or different; when (4-u) represents 2, 3 or 4, the plural X ⁴ may be the same or different.

In X ³ , the alkyl group may include, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-hexyl, n-butyl, trifluoromethyl, 3,3 , 3-trifluoropropyl, 3-aminopropyl, 3-mercaptopropyl or 3-isocyanatopropyl, and the like. The alkenyl group may include, but is not limited to, a vinyl group, a 3-propenyloxypropyl group, a 3-methylpropenyloxypropyl group, and the like. The aryl group may include, but is not limited to, phenyl, tolyl, p-hydroxyphenyl, 1-(p-hydroxyphenyl)ethyl, 2-(p-hydroxyphenyl)ethyl, 4-hydroxy-5- ( p-Hydroxyphenylcarbonyloxy)pentyl or naphthyl and the like.

In X ⁴ , the alkyl group may include, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, and the like. The thiol group can include, but is not limited to, an ethyl group. The aryl group can include, but is not limited to, a phenyl group.

The decane monomer represented by the formula (I-1) may include, but is not limited to, tetramethoxy decane, tetraethoxy decane, tetraethoxy decane, tetraphenoxy decane, methyl trimethoxy decane, Triethoxy decane, methyl triisopropoxy decane, methyl tri-n-butoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, ethyl triisopropoxy decane, B Tri-n-butoxy decane, n-propyl trimethoxy decane, n-propyl triethoxy decane, n-butyl trimethoxy decane, n-butyl triethoxy decane, n-hexyl trimethoxy decane, hexane Triethoxy decane, decyl trimethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, p-hydroxyphenyl trimethyl Oxydecane, 1-(p-hydroxyphenyl)ethyltrimethoxynonane, 2-(p-hydroxyl) Phenyl)ethyltrimethoxydecane, 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxydecane, trifluoromethyltrimethoxydecane, trifluoromethyltriethoxy Baseline, 3,3,3-trifluoropropyltrimethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, dimethyldimethoxydecane, dimethyl Diethoxy decane, dimethyl diethoxy decane, di-n-butyl dimethoxy decane, diphenyl dimethoxy decane, trimethyl methoxy decane, tri-n-butyl ethoxy Baseline, 3-mercaptopropyltrimethoxydecane, 3-propenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane or 3-methylpropenyloxypropane Triethoxy decane and the like. The decane monomers represented by the above formula (I-1) may be used singly or in combination of plural kinds.

Preferably, the polyoxynitane prepolymer for polymerization of the polyoxyalkylene polymer (A) of the present invention comprises a polyoxyalkylene represented by the following formula (I-2):

Wherein: X ⁵ , X ⁶ , X ⁷ and X ⁸ may be the same or different and are respectively selected from a hydrogen atom, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₆ alkenyl group and a C ₆ to C ₁₅ a group consisting of aryl groups; wherein the alkyl, alkenyl or aryl group preferably contains a substituent; wherein each X ⁵ may be the same or different, and each X ⁶ may be the same or different; the aforementioned alkyl group These may include, but are not limited to, methyl, ethyl or n-propyl groups and the like. The alkenyl group may include, but is not limited to, a vinyl group, a propylene methoxy propyl group, a methacryloxypropyl group, and the like. The aryl group may include, but is not limited to, phenyl, tolyl or naphthyl, etc.; s is an integer between 1 and 1000; preferably, s is an integer between 3 and 300; more preferably, s is An integer between 5 and 200.

X ⁹ and X ¹⁰ are each selected from the group consisting of a hydrogen atom, a C ₁ to C ₆ alkyl group, a C ₁ to C ₆ fluorenyl group, and a C ₆ to C ₁₅ aryl group; wherein the alkyl group and the fluorenyl group are Or an aryl group preferably contains a substituent. Preferably, the alkyl group is, for example but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, and the like; the fluorenyl group is, for example, but not limited to, an ethyl group; the aryl group is, for example, but not limited to, a phenyl group.

The polyoxyalkylene represented by the formula (I-2) may include, but is not limited to, 1,1,3,3-tetramethyl-1,3-dimethoxydioxane, 1, 1, 3, 3 -tetramethyl-1,3-diethoxydioxane, 1,1,3,3-tetraethyl-1,3-diethoxydioxanane or stanol end of Gelest Polyoxane, the models are DM-S12 (molecular weight 400 to 700), DMS-S15 (molecular weight 1500 to 2000), DMS-S21 (molecular weight 4200), DMS-S27 (molecular weight 18000), DMS -S31 (molecular weight 26000), DMS-S32 (molecular weight 36000), DMS-S33 (molecular weight: 43500), DMS-S35 (molecular weight: 49,000), DMS-S38 (molecular weight: 58,000), DMS-S42 (molecular weight 77000) or PDS-9931 (molecular weight 1000 to 1400) and the like. The polyoxyalkylene represented by the formula (I-2) may be used singly or in combination of plural kinds.

Preferably, the polyoxyalkylene polymer (A) of the present invention can be prepared by copolymerization of the decane monomer and/or polydecane prepolymer, or in combination with silicon dioxide particles. Copolymerization is carried out to prepare.

The average particle diameter of the cerium oxide particles is not particularly limited, and the average particle diameter thereof ranges from 2 nm to 250 nm. Preferably, the average particle size ranges from 5 nm to 200 nm. More preferably, the average particle diameter ranges from 10 nm to 100 nm.

The cerium oxide particles may include, but are not limited to, those manufactured by Catalyst Chemical Co., Ltd., model number OSCAR 1132 (particle diameter: 12 nm, and dispersant is methanol), OSCAR 1332 (particle diameter: 12 nm, and dispersant is n-propanol) , OSCAR 105 (particle size is 60 nm, and the dispersant is γ-butyrolactone) or OSCAR 106 (particle size is 120 nm, and the dispersant is diacetone alcohol), etc.; manufactured by Fuso Chemical Co., Ltd., model Quartron PL -1-IPA (particle size 13 nm, and dispersant is isopropanone), Quartron PL-1-TOL (particle size 13 nm, and dispersant is toluene), Quartron PL-2L-PGME (particle size 18 nm, and The dispersant is propylene glycol monomethyl ether) or Quartron PL-2L-MEK (particle size is 18nm, and the dispersant is methyl ethyl ketone); manufactured by Nissan Chemical Co., Ltd., model IPA-ST (particle size 12nm, and dispersant is isopropanol), EG-ST (particle size 12nm, and dispersant) It is a product of ethylene glycol), IPA-ST-L (having a particle diameter of 45 nm, and a dispersing agent is isopropyl alcohol) or IPA-ST-ZL (having a particle diameter of 100 nm, and the dispersing agent is isopropyl alcohol). The cerium oxide particles may be used singly or in combination of plural kinds.

The above partial condensation reaction may be carried out by a usual method, for example, by adding a solvent and water to a decane monomer and/or a polyoxyalkylene prepolymer, and optionally adding a catalyst. Next, the mixture is heated and stirred at 50 ° C to 150 ° C for 0.5 hour to 120 hours. When stirring, the reaction can remove by-products (alcohols or water, etc.) by distillation.

The total amount used based on the decane monomer and/or polydecane prepolymer is 100 g, and the solvent is used in an amount of 15 g to 1200 g. Preferably, the solvent is used in an amount of from 20 grams to 1100 grams. More preferably, the solvent is used in an amount of from 30 g to 1000 g.

The water used for the hydrolysis is used in an amount of from 0.5 mol to 2 mol based on 1 mol of the hydrolyzable group contained in the decane monomer and/or polydecane prepolymer.

The above catalyst is not particularly limited. Preferably, the catalyst may be selected from an acid catalyst or a base catalyst. The acid catalyst may include, but is not limited to, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, oxalic acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acid or anhydride thereof, or an ion exchange resin. The base catalyst may include, but is not limited to, diethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, trihexylamine, triheptylamine, trioctylamine, diethanolamine, triethanolamine, sodium hydroxide, Potassium hydroxide, an alkoxysilane having an amine group, an ion exchange resin, or the like.

The catalyst is used in an amount ranging from 0.005 g to 15 g based on the total amount of the decane monomer and/or polydecane prepolymer being 100 g. Preferably, the catalyst is used in an amount ranging from 0.01 grams to 12 grams. More preferably, the catalyst is used in an amount ranging from 0.05 g to 10 g.

Based on the viewpoint of stability, the polyoxyalkylene obtained by the condensation reaction is polymerized. The compound (A) is preferably free from by-products (e.g., alcohols or water) and a catalyst, and thus the obtained polyoxyalkylene polymer (A) can be selectively purified. The purification method is not particularly limited, and it is preferred to dilute the polyoxyalkylene polymer (A) with a hydrophobic solvent, followed by concentrating the organic layer washed several times with water by an evaporator to remove the alcohol or water. Alternatively, the catalyst can be removed using an ion exchange resin.

When the polyoxyalkylene polymer (A) is not used, the resolution of the photosensitive resin composition is not good.

The photosensitive resin composition according to the present invention contains a compound (B) having an ethylenically unsaturated group.

The compound (B) having an ethylenically unsaturated group according to the present invention may be selected from a compound having one ethylenically unsaturated group or a compound having two or more (including two) ethylenically unsaturated groups.

Specific examples of the aforementioned compound having one ethylenically unsaturated group include (meth)acrylamide, (meth)acryl morpholine, and (meth)acrylic acid-7-amino group- 3,7-Dimethyloctyl, isobutoxymethyl(meth)acrylamide, isobornyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, (meth)acrylic acid 2-ethylhexyl ester, ethyl diethylene glycol (meth) acrylate, trioctyl (meth) acrylamide, diacetone (meth) acrylamide, dimethyl (meth) acrylate Aminoethyl ester, dodecyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, nitrogen, nitrogen-dimethyl ( Methyl) acrylamide, tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, Tetrabromophenyl (meth)acrylate, 2-tetrabromophenoxyethyl (meth)acrylate, 2-trichlorophenoxyethyl (meth)acrylate, tribromobenzene (meth)acrylate Ester, 2-tribromophenoxyethyl (meth)acrylate, 2-hydroxy-(meth) propylene Ethyl ester, propyl 2-hydroxy-(meth)acrylate, vinyl caprolactam, nitrogen-vinylpyrrolidone, phenoxyethyl (meth)acrylate, pentachlorophenyl (meth)acrylate, Pentabromophenyl methacrylate, poly Ethylene (meth) acrylate, poly (mono) (meth) acrylate, methacrylate (meth) acrylate, and the like. The above compound (B-1) having one ethylenically unsaturated group may be used singly or in combination of two or more.

Specific examples of the compound having two or more (including two) ethylenically unsaturated groups include ethylene glycol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, and triethylene glycol di (Meth) acrylate, tetraethylene glycol di(meth) acrylate, tris(2-hydroxyethyl)isocyanate di(meth) acrylate, tris(2-hydroxyethyl)isocyanate (Meth) acrylate, caprolactone modified tris(2-hydroxyethyl)isocyanate tri(meth) acrylate, tris(methyl) acrylate trimethylol propyl ester, ethylene oxide ( Ethylene oxide, EO) modified trimethylolpropyl tris(meth)acrylate, propylene oxide (PO) modified tris (tri)methyl trimethacrylate, tripropylene glycol di Methyl) acrylate, neopentyl glycol di(meth) acrylate, 1,4-butanediol di(meth) acrylate, 1,6-hexanediol di(meth) acrylate, pentaerythritol III (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol Penta(meth) acrylate, Dipentaerythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, tetra(meth) acrylate tris Di(trimethylolpropane)tetra(meth)acrylate, epoxide-modified bisphenol A di(meth)acrylate, propylene oxide modified bisphenol A di(methyl) Acrylate, ethylene oxide modified hydrogenated bisphenol A di(meth)acrylate, propylene oxide modified hydrogenated bisphenol A di(meth)acrylate, propylene oxide modified Triglyceride (meth) acrylate, ethylene oxide modified bisphenol F di(meth) acrylate, novolak polyglycidyl ether (meth) acrylate or the like, or a combination thereof . The above compound having two or more (including two) ethylenically unsaturated groups may be used singly or in combination of two or more.

Specific examples of the above compound (B) having an ethylenically unsaturated group include: Trimethylolpropyl triacrylate, trimethylolpropyl triacrylate modified with ethylene oxide, trimethylolpropyl triacrylate modified with propylene oxide, pentaerythritol triacrylate, pentaerythritol tetraacrylate Ester, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, caprolactone modified dipentaerythritol hexaacrylate, ditrimethylolpropyl methacrylate, propylene oxide modified glycerol Triacrylate or an analog thereof, or a combination of the above compounds.

The compound (B) having an ethylenically unsaturated group is preferably trimethylolpropyl triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate or a combination of the above compounds.

The compound (B) having an ethylenically unsaturated group is used in an amount of 20 to 200 parts by weight, preferably 30 to 180 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer (A); It is preferably 40 to 160 parts by weight.

The photoinitiator (C) of the present invention comprises the α-ketooxime ester compound (C-1) represented by the formula (II):

The Y ¹ represents a methylphenyl group having 1 to 5 methyl groups, and a specific example thereof is , or Y ² represents a C ₁ to C ₁₀ alkyl group, a benzylidene group or a C ₃ to C ₆ cycloalkyl group. Preferably, the aforementioned alkyl group may be, for example, a methyl group; Y ³ represents a methyl group, an ethyl group, a propyl or benzhydryl group, wherein ethyl is preferred; Y ⁴ represents -H, , Wherein a represents methyl or ethyl; and b represents -H or methyl.

In a preferred embodiment of the present invention, the α-ketooxime ester compound (C-1) represented by the formula (II) includes a structure represented by the following formulas (II-1) to (II-12):

In a specific example of the present invention, the α-ketooxime ester compound (C-1) represented by the formula (II) is obtained by the following reaction: First, an oxazole compound or a ruthenium chloride compound (acyl) Chloride) and n-methyl phenyl acyl chloride are sequentially placed in the presence of aluminum chloride, and the reaction can give a mercapto compound which is catalyzed by a base catalyst. The α-ketooxime compound is reacted with isoamyl nitrite; and then the α-ketooxime compound is reacted with a ruthenium chloride compound under the catalysis of a triethylamine catalyst to obtain the above formula (II). The α-ketooxime ester compound shown.

The α-ketooxime ester compound (C-1) having a structure of the formula (II) is used in an amount of 10 to 100 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer (A); preferably. It is 12 to 90 parts by weight; more preferably 15 to 80 parts by weight. When the α-ketooxime ester compound (C-1) represented by the formula (II) is not used, the resolution and the taper angle of the photosensitive resin composition are not good.

In a preferred embodiment of the present invention, the photoinitiator (C) of the present invention further comprises a photoinitiator (C-2), which may include, but is not limited to, an embodiment of the present invention. O-mercapto lanthanide compound, triazabenzene compound, acetophenone compound, diimidazole compound, benzophenone compound, α-diketone compound, keto alcohol compound, keto alcohol ether The compound, the phosphonium oxide compound, the anthraquinone compound, the halogen-containing compound, the peroxide, and the like are described below.

Specific examples of the above O-indenyl lanthanide compound are: 1-[4-(phenylthio)phenyl]-heptane-1,2-dione 2-(O-phenylhydrazinyl), 1 -(4-(phenylthio)phenyl)-octane-1,2-dione-2-indole-oxy-benzoate (for example, OXE-01 manufactured by Ciba Specialty Chemicals), 1-[4 -(phenylhydrazino)phenyl]-heptane-1,2-dione 2-(O-phenylhydrazinyl), 1-[9-ethyl-6-(2-methylbenzhydryl) -9 hydrogen-carbazole-3-substituted]-1-(oxy-acetamidine) (for example, OXE-02 manufactured by Ciba Specialty Chemicals), 1-[9-ethyl-6-(3-methylbenzene) Mercapto)-9H-carbazole-3-substituted]-ethanone 1-(O-acetamidoxime), 1-[9-ethyl-6-benzoin-9H-carbazole-3- Substituent]-ethane ketone 1-(O-ethenyl hydrazine), ethane ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylphenyl fluorenyl)-9H-indole Zyridin-3-substituted]-1-(O-ethylindenyl), ethane ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylphenyl) -9H-carbazole-3-substituted]-1-(O-acetylindenyl), ethane ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylphenyl) )-9H-carbazole-3-substituted]-1-(O-acetamidoxime), ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyran) Benzo hydrazino)-9H-carbazole-3-substituted]-1-(O-ethenyl) Ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxyphenyl)-9H-indazole-3-substituted]-1-(O-) Ethyl hydrazide), ethane ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxyphenyl)-9H-carbazole-3- substituent ]-1-(O-acetylindenyl), ethane ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofurylmethoxyphenyl)-9H-carbazole- 3-Substituent]-1-(O-acetamidoxime), ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylmethoxyphenyl) )-9H-carbazole-3-substituted]-1-(O-acetylindenyl), ethane ketone-1-[9-ethyl-6-{2-methyl-4-(2,2 - dimethyl-1,3-dioxolanyl)phenylhydrazinyl}-9H-indazole-3-substituted]-1-(O-ethylindenyl), ethane ketone-1-[ 9-ethyl-6-{2-methyl-4- (2,2-Dimethyl-1,3-dioxolanyl)methoxybenzoinyl}-9H-indazole-3-substituted]-1-(O-ethylindenyl), etc. .

The aforementioned O-indenyl lanthanide compound is 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-phenylhydrazinyl)[OXE 01], 1 -[9-ethyl-6-(2-methylphenylhydrazino)-9H-indazole-3-substituted]-ethanone 1-(O-ethylindenyl)[OXE 02], ethane Keto-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranmethoxyphenyl)-9H-indazole-3-substituted]-1-(O-ethylindenyl) Ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoquinone} -9H-carbazole-3-substituted]-1-(O-ethylindenyl) and the like are preferred. The above O-indenyl lanthanide compounds may be used singly or in combination of plural kinds, depending on actual needs. If the O-mercaptoquinone-based compound is not used at all, the resulting photosensitive resin composition has a drawback that the adhesion after development is poor.

The above triazabenzene compounds may include, but are not limited to, vinyl-halomethyl-s-triazabenzene compounds, 2-(naphtho-1-substituted)-4,6-bis-halo A bis-s-triazabenzene compound and a 4-(p-aminophenyl)-2,6-di-halomethyl-s-triazabenzene compound.

Specific examples of the aforementioned vinyl-halomethyl-s-triazabenzene compound are: 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triaza Benzene, 2,4-bis(trichloromethyl)-3-(1-p-dimethylaminophenyl-1,3-butadienyl)-s-triazabenzene, 2-trichloro Methyl-3-amino-6-p-methoxystyryl-s-triazabenzene and the like.

Specific examples of the aforementioned 2-(naphtho-1-substituted)-4,6-bis-halomethyl-s-triazabenzene compound are: 2-(naphtho-1-substituted)-4 ,6-bis-trichloromethyl-s-triazabenzene, 2-(4-methoxy-naphtho-1-substituted)-4,6-bis-trichloromethyl-s-triazole Heterobenzene, 2-(4-ethoxy-naphtho-1-substituted)-4,6-bis-trichloromethyl-s-triazabenzene, 2-(4-butoxy-naphtho -l-substituted)-4,6-bis-trichloromethyl-s-triazabenzene, 2-[4-(2-methoxyethyl)-naphtho-1-yl]-4 ,6-bis-trichloromethyl-s-triazabenzene, 2-[4-(2-ethoxyethyl)-naphthyl-1-substituted]-4,6-bis-trichloromethyl Base-s-triazabenzene, 2-[4-(2-butoxyethyl)-naphtho-1- Substituent]-4,6-bis-trichloromethyl-s-triazabenzene, 2-(2-methoxy-naphtho-1-substituted)-4,6-bis-trichloromethyl -s-triazabenzene, 2-(6-methoxy-5-methyl-naphtho-2-substituted)-4,6-bis-trichloromethyl-s-triazabenzene, 2 -(6-methoxy-naphtho-2-substituted)-4,6-bis-trichloromethyl-s-triazabenzene, 2-(5-methoxy-naphtho-1-substituted -4,6-bis-trichloromethyl-s-triazabenzene, 2-(4,7-dimethoxy-naphtho-1-substituted)-4,6-bis-trichloro Methyl-s-triazabenzene, 2-(6-ethoxy-naphtho-2-substituted)-4,6-bis-trichloromethyl-s-triazabenzene, 2-(4 , 5-dimethoxy-naphthyl-1-substituted)-4,6-bis-trichloromethyl-s-triazabenzene and the like.

Specific examples of the aforementioned 4-(p-aminophenyl)-2,6-di-halomethyl-s-triazabenzene compound are: 4-[p-N,N-di(ethoxy) Carbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-methyl-p-N,N-di(ethoxycarbonyl) Aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[p-N,N-bis(chloroethyl)aminophenyl]-2, 6-bis(trichloromethyl)-s-triazabenzene, 4-[o-methyl-p-N,N-bis(chloroethyl)aminophenyl]-2,6-di(three Chloromethyl)-s-triazabenzene, 4-(p-N-chloroethylaminophenyl)-2,6-di(trichloromethyl)-s-triazabenzene, 4-( p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[p-N,N-di(phenyl)amine Phenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(p-N-chloroethylcarbonylaminophenyl)-2,6-di(trichloromethane) -s-triazabenzene, 4-[p-N-(p-methoxyphenyl)carbonylaminophenyl]-2,6-di(trichloromethyl)-s-triaza Benzene, 4-[m-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[inter- Bromo-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6- (trichloromethyl)-s-triazabenzene, 4-[m-chloro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloro) Methyl)-s-triazabenzene, 4-[m-fluoro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl) -s-triazabenzene, 4-[o-bromo-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s- Triazabenzene, 4-[o-chloro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl-2,6-di(trichloromethyl)-s-triazabenzene 4-[o-fluoro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4- [o-bromo-p-N,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)- S-triazabenzene, 4-[o-chloro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene 4-[o-fluoro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[m- Bromo-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-chloro-p-N, N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-fluoro-p-N,N-di(chloroethane) Aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-bromo-p-N-ethoxycarbonylmethylaminophenyl)- 2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-chloro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloro) Methyl)-s-triazabenzene, 4-(m-fluoro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl)-s-triazole Benzene, 4-(o-bromo-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl)-s-triazabenzene, 4-(o- Chloro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(o-fluoro-p-N-ethoxylate Carbocarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m- Bromo-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-chloro-p-N-chloroethylamino group Phenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-fluoro-p-N-chloroethylaminophenyl)-2,6-di(three Chloromethyl)-s-triazabenzene, 4-(o-bromo-p-N-chloroethylaminophenyl)-2,6-di(trichloromethyl)-s-triazabenzene , 4-(o-chloro-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(o-fluoro-p-N -Chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 2,4-bis(trichloromethyl)-6-[3-bromo-4- [N,N-Bis(ethoxycarbonylmethyl)amino]phenyl]-1,3,5-triazabenzene and the like.

The aforementioned triazabenzene compound is 4-[m-bromo-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s Triazine, 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazabenzene and the like are preferred. The above-mentioned triazabenzene compounds may be used singly or in combination of plural kinds, depending on actual needs.

Specific examples of the above-mentioned acetophenone compounds are: p-dimethylaminophenone, α,α'-dimethoxyoxyazopropenone, 2,2'-dimethyl-2- Phenylacetophenone, p-methoxyacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholine-1-propane Ketone, 2-benzyl-2-N,N-dimethylamine-1-(4-morpholinophenyl)-1-butanone and the like. The aforementioned acetophenone compound is 2-methyl-1-[4-(methylthio)phenyl]-2-morpholine-1-propanone, 2-benzyl-2-N,N- Dimethylamine-1-(4-morpholinophenyl)-1-butanone or the like is preferred. The above-mentioned acetophenone compounds may be used singly or in combination of plural kinds, depending on actual needs.

Specific examples of the above diimidazole compounds are: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o- Fluorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenyl Imidazole, 2,2'-bis(o-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-ethylphenyl)-4 , 4',5,5'-tetraphenyldiimidazole, 2,2'-bis(p-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2 '-Bis(2,2',4,4'-tetramethoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2-chlorophenyl) )-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole Wait. The above second imidazole compound is preferably 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole. The above-mentioned diimidazole compounds may be used singly or in combination of plural kinds, depending on actual needs.

Specific examples of the above benzophenone compounds are: thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-oxime, benzophenone, 4,4'-bis(dimethyl Amine) benzophenone, 4,4'-bis(diethylamine) benzophenone, and the like. The aforementioned benzophenone compound is preferably 4,4'-bis(diethylamine)benzophenone. The above benzophenone compounds may be used singly or in combination of plural kinds, depending on actual needs.

Specific examples of the above-mentioned α-diketone compound are benzoin, ethenyl and the like. A specific example of the above ketone alcohol compound is benzophenone. Specific examples of the above ketol ether compound are benzophenone methyl ether, benzophenone ethyl ether, and diphenylethanol ketone isopropyl ether. Specific examples of the above fluorinated phosphonium oxide compound are: 2,4,6-trimethylphenylhydrazine diphenylphosphine oxide, bis-(2,6-dimethoxybenzoquinone)-2,4, 4-trimethylphenylphosphine oxide or the like. Specific examples of the above terpenoids are: hydrazine, 1,4-naphthoquinone, and the like. Specific examples of the above halogen-containing compound are: benzoquinone methyl chloride, tribromomethylphenylhydrazine, and tris(trichloromethyl) Base)-s-triazabenzene and the like. Specific examples of the above peroxides include di-tert-butyl peroxide and the like. The above-mentioned α-diketone compound, keto alcohol compound, keto alcohol ether compound, phosphine oxide compound, quinone compound, halogen-containing compound, peroxide, or the like may be used singly or in combination of plural kinds. Depending on actual needs.

The photoinitiator (C) is used in an amount of 15 to 120 parts by weight, preferably 17 to 110 parts by weight, more preferably 20 to 10 parts by weight based on 100 parts by weight of the polyoxyalkylene polymer (A). 100 parts by weight.

The solvent (D) suitable for the present invention is such that it can dissolve the polyoxyalkylene polymer (A), the compound (B) having an ethylenically unsaturated group, the photoinitiator (C), the black pigment (E), and having an unsaturated state. The base resin (F) and the hot starter (G) are preferably not reactive with the above components and have a suitable volatility.

Specific examples of the aforementioned solvent (D) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, and triethyl ethane. Glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol single An alkyl glycol monoalkyl ether compound such as methyl ether or tripropylene glycol monoethyl ether; an alkyl glycol monoalkane such as ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate or propylene glycol methyl ether acetate or propylene glycol diethyl ether acetate Ether acetate compound; diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether or tetrahydrofuran and other ether compounds; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone Or a ketone compound such as diacetone alcohol; an alkyl lactate compound such as methyl lactate or ethyl lactate; methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, 3 Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, Ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxy Butyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, butyrate B Ester, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate or 2- Other ester compounds such as ethyl oxybutyrate; aromatic hydrocarbon compounds such as toluene or xylene; N-methylpyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide An carboxylic acid amine compound; or any combination of the above. The aforementioned solvent (D) can be generally used singly or in combination of plural kinds.

The solvent (D) is used in an amount of from 1200 to 10,000 parts by weight, based on the amount of the polyoxyalkylene polymer (A), preferably from 1600 to 9000 parts by weight; more preferably from 2,000 to 8,000 parts by weight. .

The black pigment (E) suitable for use in the present invention is preferably a black pigment having heat resistance, light resistance and solvent resistance.

Specific examples of the aforementioned black pigment (E) include black organic pigments such as perylene black, cyanine black, and aniline black; and red, blue, green, purple, and yellow colors. Among the pigments such as cyanine and magenta, two or more pigments are selected and mixed to form a nearly blackened mixed color organic pigment; carbon black, chromium oxide, iron oxide A light-shielding material such as titanium black or graphite, wherein the carbon black may include, but not limited to, CIpigment black 7, etc., and the carbon black is specifically manufactured by a product such as Mitsubishi Chemical Corporation (trade name: MA100, MA230). , MA8, #970, #1000, #2350, #2650). The above-mentioned black pigments (E) can be generally used singly or in combination of plural kinds.

The black pigment (E) is used in an amount of from 200 parts by weight to 1200 parts by weight, based on the polyoxymethane polymer (A), in an amount of from 200 parts by weight to 1200 parts by weight; more preferably from 250 to 1100 parts by weight; more preferably from 300 to parts by weight 1000 parts by weight.

The resin (F) having an unsaturated group according to the present invention is obtained by polymerization of a mixture, and the mixture contains an epoxy compound (i) having at least two epoxy groups, and having at least one carboxylic acid group and At least one ethylenically unsaturated compound (ii). Besides, the aforementioned mixture may more optionally contain a carboxylic anhydride compound (iii) and/or an epoxy group-containing compound (iv).

The epoxy compound (i) having at least two epoxy groups has a structure represented by the following formula (III):

Wherein R ¹ , R ² , R ³ and R ⁴ are each the same or different hydrogen atom, a halogen atom, a C ₁ to C ₅ alkyl group, a C ₁ to C ₅ alkoxy group, or a C ₆ to C ₁₂ An aryl group or a C ₆ to C ₁₂ aralkyl group.

The epoxy compound (i) having at least two epoxy groups having a structure represented by the formula (III) may include, but is not limited to, a reaction of a bisphenol fluorene with an epihalohydrin. The epoxy group-containing bisphenol quinone type compound is obtained.

Specific examples of the above bisphenol quinoid compound are, for example, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3- [9,9-bis(4-hydroxy-3-methylphenyl)fluorene], 9,9-bis(4-hydroxy-3-chlorophenyl)indole [9,9-bis(4- Hydroxy-3-chlorophenyl)fluorene], 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-double (9,9-bis(4-hydroxy-3-bromophenyl)fluorene] 4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene [9] ,9-bis(4-hydroxy-3-methoxyphenyl)fluorene], 9,9-bis(4-hydroxy-3,5-dimethylphenyl)anthracene [9,9-bis(4-hydroxy-3, 5-dimethylphenyl)fluorene], 9,9-bis(4-hydroxy-3,5-dichlorophenyl)indole [9,9-bis(4- Hydroxy-3,5-dichlorophenyl)fluorene],9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene] And other compounds.

Suitable epihalohydrins as described above may include, but are not limited to, 3-chloro-1,2-epoxyhydrin or 3-bromo-1,2-epoxyhydrin.

The epoxy group-containing bisphenol quinoid compound obtained above includes, but is not limited to, (1) a product manufactured by Nippon Steel Chemical Co., Ltd., such as ESF-300, etc.; (2) a product manufactured by Osaka Gas, such as PG-100, EG- 210, etc.; (3) Goods manufactured by SMS Technology Co.: for example, SMS-F9PhPG, SMS-F9CrG, SMS-F914PG, and the like.

Next, the epoxy compound (i) having at least two epoxy groups may further have a structure represented by the following formula (IV):

Wherein R ⁵ to R ¹⁸ are each the same or different hydrogen atom, a halogen atom, a C ₁ to C ₈ alkyl group or a C ₆ to C ₁₅ aromatic group, and n represents an integer of 0 to 10.

The epoxy compound (i) having at least two epoxy groups having a structure represented by the formula (IV) can give a compound having the structure of the following formula (IV-1), for example, in the presence of an alkali metal hydroxide The halogenated propylene oxide is reacted to obtain:

The (IV-1), the formula is R ⁵ to R ¹⁸ (IV) are the same, respectively, and n are defined as ⁵ to R ¹⁸ and R n is defined, which is not repeated herein.

Further, the epoxy compound (i) having at least two epoxy groups having a structure represented by the formula (IV) is a compound having a structure of the following formula (IV-2) in the presence of an acid catalyst. After the condensation reaction of phenols, a compound having the structure of the formula (IV-1) is formed. Next, an excess of halogenated propylene oxide is added for dehydrohalogenation to obtain an epoxy compound (i) having at least two epoxy groups having a structure represented by the formula (IV):

Wherein R ¹⁹ and R ²⁰ are the same or different hydrogen atom, a halogen atom, a C ₁ to C ₈ alkyl group or a C ₆ to C ₁₅ aromatic group; and Z ¹ and Z ² are the same or different halogen atoms, respectively. a C ₁ to C ₆ alkyl group or a C ₁ to C ₆ alkoxy group. Preferably, the aforementioned halogen atom may be, for example, chlorine or bromine, and the aforementioned alkyl group may be, for example, a methyl group, an ethyl group or a third butyl group, and the aforementioned alkoxy group may be, for example, a methoxy group or an ethoxy group.

Specific examples of the above suitable phenols are: phenol, cresol, ethylphenol, n-propylphenol, isobutylphenol, t-butanol (t- Butyl phenol, octylphenol, nonylphenol, xylenol, methylbutylphenol, di-t-butylphenol, vinylphenol , propenylphenol, ethinylphenol, cyclopentylphenol, cyclohexylphenol or cyclohexylcresol. The aforementioned phenols can be generally used singly or in combination of plural kinds.

The compound having the structure of the above formula (IV-2) is used in an amount of 1 mol, and the phenol is used in an amount of from 0.5 mol to 20 mol, preferably from 2 mol to 15 mol.

Specific examples of the aforementioned acid catalyst are: hydrochloric acid, sulfuric acid, p-toluenesulfonic acid (p-toluenesulfonic acid), oxalic acid, boron trifluoride, aluminum chloride anhydrous, zinc chloride, etc., but with p-toluenesulfonic acid, sulfuric acid or Hydrochloric acid is preferred. The above acid catalysts may be used singly or in combination of plural kinds.

Further, the amount of the acid catalyst to be used is not particularly limited, but preferably, the amount of the compound having the structure of the above formula (IV-2) is 100 weight percent (wt%), and the acid catalyst is used. The amount used is from 0.1% by weight to 30% by weight.

The aforementioned condensation reaction can be carried out in the absence of a solvent or in the presence of an organic solvent. Next, specific examples of the above organic solvent include toluene, xylene, or methyl isobutyl ketone. The above organic solvents may be used singly or in combination of plural kinds.

The organic solvent is used in an amount of from 50% by weight to 300% by weight based on the total weight of the compound having the structure of the formula (IV-2) and the phenol, and is preferably from 100% by weight to 250% by weight. Further, the aforementioned condensation reaction has an operation temperature of 40 ° C to 180 ° C, and the operation time of the condensation reaction is 1 hour to 8 hours.

After completion of the aforementioned condensation reaction, a neutralization treatment or a water washing treatment may be performed. The neutralization treatment described above is to adjust the pH of the solution after the reaction to pH 3 to pH 7, and preferably pH 5 to pH 7. The water washing treatment may be carried out using a neutralizing agent, wherein the neutralizing agent is a basic substance, and specific examples thereof include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; hydrogen Alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; diethylene triamine, triethylenetetramine, aniline, phenylenediamine (diethyltetramine) Organic amines such as phenylene diamine; and ammonia, sodium dihydrogen phosphate, and the like. The aforementioned washing treatment can be carried out by a conventional method. For example, an aqueous solution containing a neutralizing agent is added to the solution after the reaction, and extraction can be carried out repeatedly. Neutralized or washed After the treatment, the unreacted phenols and the solvent are distilled off by heat treatment under reduced pressure, and concentrated to obtain a compound having the structure of the formula (IV-1).

Specific examples of the above-mentioned suitable halogenated propylene oxide are, for example, 3-chloro-1,2-epoxypropane, 3-bromo-1,2-epoxypropane or any combination thereof. An alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be added in advance or added to the reaction before the dehydrohalogenation reaction. The aforementioned dehydrohalogenation reaction has an operating temperature of from 20 ° C to 120 ° C and an operation time ranging from 1 hour to 10 hours.

In one embodiment, an aqueous solution of the alkali metal hydroxide added to the above dehydrohalogenation reaction may also be used. In this embodiment, while the above aqueous alkali metal hydroxide solution is continuously added to the dehydrohalogenation reaction system, water and halogenated propylene oxide can be continuously distilled off under reduced pressure or normal pressure, thereby separating and removing. Water, at the same time, the halogenated propylene oxide can be continuously refluxed into the reaction system.

Before the above dehydrohalogenation reaction is carried out, tetramethyl ammonium chloride, tetramethyl ammonium bromide, trimethyl benzyl ammonium chloride or the like may be added. The quaternary ammonium salt is used as a catalyst, and reacted at 50 ° C to 150 ° C for 1 hour to 5 hours, and then an alkali metal hydroxide or an aqueous solution thereof is added thereto, and the reaction is allowed to proceed for 1 hour at a temperature of 20 ° C to 120 ° C. Up to 10 hours to carry out the dehydrohalogenation reaction.

The total hydroxyl group equivalent weight in the compound having the structure of the above formula (IV-1) is 1 equivalent, and the above halogenated propylene oxide is used in an amount of from 1 equivalent to 20 equivalents, preferably from 2 equivalents to 10 equivalents. The total equivalent weight of the hydroxyl group in the compound having the structure of the above formula (IV-1) is 1 equivalent, and the alkali metal hydroxide added in the above dehydrohalogenation reaction is used in an amount of 0.8 to 15 equivalents, and then 0.9 equivalents. It is preferably up to 11 equivalents.

Further, in order to smoothly carry out the above-described dehydrohalogenation reaction, an aprotic such as dimethyl sulfone or dimethyl sulfoxide may be added in addition to an alcohol such as methanol or ethanol. The reaction is carried out by a polar solvent or the like. In the case of using an alcohol, the total amount of the halogenated propylene oxide based on the above is 100% by weight, and the amount of the alcohol used is 2% by weight to 20% by weight. However, it is preferably from 4% by weight to 15% by weight. In the case of using an aprotic polar solvent, the total amount of the halogenated propylene oxide is 100% by weight, and the aprotic polar solvent is preferably used in an amount of 5 wt% to 100 wt%, preferably 10 wt% to 90 wt%.

After completion of the dehydrohalogenation reaction, a water washing treatment can be selectively performed. Thereafter, the halogenated propylene oxide, the alcohol, and the aprotic polar solvent are removed by heating and depressurizing, for example, at a temperature of 110 ° C to 250 ° C and a pressure of 1.3 kPa (10 mmHg) or less.

In order to prevent the formed epoxy resin from containing a hydrolyzable halogen, the solution after the dehydrohalogenation reaction may be added to a solvent such as toluene or methyl isobutyl ketone, and a base such as sodium hydroxide or potassium hydroxide may be added. The metal hydroxide aqueous solution is again subjected to a dehydrohalogenation reaction. The total hydroxyl group equivalent weight in the compound having the structure of the above formula (IV-1) is 1 equivalent, and the alkali metal hydroxide is used in an amount of 0.01 mol to 0.3 mol, and is 0.05 mol to 0.2 mol. good. Further, the above dehydrohalogenation reaction has an operating temperature ranging from 50 ° C to 120 ° C and an operation time ranging from 0.5 hour to 2 hours.

After completion of the dehydrohalogenation reaction, the salts are removed by filtration, washing, and the like. Further, by evaporating a solvent such as toluene or methyl isobutyl ketone by heating and depressurizing, an epoxy compound having at least two epoxy groups having a structure represented by the formula (IV) can be obtained. (i). The above epoxy compound (i) having at least two epoxy groups as shown in the formula (IV) may include, but is not limited to, for example, trade names NC-3000, NC-3000H, NC-3000S, and NC-3000P. Chemical products.

The compound (ii) having at least one carboxylic acid group and at least one ethylenically unsaturated group is selected from the group consisting of (1) to (3): (1) acrylic acid, methacrylic acid, 2- 2-methacryloyloxyethylbutanedioic acid, 2-methylpropenyloxybutyl succinic acid, 2-methylpropenyloxyethyl adipate, 2- Methyl propylene oxide oxybutyl adipate, 2-methyl propylene oxiranyl hexahydrophthalic acid, 2-methyl propylene oxirane maleic acid, 2-methyl propylene methoxy propyl horse Acid, 2-methylpropenyloxybutyl maleic acid, 2-methylpropenyloxypropyl succinic acid, 2-methylpropenyloxypropyl adipate, 2-methylpropene oxalate Tetrahydrophthalic acid, 2-methylpropenyl propyl phthalate, 2-methylpropenyl butyl phthalate, or 2-methyl propylene oxybutyl phthalate Formic acid; (2) a compound obtained by reacting a hydroxyl group-containing (meth) acrylate with a dicarboxylic acid compound, wherein the dicarboxylic acid compound includes, but is not limited to, adipic acid, succinic acid, maleic acid, ortho (3) a half ester compound obtained by reacting a hydroxyl group-containing (meth) acrylate with a carboxylic anhydride compound (iii), wherein the hydroxyl group-containing (meth) acrylate includes, but not limited to, 2-hydroxy ethane 2-(hydroxyethyl)acrylate, 2-hydroxyethylmethacrylate, 2-hydroxypropylacrylate, 2-hydroxypropyl Base armor Acrylate [(2-hydroxypropyl)methacrylate], 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, or pentaerythritol trimethacrylate Wait. Further, the carboxylic anhydride compound described herein may be the same as the carboxylic anhydride compound (iii) contained in the mixture of the following unsaturated group-containing resin (F-1), and therefore will not be further described.

As described above, the mixture of the unsaturated group-containing resin (F-1) may more optionally contain a carboxylic anhydride compound (iii) and/or an epoxy group-containing compound (iv). The aforementioned carboxylic anhydride compound (iii) may be selected from the group consisting of (1) to (2): (1) butanedioic anhydride, maleic anhydride, and itacona Anhydride (phthalic anhydride), phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, Methyl hexahydrophthalic anhydride, methyl endo-methylene tetrahydro phthalic anhydride, chlorendic anhydride, glutaric acid a dicarboxylic anhydride compound such as an acid anhydride or a trimellitic anhydride (1,3-dioxoisobenzofuran-5-carboxylic anhydride); and (2) benzophenone tetracarboxylic dianhydride (BTDA), diphenyltetracarboxylic acid A tetracarboxylic carboxylic anhydride compound such as formic acid dianhydride or diphenyl ether tetracarboxylic acid dianhydride.

The above epoxy group-containing compound (iv) is selected from the group consisting of glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, an unsaturated group-containing glycidyl ether compound, and an epoxy group. A group of unsaturated compounds of the group or any combination of the above. The unsaturated group-containing glycidyl ether compound includes, but is not limited to, the trade names Denacol EX-111, EX-121 Denacol, Denacol EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171, and Denacol EX-192. Etc. (The above is a product of Changchun Chemical Industry Co., Ltd.).

The unsaturated group-containing resin (F-1) may have an epoxy compound (i) having at least two epoxy groups having a structure represented by the formula (III) and having at least one carboxylic acid group and at least one ethyl group. The unsaturated group compound (ii) is subjected to a polymerization reaction to form a hydroxyl group-containing reaction product, followed by addition of a carboxylic anhydride compound (iii) to carry out a reaction. Preferably, the hydroxyl group-based reaction product has a total hydroxyl equivalent of 1 equivalent, and the carboxylic anhydride compound (iii) has an acid anhydride group equivalent of 0.4 equivalent to 1 equivalent, preferably 0.75 equivalent to 1 equivalent. . When a plurality of carboxylic anhydride compounds (iii) are used, they may be added sequentially or simultaneously in the reaction. Preferably, when the carboxylic anhydride compound (iii) is a dicarboxylic anhydride compound and a tetracarboxylic anhydride compound, the molar ratio of the dicarboxylic anhydride compound and the tetracarboxylic anhydride compound is from 1/99 to 90/10, It is preferably 5/95 to 80/20. Further, the above reaction has an operating temperature in the range of 50 ° C to 130 ° C.

The unsaturated group-containing resin (F-1) may have an epoxy compound (i) having at least two epoxy groups having a structure represented by the formula (IV) and having at least one carboxylic acid group and at least one ethyl group. The unsaturated group compound (ii) is reacted to form a hydroxyl group-containing reaction product, followed by the addition of the carboxylic anhydride compound (iii) and/or the epoxy group-containing compound (iv). It is obtained by a polymerization reaction. Preferably, the total epoxy group equivalent weight based on the epoxy compound (i) having at least two epoxy groups having a structure represented by the formula (IV) is 1 equivalent, and the above has at least one carboxylic acid group and The compound (ii) of at least one ethylenically unsaturated group has an acid value equivalent of from 0.8 equivalents to 1.5 equivalents, preferably from 0.9 equivalents to 1.1 equivalents. The total amount of hydroxyl groups based on the aforementioned hydroxyl group-containing reaction product is 100 mol% (mol%), and the carboxylic anhydride compound (iii) is used in an amount of 10 mol% to 100 mol%, and then 20 mol% to More preferably, 100% by mole is more preferably 30% by mole to 100% by mole.

In the preparation of the unsaturated group-containing resin (F-1), in order to accelerate the reaction, a basic compound is usually added as a reaction catalyst to the reaction solution. The aforementioned reaction catalysts may be used singly or in combination, and the aforementioned reaction catalysts include, but are not limited to, triphenyl phosphine, triphenyl stibine, triethylamine, triethanolamine. ), tetramethylammonium chloride, benzyltriethylammonium chloride, and the like. Preferably, the reaction is based on 100 parts by weight of the total weight of the epoxy compound (i) having at least two epoxy groups and the compound (ii) having at least one carboxylic acid group and at least one ethylenically unsaturated group. The catalyst is used in an amount of from 0.01 part by weight to 10 parts by weight, preferably from 0.3 part by weight to 5 parts by weight.

Further, in order to control the degree of polymerization, a polymerization inhibitor is usually added to the reaction solution. The above polymerization inhibitor may include, but is not limited to, methoxyphenol, methylhydroquinone, hydroquinone, 2,6-di-t-butyl-p-cresol (2,6-di). -t-butyl-p-cresol), or phenothiazine or the like. The above-mentioned polymerization inhibitors can be generally used singly or in combination of plural kinds. The use of a polymerization inhibitor based on the total weight of the above epoxy compound (i) having at least two epoxy groups and compound (ii) having at least one carboxylic acid group and at least one ethylenically unsaturated group is 100 parts by weight The amount is preferably from 0.01 part by weight to 10 parts by weight, more preferably from 0.1 part by weight to 5 parts by weight.

When preparing the unsaturated group-containing resin (F-1), it is possible to use a poly The reaction solvent. Specific examples of the above polymerization solvent include alcohols such as ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol or ethylene glycol; ketone compounds such as methyl ethyl ketone or cyclohexanone; An aromatic hydrocarbon compound such as toluene or xylene; a cellosolve compound such as celecin or butyl cellosolve; a carbital compound such as carbital or butyl carbitol a propylene glycol alkyl ether compound such as propylene glycol monomethyl ether; a poly(propylene glycol alkyl ether) compound such as di(propylene glycol) methyl ether; ethyl acetate, acetic acid Acetate compound such as butyl ester, ethylene glycol monoethyl ether acetate or propylene glycol methyl ether acetate; ethyl lactate or butyl lactate An alkyl lactate compound; or a dialkyl glycol ether. The above-mentioned polymerization solvent can be generally used singly or in combination of plural kinds. Further, the acid value of the above-mentioned unsaturated group-containing resin (F-1) is preferably from 50 mgKOH/g to 200 mgKOH/g, and more preferably from 60 mgKOH/g to 150 mgKOH/g.

The resin (F) having an unsaturated group is used in an amount of 15 to 150 parts by weight, preferably 20 to 130 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer (A); More preferably, it is 30 to 110 parts by weight. When the resin (F) having an unsaturated group is used, the taper angle of the photosensitive resin composition can be further improved.

The thermal initiator (G) of the present invention is not particularly limited, and in one embodiment of the present invention, it may include, but is not limited to, an azo compound, an organic peroxide, a hydrogen peroxide compound, and the like.

Specific examples of the above azo compound are: 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile) [ 2,2'-azobis(2-methyl butyronitrile)], 1,1'-azobis(cyclohexane-1-carbonitrile), 1, 2'-Azobis(2,4-dimethylvaleronitrile)[2,2'-azobis(2,4-dimethylvaleronitrile), 1-[(1-cyano-1-methylethyl) couple Nitro]carbamamine {1-[(1-cyano-1-methylethyl)azo]formamide}, 2,2-azobis{2-methyl-nitro-[1,1-di(hydroxymethyl)- 2-hydroxyethyl]propanamide {2,2-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide}, 2,2'-azobis[nitrogen- (2-propenyl)-2-methylpropionamide] {2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-azobis[nitrogen-(2- Propylene)-2-ethylpropanamide] {2,2'-azobis[N-(2-propenyl)-2-ethyl propionamide], 2,2'-azobis(nitro-butyl-2- Methylpropanamide) {2,2'-azobis(N-butyl-2-methylpropionamide)}, 2,2'-azobis(nitro-cyclohexyl-2-methylpropionamide) [2,2 '-azobis(N-cyclohexyl-2-methyl propionamide)], 2,2'-azobis(dimethyl-2-methylpropionamide) [2,2'-azobis(dimethyl-2-methyl propionamide) )], 2,2'-azobis(dimethyl-2-methylpropionate) or 2,2'-azobis (2) 4,4-'-azobis(2,4,4-trimethyl pentene) and the like.

Specific examples of the above organic peroxides include: benzamidine peroxide, dibutylbutyl peroxide, diisobutyryl peroxide, cumyl peroxyneodecanoate, Di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, 1,1 ,3,3-tetramethylbutyl peroxyneodecanoate, di(4-tert-butylcyclohexyl)peroxydicarbonate [di(4- T-butyl cyclohexyl)peroxydicarbonate], 1-cyclohexyl-1-methylethyl peroxyneodecanoate, bis(2-ethoxyethyl)peroxydicarbonate [di(2-ethoxy-ethyl)peroxydicarbonate], bis(2-ethylhexyl)peroxydicarbonate, and t-hexyl peroxyneodecanoate Dimethoxybutyl peroxydicarbonate, third butyl peroxidation Ester (t-butyl Peroxyneodecanoate), t-hexyl peroxypivalate, t-butyl peroxypivalate, bis(3,5,5-trimethylhexyl peroxide)醯)[di(3,5,5-trimethyl hexanoyl)peroxide], di-n-octanoyl peroxide, dilauroyl peroxide, distearoyl peroxide ), 2-ethyl peroxyhexanoic acid-1,1,3,3-tetramethylbutylate (1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate), 2,5-dimethyl-2, 5-bis(2-ethylhexanoic acid peroxy)hexane [2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane], 2-ethylperoxyhexanoic acid trihexyl ester (t- Hexylperoxy-2-ethylhexanoate), di(4-methylbenzoyl)peroxide, t-butylperoxy-2-ethylhexanoate , dibenzoyl peroxide, t-butyl peroxyisobutyrate, 1,1-di(t-butylperoxy)-2-methylcyclohexane ( 1,1-di(t-butylperoxy)-2-methylcyclohexane), 1,1-di(t-butylperoxy)-3,3,5-trimethyl 1,1 -1-di(t-hexyl peroxy-3,3,5-trimethylcyclohexane), 1,1-di(trihexylperoxy)cyclohexane [1,1-di(t- Hexyl peroxy)cyclohexane], 1,1-di(t-butylperoxycyclohexane), 2,2-di[4,4-di (third Butyl peroxy)cyclohexyl]propane {2,2-di[4,4-di(t-butylperoxy)cyclohexyl]propane}, t-hexyl peroxy isopropyl monocarbonate, T-butylperoxy maleate, t-butyl peroxy-3,5,5-trimethyl hexanoate ), t-butyl peroxy laurate, 2,5-dimethyl-2,5-bis(3-methylbenzhydrazyl peroxy)hexane [2,5- Dimethyl-2,5-di-(3-methyl benzoyl peroxy)hexane, t-butyl peroxy isopropyl monocarbonate, tert-butylperoxy-2-ethylhexyl T-butyl peroxy-2-ethylhexyl monocarbonate, third hexyl peroxybenzoate (t-hexyl) Peroxy benzoate), 2,5-dimethyl-2,5-di(benzoyl peroxy)hexane, 2,5-dimethyl-2,5-di(benzoyl peroxy)hexane T-butyl peroxy acetate, 2,2-di(t-butylperoxybutane), tert-butylperoxybenzoate (t-butyl peroxy benzoate), butyl-4,4-di(n-butyl-4,4-di(t-butylperoxy)valerate], two (2-third Di(2-t-butyl peroxy isopropyl)benzene, dicumyl peroxide, di-t-hexyl peroxide, 2 ,5-Dimethyl-2,5-di(t-butyl peroxy)hexane, 2,3,3-butyl peroxy hexane Di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne [2,5-dimethyl-2,5-di(t-butylperoxy) Hexyne-3], t-butyl trimethylsilyl peroxide, di(3-methylbenzoyl)peroxide, and benzamidine (3-methylpropionyl) peroxide [benzoyl (3-m A mixture of ethylbenzoyl)peroxide and dibenzoyl peroxide.

Specific examples of the above hydrogen peroxide compound are: p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl Hydrogen peroxide (1,1,3,3-tetramethyl butyl hydroperoxide), cumene hydroperoxide, t-butyl hydroperoxide, and the like.

The aforementioned thermal initiator (G) is 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis (2, 4-dimethylvaleronitrile), diisobutylphosphonium peroxide, benzamidine peroxide, tert-butyl peroxyisobutyrate, cumene hydroperoxide, cumene peroxynonanoate, etc. It is better. The above-mentioned hot starter (G) may be used singly or in combination of plural kinds, depending on actual needs.

In a specific embodiment of the present invention, based on the polyoxyalkylene polymer (A) The amount of the hot start agent (G) used is from 5 parts by weight to 45 parts by weight, preferably from 7 to 40 parts by weight, more preferably from 10 to 35 parts by weight, per 100 parts by weight. When the thermal initiator (G) is used, the resolution of the photosensitive resin composition can be further improved.

The photosensitive resin composition of the present invention may be further optionally further added with an additive (H) including, but not limited to, a surfactant, a filler, a adhesion promoter, a bridging agent, and an anti-aging agent, without affecting the efficacy of the present invention. An oxidizing agent, an anti-agglomerating agent, or a polymer other than the polyoxyalkylene polymer (A) which can increase various properties such as mechanical properties.

The surfactant may be selected from the group consisting of cationic, anionic, nonionic, amphoteric, polyoxyalkylene, fluorosurfactant or any combination thereof. Further, the aforementioned surfactant may include, but is not limited to, polyethoxylated alkyl ethers such as polyethoxydodecyl ether, polyethoxylated oxime ether or polyethoxylated oleyl ether; Polyethoxylated alkylphenyl ethers such as ethoxyoctylphenyl ether or polyethoxylated nonylphenyl ether; polyethylene glycol such as polyethylene glycol dilaurate or polyethylene glycol distearate Diol diesters; sorbitan fatty acid esters; fatty acid modified polyesters; and tertiary amine modified polyurethanes. The above surfactants may be used singly or in combination of plural kinds.

Specific examples of suitable surfactants include: KP (manufactured by Shin-Etsu Chemical Co., Ltd.), SF-8427 (made by Dow Corning Dongli Polyxanthate Co., Ltd.), Polyflow (manufactured by Kyoei Oil & Fat Chemical Industry Co., Ltd.), F-Top (Tochem Product) Co., Ltd., Megafac (manufactured by Dainippon INK Chemical Industry Co., Ltd.), Fluorade (manufactured by Sumitomo 3M), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), or SINOPOL E8008 (manufactured by Nippon Synthetic Chemical Co., Ltd.).

Specific examples of suitable fillers are, for example, glass or aluminum.

Specific examples of suitable adhesion promoters are, for example, vinyltrimethoxydecane, vinyltriethoxydecane, vinyltris(2-methoxyethoxy)decane, N-(2-aminoethyl) 3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethyl Oxydecane, 3-aminopropyltriethoxydecane, 3-glycidylpropyltrimethoxydecane, 3-glycidylpropylmethyldiethoxydecane, 2-(3,4 -Epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropoxypropyltrimethoxydecane Or 3-mercaptopropyltrimethoxydecane, and the like.

Specific examples of suitable antioxidants are, for example, 2,2-thiobis(4-methyl-6-tert-butylphenol) or 2,6-di-t-butylphenol.

Specific examples of suitable anti-agglomerating agents are, for example, sodium polyacrylate.

Specific examples of suitable bridging agents include epoxy compounds such as 1031S and 157S-70 manufactured by Nippon Epoxy Co., Ltd., and resins.

The total amount of the polyoxyalkylene polymer (A) is 100 parts by weight, other than the filler, the adhesion promoter, the antioxidant, the anti-agglomerating agent or the polyoxyalkylene polymer (A) in the additive (H). The content of the polymer is in the range of 10 parts by weight or less, preferably 6 parts by weight or less.

The content of the surfactant in the additive (H) is preferably 6 parts by weight or less, preferably 4 parts by weight or less, based on 100 parts by weight of the total of the polyoxyalkylene polymer (A).

The content of the bridging agent in the additive (H) is preferably 100 parts by weight or less, preferably 80 parts by weight or less, based on 100 parts by weight of the total of the polyoxyalkylene polymer (A).

The photosensitive resin composition of the present invention generally comprises the above polyoxyalkylene polymer (A), a compound (B) having an ethylenically unsaturated group, a photoinitiator (C), a solvent (D), and a black pigment. (E), the unsaturated group-containing resin (F) and the hot starter (G) are placed in a stirrer and stirred to uniformly mix into a solution state, and if necessary, a surfactant, a filler, and a sealant may be added. The additive (H) such as an accelerator, a bridging agent, an antioxidant, and an anti-agglomerating agent is uniformly mixed, and then a photosensitive resin composition in a solution state can be prepared.

Next, the method for preparing the photosensitive resin composition of the present invention is not particularly limited. For example, the black pigment (E) may be directly added to the photosensitive resin composition, or a part of the black pigment (E) may be previously prepared. Dispersing a part of the resin containing the unsaturated group-containing resin (F) and the solvent (D) to form a pigment dispersion, and then mixing the polyoxyalkylene polymer (A) and the compound having an ethylenically unsaturated group (B), a photoinitiator (C), a hot starter (G), a resin (F) having an unsaturated group, and the remainder of the solvent (D) are obtained. The dispersion step of the above black pigment (E) can be carried out by mixing the above components by a mixer such as a beads mill or a roll mill.

The present invention also provides a black matrix formed of the aforementioned photosensitive resin composition.

The black matrix is obtained by sequentially pre-baking, exposing, developing, and post-baking the photosensitive resin composition as described above, wherein the optical density of the black matrix is in a film thickness of 1 μm. 3.0 or more. Preferably, the optical density of the black matrix ranges from 3.2 to 5.5 at a film thickness of 1 μm; more preferably, the optical density of the black matrix ranges from 3.5 to 5.5 at a film thickness of 1 μm.

The black matrix of the present invention can be applied to a substrate by a coating method such as spin coating or cast coating, and the solvent can be removed by drying under reduced pressure and pre-baking. Further, a pre-baked coating film is formed on the substrate. The conditions for the drying under reduced pressure and the pre-baking are different depending on the type and blending ratio of each component. Usually, the drying under reduced pressure is carried out at a pressure of less than 200 mmHg for 1 second to 20 seconds, and the pre-baking treatment is performed at It is carried out at a temperature of 70 ° C to 110 ° C for 1 minute to 15 minutes. After pre-baking, the coating film is exposed to a designated mask, and then immersed in a developer at a temperature of 23±2° C. for 15 seconds to 5 minutes to remove unnecessary portions to form a specific one. pattern. The light used for the exposure is preferably ultraviolet rays such as g-line, h-line or i-line, and the ultraviolet irradiation device may be an (ultra) high-pressure mercury lamp and a metal halide lamp.

Specific examples of the aforementioned suitable developer are, for example, sodium hydroxide, potassium hydroxide, Sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, sodium citrate, sodium methyl citrate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylamine hydroxide, A basic compound such as choline, pyrrole, piperidine or 1,8-diazabicyclo-[5,4,0]-7-undecene. The concentration of the developer is generally from 0.001% by weight (% by weight) to 10% by weight, preferably from 0.005% by weight to 5% by weight, more preferably from 0.01% by weight to 1% by weight.

When such a developer is used, it is usually washed with water after development, and then air-dried with compressed air or compressed nitrogen, and then post-baked by a heating device such as a hot plate or an oven. The post-baking temperature is usually from 150 to 250 ° C, wherein the heating time using the hot plate is from 5 minutes to 60 minutes, and the heating time in the oven is from 15 minutes to 150 minutes. After the above processing steps, a black matrix can be formed on the substrate.

Specific examples of the substrate include: alkali-free glass, soda-lime glass, hard glass (Pyrus glass), quartz glass, and the like, and a transparent conductive film attached to the glass; or A photoelectric conversion device substrate (such as a germanium substrate) such as a device.

The present invention further provides a color filter comprising the aforementioned black matrix.

The method for forming a color filter of the present invention can be applied to a color filter prepared by mixing the solution into a solution state by a coating method such as rotary coating, cast coating or roll coating. On the substrate, wherein the substrate has previously formed a black matrix separating the pixel colored layers by using the aforementioned photosensitive resin composition. After coating, most of the solvent is removed by drying under reduced pressure, and the solvent is removed by pre-bake to form a pre-baked coating film. Among them, the conditions of drying under reduced pressure and pre-baking vary depending on the type of each component and the blending ratio. Usually, the drying under reduced pressure is carried out at a pressure of 0 mmHg to 200 mmHg for 1 second to 60 seconds, and the pre-bake is at 70. It is carried out at a temperature of from ° C to 110 ° C for 1 minute to 15 minutes. After pre-baking, the pre-baked coating film is exposed between the specified masks, and immersed in the above-mentioned developing solution at a temperature of 23±2° C. for 15 seconds to 5 minutes for development, and is not partially removed. It has a pattern. For the light used for exposure, ultraviolet rays such as g-line, h-line, and i-line are preferable, and the ultraviolet device may be a (super) high-pressure mercury lamp and a metal halide lamp.

After the above-mentioned development, it is washed with water, and the pattern is air-dried by compressed air or compressed nitrogen, and then subjected to post-baking treatment by a heating device such as a hot plate or an oven. The conditions of the post-baking treatment are as described above, and are not described herein.

The color layer of the color filter can be obtained by repeating the above steps for each color (mainly including red, green, and blue colors). Next, an indium tin oxide (ITO) vapor-deposited film is formed on the pixel layer in a vacuum environment at a temperature of 220 ° C to 250 ° C, and if necessary, the ITO coating film is subjected to etching and wiring, and then the liquid crystal alignment film is coated with a polymerized film. The imine, which is further fired, can be used as a color filter for a liquid crystal display element.

The present invention further provides a liquid crystal display element comprising the aforementioned color filter.

The liquid crystal display device of the present invention is a color filter substrate formed by the method for producing a color filter, and a driving substrate provided with a thin film transistor (TFT), between the two substrates The intervening gap (cell gap) is disposed oppositely, and the peripheral portions of the two substrates are bonded together with a sealing agent, and the liquid crystal is filled in the gap between the surface of the substrate and the sealing agent to seal the injection hole. A liquid crystal cell is formed. Then, on the outer surface of the liquid crystal cell, that is, on the other side faces of the respective substrates constituting the liquid crystal cell, the polarizing plate is bonded to each other to obtain a liquid crystal display element.

The liquid crystal used in the above, that is, the liquid crystal compound or the liquid crystal composition is not particularly limited herein, and any liquid crystal compound and liquid crystal composition can be used.

Further, the liquid crystal alignment film used as described above is used to restrict the alignment of liquid crystal molecules, and is not particularly limited herein, and any of an inorganic substance or an organic substance may be used. The technique for forming a liquid crystal alignment film is well known to those of ordinary skill in the art to which the present invention pertains, and is not the focus of the present invention, and therefore will not be further described.

The invention is illustrated by the following examples, which are not intended to be limited to the scope of the invention.

<Synthesis of polyoxyalkylene polymer (A)>

Synthesis Example A-1:

In a 500 ml three-necked flask, 0.3 mol of methyltrimethoxydecane (hereinafter referred to as MTMS), 0.45 mol of phenyltrimethoxydecane (hereinafter referred to as PTMS), 0.05 mol of 3- (triethoxymethyl) propyl succinic anhydride (hereinafter referred to as GF-20), 0.2 mol of 3-(trimethoxyindolyl) propyl methacrylate (hereinafter referred to as KBM-503) and 180 g of 4-Hydroxy-4-methyl-2-pentanone (hereinafter abbreviated as DAA), and an aqueous oxalic acid solution (0.4 g of oxalic acid dissolved in 75 g of water) was added thereto over 30 minutes while stirring at room temperature. Next, the flask was immersed in an oil bath at 30 ° C, and after stirring for 30 minutes, the above reaction solution was heated to 110 ° C, and stirring was continued to carry out a polycondensation reaction. After reacting for 6 hours, the solvent in the solution was removed by distillation to obtain a polyoxyalkylene polymer (A-1).

Synthesis Examples A-2 to A-6 and A':

Synthesis Examples 2 to 6 and A' used the same preparation method as that of the polyoxyalkylene polymer (A-1) of Synthesis Example A-1 except that Synthesis Examples 2 to 6 and A' changed the polymerization. The type and amount of the raw materials in the siloxane polymer and the polymerization conditions, and the formulation and polymerization conditions thereof are shown in Table 1, and are not described here.

<Synthesis of Resin (F) with Unsaturated Group>

Synthesis Example F-1

100 parts by weight of an antimony epoxy compound (Model ESF-300, manufactured by Nippon Steel Chemical Co., Ltd.; epoxy equivalent 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 part by weight 2,6-di-t-butyl-p-cresol, and 130 parts by weight of propylene glycol methyl ether acetate were continuously added to a 500 mL four-necked flask, and the feed rate was controlled at 25 parts by weight/min. The temperature of the reaction process is maintained at 100 ° C to 110 After reacting for 15 hours at ° C, a pale yellow transparent mixture having a solid concentration of 50% by weight was obtained.

Next, 100 parts by weight of the above-obtained pale yellow transparent mixed solution was dissolved in 25 parts by weight of ethylene glycol ethyl ether acetate, and 6 parts by weight of tetrahydrophthalic anhydride and 13 parts by weight of diphenyl were simultaneously added. The ketone tetracarboxylic dianhydride was heated to 110 ° C to 115 ° C for 2 hours to obtain an unsaturated group-containing resin having an acid value of 98.0 mg KOH/g (hereinafter abbreviated as F-1).

Synthesis Example F-2

100 parts by weight of an antimony epoxy compound (Model ESF-300, manufactured by Nippon Steel Chemical Co., Ltd.; epoxy equivalent 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 part by weight 2,6-di-t-butyl-p-cresol, and 130 parts by weight of propylene glycol methyl ether acetate were continuously added to a 500-mL four-necked flask, and the feed rate was controlled at 25 parts by weight/min. The reaction was maintained at a temperature of from 100 ° C to 110 ° C for 15 hours to obtain a pale yellow transparent mixture having a solid concentration of 50% by weight.

Next, 100 parts by weight of the above-obtained pale yellow transparent mixture is dissolved in 25 parts by weight of ethylene glycol ethyl ether acetate, and 13 parts by weight of benzophenone tetracarboxylic dianhydride is added at 90 ° C to 95 ° C. The reaction was carried out for 2 hours, and then, 6 parts by weight of tetrahydrophthalic anhydride was added, and reacted at 90 ° C to 95 ° C for 4 hours to obtain an unsaturated group-containing resin having an acid value of 99.0 mgKOH/g. (hereinafter referred to as F-2).

Synthesis Example F-3

400 parts by weight of an epoxy compound (Model NC-3000, manufactured by Nippon Kayaku Co., Ltd.; epoxy equivalent 288), 102 parts by weight of acrylic acid, 0.3 parts by weight of methoxyphenol, and 5 parts by weight Triphenylphosphine, and 264 parts by weight of propylene glycol methyl ether acetate were placed in a reaction flask, and the temperature of the reaction was maintained at 95 ° C for 9 hours to obtain an intermediate product having an acid value of 2.2 mg KOH / g. . Next, adding 151 parts by weight Tetrahydrophthalic anhydride, reacted at 95 ° C for 4 hours, to obtain a resin having an acidity of 102 mg KOH / g and an average molecular weight of 3,200 having an unsaturated group (hereinafter referred to as F- 3).

<Example and Comparative Example of Photosensitive Resin>

Example 1

100 parts by weight of the polyoxyalkylene polymer (A-1), 40 parts by weight of dipentaerythritol tetraacrylate (hereinafter referred to as B-2), and 10 parts by weight of the α-ketone represented by the formula (7-1) An oxime ester compound (hereinafter referred to as C-1-1), 5 parts by weight of 1-[9-ethyl-6-(2-methylbenzylidenyl)-9hydro-indazole-3-substituent]- 1-(oxy-acetonitrile) (trade name: OXE-02; manufactured by Ciba Specialty Chemicals Co., Ltd.; hereinafter referred to as C-2-1), and 1200 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as D-1) 200 parts by weight of CIPigment BK7 (hereinafter referred to as E-1), and 15 parts by weight of the unsaturated group-containing resin (F-1) can be formed into a uniform solution state by a rocking stirrer, thereby obtaining an invention. A photosensitive resin composition. The obtained photosensitive resin composition was subjected to characteristic measurement in each evaluation method described later, and the obtained results are shown in Table 1.

Examples 2 to 10 and Comparative Examples 1 to 4

Examples 2 to 10 and Comparative Examples 1 to 4 were prepared in the same manner as in Example 1, and were distinguished by changing the kinds of components of the photosensitive resin composition and the amounts thereof used (as shown in Tables 2 and 3). Show). The obtained photosensitive resin composition was evaluated by the following evaluation methods, and the results are shown in Table 2 and Table 3.

In Table 2 and Table 3:

<Evaluation method>

Resolution:

Various photosensitive resin compositions obtained in the examples and the comparative examples were applied onto a glass substrate by spin coating. Next, prebaking at 100 ° C for 2 minutes gave a pre-baked coating film of about 1.2 μm. Then, the above prebaked coating film was placed under a line and space mask (manufactured by Nibbon Filcon, Japan), and ultraviolet light of 50 mJ/cm ² was used (exposure model AG500- 4N; manufactured by M&R Nano Technology) for exposure. Subsequently, development was carried out at 23 ° C for 1 minute in a 0.045% potassium hydroxide aqueous solution to remove the coating film on the unexposed portion of the substrate. Then, the glass substrate having a specific pattern is washed with water. Finally, the minimum value of the line width of the pattern formed on the glass substrate is defined as the resolution. The line amplitude was evaluated in the following manner. It is to be noted that the smaller the minimum pattern line width, the better the resolution of the photosensitive resin composition.

◎: Minimum pattern width ≦ 4μm

○: 4 μm < minimum pattern width ≦ 6 μm

△: 6 μm < minimum pattern width ≦ 8 μm

×: 8 μm < minimum pattern line width

Taper angle:

Various photosensitive resin compositions obtained in the examples and the comparative examples were applied onto a glass substrate by spin coating. Next, prebaking at 100 ° C for 2 minutes gave a pre-baked coating film of about 1.2 μm. Then, the prebaked coating film was placed under a reticle for exposure (exposure model AG500-4N; manufactured by M&R Nano Technology). Subsequently, development was carried out at 23 ° C for 1 minute in a 0.045% potassium hydroxide aqueous solution to remove the coating film on the unexposed portion of the substrate. Then, the glass substrate having a specific pattern was washed with water to obtain a photoresist pattern. The taper angle of the resist pattern was observed with a scanning electron microscope (S-4800, manufactured by Hitachi High-Technologies) (refer to Fig. 1).

◎: 50 degree ≦ taper angle ≦ 60 degrees

○: 60 degrees < taper angle ≦ 65 degrees or 45 degrees ≦ taper angle < 50 degrees

△: 65 degrees < taper angle ≦ 80 degrees or 30 degrees ≦ taper angle < 45 degrees

×: 80 degrees < taper angle or taper angle < 30 degrees

The above-described embodiments are merely illustrative of the principles and effects of the invention, and are not intended to limit the invention. Modifications and variations of the embodiments described above will be apparent to those skilled in the art without departing from the spirit of the invention. The scope of the invention should be as set forth in the appended claims.

Claims (11)

A photosensitive resin composition comprising: a polyoxyalkylene polymer (A); a compound (B) having an ethylenically unsaturated group; a photoinitiator (C); a solvent (D); and a black pigment (E) Wherein: the polymerization decane monomer of the polyoxyalkylene polymer (A) comprises at least one decane monomer having the structure of the formula (I): Si(X ¹ ) _t (OX ² ) _4-t (I) t is an integer from 1 to 3, and when t represents 2 or 3, the plurality of X ¹ are each the same or different; and when 4-t represents 2 or 3, the plurality of X ² are each the same or different; at least one X ¹ represents a substituted alkyl group of an anhydride-C ₁ to C _10, the epoxy-substituted the C ₁ to C ₁₀ alkyl group or of the epoxy-substituted alkoxy group, and the remaining X ¹ represents hydrogen, C _a C ₁ alkyl group, a C ₂ to C ₁₀ alkenyl group or a C ₆ to C ₁₅ aryl group; and X ² represents hydrogen, a C ₁ to C ₆ alkyl group, a C ₁ to C ₆ fluorenyl group or An aromatic group of C ₆ to C ₁₅ ; the photoinitiator (C) comprising the α-ketoxime ester compound (C-1) represented by the formula (II): In the formula (II): Y ¹ represents a methylphenyl group having 1 to 5 methyl groups; Y ² represents a C ₁ to C ₁₀ alkyl group, a benzamidine group or a C ₃ to C ₆ cycloalkyl group; ; Y ³ represents a methyl group, an ethyl group, a propyl group or a benzamidine group; and Y ⁴ represents or Wherein a represents a methyl group or an ethyl group; and b represents -H or a methyl group; the photosensitive resin composition comprises a hot starter (G), and the hot starter (G) is selected from the group consisting of At least one of the group consisting of a nitrogen compound, a peroxide, and a hydrogen peroxide compound; and the amount of the hot starter (G) used is 100 parts by weight based on the polyoxyalkylene polymer (A). 5 to 45 parts by weight. The photosensitive resin composition of claim 1, further comprising a resin (F) having an unsaturated group, the resin (F) having an unsaturated group obtained by polymerization of a mixture, and the mixture comprising An epoxy compound (i) having at least two epoxy groups, and a compound (ii) having at least one carboxylic acid group and at least one ethylenically unsaturated group. The photosensitive resin composition of claim 2, wherein the epoxy compound (i) having at least two epoxy groups comprises a compound having a structure represented by the following formula (III), and a structure represented by the following formula (IV) a compound or a combination of the above: Wherein R ¹ , R ² , R ³ and R ⁴ are each the same or different hydrogen atom, a halogen atom, a C ₁ to C ₅ alkyl group, a C ₁ to C ₅ alkoxy group, or a C ₆ to C ₁₂ An aryl group or a C ₆ to C ₁₂ aralkyl group; Wherein R ⁵ to R ¹⁸ are each the same or different hydrogen atom, a halogen atom, a C ₁ to C ₈ alkyl group or a C ₆ to C ₁₅ aryl group, and n represents an integer of 0 to 10. The photosensitive resin composition according to claim 1, wherein the azo compound is selected from the group consisting of 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-2-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 1-[(1-cyano-1- Methylethyl)azo]mercaptoamine, 2,2-azobis{2-methyl-nitro-[1,1-di(hydroxymethyl)-2-hydroxyethyl]propanamide, 2 , 2'-azobis[nitro-(2-propenyl)-2-methylpropionamide], 2,2'-azobis[nitro-(2-propenyl)-2-ethylpropionate Amine], 2,2'-azobis(nitro-butyl-2-methylpropionamide), 2,2'-azobis(nitro-cyclohexyl-2-methylpropionamide), 2 , 2'-azobis(dimethyl-2-methylpropanamide), 2,2'-azobis(dimethyl-2-methylpropionate), and 2,2'-azo At least one of the groups of bis(2,4,4-trimethylpentene). The photosensitive resin composition according to claim 1, wherein the peroxide is selected from the group consisting of benzamidine peroxide, dibutyl peroxide, diisobutylammonium peroxide, and cumene peroxynonanoate. Ester, dipropyl peroxydicarbonate, diisopropyl peroxydicarbonate, dibutyl phthalate, 1,1,3,3-tetramethylbutyl peroxy neodecanoate, (4-tert-butylcyclohexyl)peroxydicarbonate, 1-cyclohexyl-1-methylethylperoxydicarbonate, bis(2-ethoxyethyl)peroxydicarbonate, double (2-ethylhexyl)peroxydicarbonate, perhexyl neodecanoate, dimethoxybutyl peroxydicarbonate, tert-butyl peroxy neodecanoate, third hexyl Oxidized pivalate, tert-butyl peroxypivalate, bis(3,5,5-trimethylhexyl peroxide), dioctyl peroxide, dilaurin peroxide, peroxydibenzoate Fatty acid, 2-ethylperoxyhexanoic acid-1,1,3,3-tetramethylbutyl ester, 2,5-dimethyl-2,5-di(2-ethylhexanoic acid peroxidation) Alkane, 3-hexyl peroxyhexanoate, bis(4-methylbenzhydryl) peroxide, tert-butyl 2-ethylperoxyhexanoate, dibenzoguanidine peroxide, peroxidation Tert-butyl isobutyrate, 1,1-di(t-butylperoxy)-2-methylcyclohexane, 1,1-di(t-butylperoxy)-3,3,5- Trimethylcyclohexane, 1,1-di(trihexylperoxy)cyclohexane, 1,1-di(t-butylperoxy)cyclohexane, 2,2-di[4,4- Di(t-butylperoxy)cyclohexyl]propane, third hexylperoxy isopropyl carbonate, tert-butylperoxymaleate, tert-butylperoxy-3,5,5-three Methylhexanoate, tert-butylperoxylaurate, 2,5-dimethyl-2,5-bis(3-methylbenzhydrazide peroxy)hexane, tert-butylperoxidation Propyl carbonate, tert-butylperoxy-2-ethylhexyl carbonate, Trihexyl peroxybenzoate, 2,5-dimethyl-2,5-di(benzhydrazide peroxy)hexane, tert-butyl peroxyacetate, 2,2-di (third dibutyl) Base oxidized) butane, tert-butyl peroxybenzoate, butyl-4,4-di (t-butylperoxy valerate, bis(2-tert-butylperoxyisopropyl) Benzene, cumene peroxide, di-thylhexyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, di-tert-butyl peroxide ( Di-t-butyl peroxide), 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne, tert-butyltrimethylperoxydecane, bis(3-methylbenzene) At least one of the group consisting of a mixture of a perylene group and a benzamidine (3-methylpropionyl) peroxide and a benzhydryl peroxide. The photosensitive resin composition according to claim 1, wherein the hydrogen peroxide compound is selected from the group consisting of decane hydrogen peroxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl group. At least one of the group consisting of hydrogen peroxide, cumene hydroperoxide, and t-butyl hydroperoxide. A photosensitive resin composition according to claim 1, wherein the polyoxyalkylene polymer is based (A) is used in an amount of 100 parts by weight, the compound (B) having an ethylenically unsaturated group is used in an amount of 20 to 200 parts by weight; and the photoinitiator (C) is used in an amount of 15 to 120 parts by weight. The α-ketooxime ester compound (C-1) represented by the formula (II) is used in an amount of 10 to 100 parts by weight; the solvent (D) is used in an amount of 1200 to 10000 parts by weight; and black The pigment (E) is used in an amount of from 200 to 1200 parts by weight. The photosensitive resin composition of claim 2, wherein the unsaturated group-containing resin (F) is used in an amount of 15 to 150 parts by weight based on 100 parts by weight of the polyoxyalkylene polymer (A). . A black matrix formed of the photosensitive resin composition according to any one of claims 1 to 8. A color filter comprising a black matrix according to claim 9. A liquid crystal display element comprising a color filter according to claim 10.