JP2011090275A - Photosensitive resin composition and color filter protective film - Google Patents

Abstract

Provided is a photosensitive resin composition having higher properties such as light transmittance, heat resistance, acid resistance, alkali resistance and heat discoloration.
SOLUTION: (A) an alkali-soluble resin pressure-sensitive adhesive, (B) a compound containing a photopolymerizable ethylenically unsaturated group, (C) a photopolymerization initiator, (D) an organic acid anhydride, (E) a compound having at least two epoxy groups in the molecule and (F) an organic solvent. (A) The alkali-soluble resin pressure-sensitive adhesive has an unsaturated group in the side chain and a fluorene structure between molecules.
[Selection figure] None

Description

  The present invention relates to a photosensitive resin composition and a protective film for a color filter, and in particular, a photosensitive resin composition having characteristics such as higher light transmittance, heat resistance, acid resistance, alkali resistance and heat discoloration. And a protective film for a color filter.

  Generally, a color filter for LCD panels is formed by first forming a plurality of black matrices on a glass substrate, and then sequentially arranging red, green, and blue color layers between neighboring black matrices. Forming a pixel so that the color can be displayed as soon as the light beam passes through the pixel.

  Further, after the creation of the color filter is completed, a transparent electrode is subsequently formed to cover the black matrix and the color layer. Usually, an additional overcoating layer is formed between the color filter and the transparent electrode to make the surface of the color filter flatter, which helps in the production of the transparent electrode. It can also be protected from being affected by the manufacturing process. Generally, the protective film described above must have high light transmittance, adhesiveness, heat resistance, acid resistance and alkali resistance.

US Application No. 6,582,862 US Application No. 7,097,959 International Application No. 2006/129924

  For example, there are several documents that have submitted technologies relating to protective films for color filters, such as US Application No. 6,582,862, US Application No. 7,097,959, and International Application No. 2006/129924. These documents describe a negative resist composition in which the color filter protective film contains an alkali-soluble resin adhesive, a photopolymerization compound, a photopolymerization initiator, and a solvent. It discloses that it is a negative resist composition. However, the properties such as alkali resistance, acid resistance, and heat discoloration properties of the compositions submitted in these documents are relatively inferior.

  Therefore, research and development of a composition used for a protective film of a color filter and improvement of its properties have already become one of the important issues in the industry development.

  An object of this invention is to provide the photosensitive resin composition which has characteristics, such as higher light transmittance, heat resistance, acid resistance, alkali resistance, and heat discoloration.

  Another object of the present invention is to provide a protective film for a color filter that can effectively protect the color filter.

ａは１〜１０モル百分率、ｂは３０〜６０モル百分率、ｃは５〜３０モル百分率、ｄは５〜５０モル百分率、Ｒはベンジル基、フェニル基、ＣＮまたはＣ（Ｏ）ＯＲ₂であり、そのうちＲ₂はＣ１〜Ｃ１５の直鎖または環状のアルキル基、フェニル基、ベンジル基またはアリル基、Ｒ₁はＨ、Ｃ１〜Ｃ４のアルキル基である。 The present invention includes (A) an alkali-soluble resin pressure-sensitive adhesive, (B) a compound containing a photopolymerizable ethylenically unsaturated group, (C) a photopolymerization initiator, (D) an organic acid anhydride, (E) Provided is a photosensitive resin composition comprising a compound having at least two epoxy groups in a molecule and (F) an organic solvent. (A) The alkali-soluble resin pressure-sensitive adhesive has a polymer represented by Chemical Formula 1,

a is 1 to 10 mole percentage, b is 30 to 60 mole percentage, c is 5 to 30 mole percentage, d is 5 to 50 mole percentage, R is benzyl group, phenyl group, CN or C (O) OR ₂ R ₂ is a C1 to C15 linear or cyclic alkyl group, phenyl group, benzyl group or allyl group, and R ₁ is H or a C1 to C4 alkyl group.

  In the photosensitive resin composition according to the embodiment of the present invention, the above-described (A) alkali-soluble resin pressure-sensitive adhesive has a weight average molecular weight of, for example, between 3,000 and 100,000.

  In the photosensitive resin composition according to the embodiment of the present invention, the solid component of the (A) alkali-soluble resin pressure-sensitive adhesive described above is, for example, between 10 and 50%.

  In the photosensitive resin composition according to the embodiment of the present invention, the acid value of the above-described (A) alkali-soluble resin pressure-sensitive adhesive is, for example, between 10 and 400 mgKOH / g.

  In the photosensitive resin composition according to the embodiment of the present invention, when (A) the alkali-soluble resin adhesive is 100 parts by weight, (B) the content of the compound containing a photopolymerizable ethylenically unsaturated group is For example, between 1 and 250 parts by weight.

  In the photosensitive resin composition according to the embodiment of the present invention, when (A) the alkali-soluble resin adhesive is 100 parts by weight, the content of (C) the photopolymerization initiator is, for example, 0.1 to 100 weights. Between departments.

  In the photosensitive resin composition according to the embodiment of the present invention, when (A) the alkali-soluble resin pressure-sensitive adhesive is 100 parts by weight, the content of (D) the organic acid anhydride is, for example, 0.1 to 100% by weight. Between departments.

  In the photosensitive resin composition according to the embodiment of the present invention, when (A) the alkali-soluble resin pressure-sensitive adhesive is 100 parts by weight, (E) the content of the compound having at least two epoxy groups in the molecule is: For example, it is between 0.1 and 100 parts by weight.

  In the photosensitive resin composition according to the embodiment of the present invention, when (A) the alkali-soluble resin pressure-sensitive adhesive is 100 parts by weight, the content of the organic solvent (F) is, for example, 10 to 2,500 parts by weight. Between.

  As for the photosensitive resin composition which concerns on embodiment of this invention, the adhesiveness of the photosensitive resin composition mentioned above is between 1-200 cps, for example.

  The present invention also provides a protective film for a color filter obtained by polymerizing the above-described photosensitive resin composition.

  As described above, since the photosensitive resin composition of the present invention has characteristics such as higher light transmittance, heat resistance, acid resistance, alkali resistance, and heat discoloration, the photosensitive resin composition of the present invention is polymerized. The protective film of the color filter formed as described above can effectively protect the color filter and further improve the function of the constituent elements.

  In order to make the above and other objects, features and advantages of the present invention more comprehensible, several embodiments accompanied with figures are described below.

  The present invention provides a photosensitive resin composition having higher light transmittance, heat resistance, acid resistance, alkali resistance, and heat discoloration characteristics, and a color filter obtained by polymerizing the photosensitive resin composition. This protective film can effectively protect the color filter.

The photosensitive resin composition of the present invention comprises (A) an alkali-soluble resin pressure-sensitive adhesive, (B) a compound containing a photopolymerizable ethylenically unsaturated group, (C) a photopolymerization initiator, and (D). An organic acid anhydride, (E) a compound having at least two epoxy groups in the molecule, and (F) an organic solvent.
(A) Alkali-soluble resin adhesive:

ここで、ａは１〜１０モル百分率、ｂは３０〜６０モル百分率、ｃは５〜３０モル百分率、ｄは５〜５０モル百分率、Ｒはベンジル基、フェニル基、ＣＮまたはＣ（Ｏ）ＯＲ₂であり、そのうちＲ₂はＣ１〜Ｃ１５の直鎖または環状のアルキル基、フェニル基、ベンジル基またはアリル基、Ｒ₁はＨ、Ｃ１〜Ｃ４のアルキル基である。 (A) The alkali-soluble resin pressure-sensitive adhesive is a solution having a polymer represented by Chemical Formula 1.

Here, a is 1 to 10 mole percentage, b is 30 to 60 mole percentage, c is 5 to 30 mole percentage, d is 5 to 50 mole percentage, R is benzyl group, phenyl group, CN or C (O) OR _2, of which R ₂ is a straight-chain or cyclic alkyl group of C1 to C15, a phenyl group, a benzyl group or an allyl group, R ₁ is H, C1 -C4 alkyl groups.

  (A) The weight average molecular weight of the alkali-soluble resin pressure-sensitive adhesive is, for example, between 3,000 and 300,000, and more preferably between 10,000 and 19,000. The solid component is, for example, between 10 and 50%, and more preferably between 20 and 27%. The acid value is, for example, between 10 and 400 mgKOH / g, and more preferably between 20 and 100 mgKOH / g.

In the above solution, commonly used solvents include, for example, benzene, toluene, xylene, methanol, ethanol, ethylene glycol monopropyl ether, Diethylene glycol dimethyl ether (DGDE), diethylene glycol methyl ether (MEC), methyl methoxypropionate, ethyl ethoxypropionate (EEP), ethyl lactate, tetrahydrofuran (Tetrahydrofuran, THF), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate (methyl) cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate ( propylene glycol methyl ether acetate (PGMEA), propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, 3-methoxy butyl acetate (MBA), Methyl isobutyl ketone, methyl ether ketone, acetone, cyclohexanone ohexanone), dimethylformamide (DMF), N, N-dimethylacetamide (N, Nc), N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (NMP) γ-butyrolactone).
(B) Compound containing photopolymerizable ethylenically unsaturated group

  When (A) the alkali-soluble resin pressure-sensitive adhesive is 100 parts by weight, the content of the compound containing (B) a photopolymerizable ethylenically unsaturated group is, for example, between 1 and 250 parts by weight, and more Preferably, it is between 20 and 60 parts by weight.

(B) The compound containing a photopolymerizable ethylenically unsaturated group is an ethylenically unsaturated compound having at least one ethylenically unsaturated group. (B) The compound containing a photopolymerizable ethylenically unsaturated group has, for example, ethylene glycol di (meth) acrylate (ethylene glycol di (meth) acrylate) and 2 to 14 ethyleneoxide groups. Polyethylene glycol di (meth) acrylate, trimethylol propane di (meth) acrylate, trimethylol propane tri (meth) acrylate (trimethylol propane tri (meth) acrylate) acrylate), pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, propylene having 2 to 14 propylene oxide groups Glycol di (meth) acrylate (propyleneglyco l di (meth) acrylate), dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate (DPHA), trimethylolpropane triglycidyl ether Acrylic acid additives (trimethylolpropane triglycidylether acrylic acid additives), bisphenol A diglycidyl ether acrylic acid additives, phthalate diesters of β-hydroxyethyl (meth) acrylate ) acrylate), β-hydroxyethyl (meth) acrylate toluene diisocyanate additives of β-hydroxyethyl (meth) acrylate, or ethylenically unsaturated bonds with polymeric compounds (polymeric compou nd), of which high molecular weight compounds unsaturatedly bonded with ethylene include ditrimethylol propanetetraacrylate, tris (2-acryloxyethyl) isocyanurate, ethoxylated penta Ethoxylated pentaerylthritoltetraacrylate (EO 4 mol), pentaerythritol tetraacrylate (EO 35 mol), ethoxylated trimethylolpropanetriacrylate (EO 9 mol), ethoxylated trimethylolpropane triacrylate (EO 3 mol), propoxylated pentaerythritol tetraacrylate (PO 4 mol), nonaethylene glycol diac rylate), caprolactone-modified dipentaerythritol hexaacrylate (dipentaerythritolhexaacrylate-modified caprolactone), and trimethylolpropanepropoxylate triacrylate, of which dipentaerythritol hexa (meth) acrylate is More preferred.
(C) Photopolymerization initiator

  When (A) the alkali-soluble resin pressure-sensitive adhesive is 100 parts by weight, the content of (C) the photopolymerization initiator is, for example, between 0.1 and 100 parts by weight, and more preferably 0.5. Between 10 parts by weight.

  (C) The photopolymerization initiator is, for example, a phosphine oxide compound, a carbonyl compound, an aminocarbonyl compound, a triazine compound, or an oxime compound. And can be used in combination with a co-photoinitiator. The co-photopolymerization initiator is, for example, an amine compound, an alkoxyanthracene compound, or a thioxanthone compound.

  Phosphine oxide compounds include, for example, arylphosphine oxide, acylphosphine oxide, bisacylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (2,4, 6-trimethylbenzoyldiphenylphosphine oxide (TPO), 2,6-diethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyl 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi (2,6-dimethylphenyl) phospho Benzoyldi (2,6-dimethylphenyl) phosphonate, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine ( bis (2,4,6-trimethylbenzoyl) phenylphosphine (I-819)), or bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide (bis (2,6-dimethoxybenzoyl) -2 , 4,4-trimethylpentylphosphine oxide)).

Examples of series compounds such as carbonyl compounds, aminocarbonyl compounds, triazine compounds, or oxime compounds include acetophenone, benzophenone, diphenylketone, and 1-hydroxy-1-benzoylcyclohexane. (1-hydroxy-1-benzoylcyclohexane (I-184)), benzyldimethylketal 2,2-dimethoxy-1,2-diphenylethane-1-one (benzyldimethylketal 2,2-dimethoxy-1,2-diphenylethane-1-) one (I-651)), 1-benzyl-1-dimethylamino-1- (4-morpholino-benzoyl) propane (I-369 )), 2-morpholyl-2- (4-Chiruchimerukaputo) benzoyl propane (2-morpholyl-2- (4 -methylmercapto) benzoylpropane (I-907)), ethyl anthraquinone (ethylant h raquinone), 4- benzoyl - 4-methyl 4-benzoyl-4-methyldiphenylsulfide, benzoinbutylether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2- (4-isopropyl) benzoylpropane (2-hydroxy-2- (4-isopropyl) benzoylpropane), 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, benzoylmethylformate, 1,7- Bis (9-acridinyl) heptane (1,7-bis (9-acridinyl) heptane), 9-n-butyl-3,6-bis (2-morpholino-isobutyroyl) carbazole (9-n-butyl-3,6 -bis (2-morpholino-isobutyloyl) carbazole), 10-butyl-2-chloroacridone, 2- [2- (4-methoxy-phenyl) -vinyl] -4,6 -Bi -Trichloromethyl- [1,3,5] triazine (2- [2- (4-methoxy-phenyl) -vinyl] -4,6-bis-trichloromethyl- [1,3,5] triazine), 2- ( 4-Methoxy-naphthalen-1-yl) -4,6-bis-trichloromethyl- [1,3,5] triazine (2- (4-methoxy-naphthalen-1-yl) -4,6-bis-trichloromethyl) -[1,3,5] triazine), 2-benzo [1,3] dioxol-5-yl-4,6-bis-trichloromethyl- [1,3,5] triazine (2-benzo [1,3 ] dioxol-5-yl-4,6-bis-trichloromethyl- [1,3,5] triazine), 2-methyl-4,6-bis (trichloromethyl) -s-triazine (2-methyl-4,6 -bis (trichloromethyl) -s-triazine), 2-phenyl-4,6-bis (trichloromethyl) -s-triazine (2-phenyl-4,6-bis (trichloromethyl) -s-triazine), or 2- It is naphthyl-4,6-bis (trichloromethyl) -s-triazine (2-naphthyl-4,6-bis (trichloromethyl) -s-triazine).

  Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropylamine, 4-dimethylaminomethyl benzoate, and 4-dimethylaminoethyl benzoate. benzoate), 4-methylaminoisoamyl benzoate, 2-methylaminoethyl benzoate, 4-dimethylamino-2-ethylhexyl benzoate, N , N-methylparatoluidine, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone (4 , 4'-bis (diethylamino) benzophenone), or 4,4'-bis Ethyl methyl amino) benzophenone (4,4'-bis (ethylmethylamino) benzophenone).

  Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl 9,10-dimethoxyanthracene. -9,10-dimethoxyanthracene) or 2-ethyl-9,10-diethoxyanthracene.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, IPTX, 2,4-diethylthioxanthone, DETX, and 2,4-trichloro. It is thioxanthone (2,4-trichlorothioxanthone) or 1-chloro-4-propoxythioxanthone.
(D) Organic acid anhydride

  When (A) the alkali-soluble resin pressure-sensitive adhesive is 100 parts by weight, the content of (D) the organic acid anhydride is, for example, between 0.1 and 100 parts by weight, and more preferably 2 to 5 parts. Between parts by weight.

(D) The organic acid anhydride is, for example, maleic anhydride (MA), itaconic anhydride, tetrahydrophthalic anhydride, citraconic anhydride, or mesaconic anhydride (Mesaconic anhydride), of which maleic anhydride is more preferred. The organic acid anhydrides described above may be used alone or in combination of several kinds.
(E) Compound having at least two epoxy groups in the molecule

  (A) When the alkali-soluble resin pressure-sensitive adhesive is 100 parts by weight, (E) the content of the compound having at least two epoxy groups in the molecule is, for example, between 0.1 and 100 parts by weight, More preferably, it is between 2 and 10 parts by weight.

(E) Compounds having at least two epoxy groups in the molecule include, for example, bisphenol A type epoxy compounds, bisphenol S type epoxy compounds, and fluorene-9-bisphenol diglycidyl. Ether (fluorene-9-bisphenol diglycidyl Ether, FBDE), bisphenol A type epoxy resin (for example, Epikote 828, 1001, 1002, 1004, etc. manufactured by Yuka Shell Epoxy Co., Ltd.), bisphenol Epoxy resin obtained by reacting alcoholic hydroxyl group of type A epoxy resin with epichlorohydrin (for example, trade name NER-1302 manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 323, softening) 76 ° C), bisphenol F type epoxy resin (for example, oily shell Epoxyte 807, 4001, 4002, 4004, etc., manufactured by Epoxy Co., Ltd., epoxy resins obtained by reacting bisphenol F type epoxy resins with alcoholic hydroxyl groups and epichlorohydrin (for example, , Nippon Kayaku Co., Ltd., trade name NER-7406, epoxy equivalent 350, softening point 66 ° C.), biphenyl glycidyl ether (for example, trade name Epikote YX4000, Yuka Shell Epoxy Co., Ltd.), phenol Phenol novolac type epoxy resin (for example, trade name EPPN-201 manufactured by Nippon Kayaku Co., Ltd., trade names Epikote 152, 154, 157S65, 157S70 manufactured by Yuka Shell Epoxy Co., Ltd., Dow Chemical Company name DEN-438), cresol novolac type epoxy resin (eg Nippon Kayaku Co., Ltd.) Product names EOCN-102S, 1020, 104S), triglycidyl isocyanurate (trade name TEPIC manufactured by Nissan Chemical Co., Ltd.), trisphenol methane type epoxy resin ( For example, Nippon Kayaku Co., Ltd. trade name EPPN-501, 502, 503), fluorene type epoxy resin (for example, trade name ESF-300 made by Nippon Steel Chemical Co., Ltd.), alicyclic epoxy Resin (for example, trade name Celloxide 2021P, EHPE manufactured by Daicel Chemical Industries, Ltd.) or epoxidized polybutadiene (for example, trade name Epolead PB3600 manufactured by Daicel Chemical Industries, Ltd.), of which fluorene-9- Bisphenol diglycidyl ether is more preferred. The above-mentioned compounds having at least two epoxy groups in the molecule may be used alone or in combination of several kinds.
(F) Organic solvent

  (A) When the alkali-soluble resin pressure-sensitive adhesive is 100 parts by weight, the content of the organic solvent (F) is, for example, between 10 and 2,500 parts by weight, and more preferably 80 to 250 parts by weight. Between.

  (F) Organic solvents are, for example, benzene, toluene, xylene, methanol, ethanol, ethylene glycol monopropyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ether, methyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, tetrahydrofuran, ethylene glycol monomethyl. Ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate , Methyl isobutyl ketone, methyl ether ketone, acetone, cyclohexanone, dimethylformamide, N, N- dimethylacetamide, N- methyl-2-pyrrolidone, a γ- butyrolactone. The organic solvents described above may be used alone or in combination of several kinds.

  Further, as the protective film of the color filter, the photosensitive resin composition of the present invention mainly comprises (A) an alkali-soluble resin pressure-sensitive adhesive, (B) a compound containing a photopolymerizable ethylenically unsaturated group, (C The main components are a photopolymerization initiator, (D) an organic acid anhydride, and (E) a compound having at least two epoxy groups in the molecule. Of course, according to actual demand, the following various additives may be added when necessary.

  In an embodiment, a coupling agent may be further added to increase the adhesion between the photosensitive resin composition and the color filter, and to increase the adhesion between the photosensitive resin composition and the transparent electrode. . When the photosensitive resin composition is 100 parts by weight, the amount of coupling agent used is between 0.01 and 30 parts by weight, and more preferably between 0.5 and 3 parts by weight. The coupling agent is, for example, a silicon compound containing an epoxy group or an amino group. For example, β- (3,4-epoxycyclohexyl) ethyl trimethoxysilane (β- (3,4-epoxycyclohexyl) ethyl trimethoxysilane), β- (3,4-epoxycyclohexyl) ethyltriethoxysilane (β- (3,4-epoxycyclohexyl) ethyl triethoxysilane), γ-glycidoxypropyl trimethoxysilane (GTS), γ-glycid Γ-glycidoxypropyl methyldimethoxysilane, γ-glycidoxypropyl methyldiethoxysilane, γ-glycidoxypropyl dimethoxy (ethoxy) silane , Γ-glycidoxypropyl dimethyl (methoxy) silane γ-glycidoxypropyl dimethyl (ethoxy) silane, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane (3 , 4-epoxybutyltriethoxysilane), N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane (N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane), (3-aminopropyl) trimethoxysilane ((3-aminopropyl) ) trimethoxysilane), (3-aminopropyl) triethoxysilane, (N, N-diethyl-3-aminopropyl) triethoxysilane ((N, N-diethyl-3-aminopropyl) trimethoxysilane) Or N-beta (aminoethyl) γ-aminopropyltrimethoxysilane (N-β (aminoethyl) γ-aminopropyltrimethoxysilane). The above-described coupling agents may be used alone or in combination of several kinds.

  In embodiments, a surfactant may further be added. When the photosensitive resin composition is 100 parts by weight, the amount of the surfactant used is between 0.01 and 30 parts by weight, and more preferably between 0.5 and 3 parts by weight. Surfactants include, for example, polyoxyethylene alkyl ethers (for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether). ether)), polyoxyethylene aryl ethers (eg, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether), polyethylene glycol dialkyl esters (polyethylene) glycol dialkyl esters (eg, polyethylene glycol dilaurate), polyethylene glycol distearate , Organosiloxane polymer (e.g., KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.)), or (meth) acrylic acid polymer (e.g., Polyflow No. 75, 90, 95 (manufactured by Kyoeisha Chemical Co., Ltd.), Megafac F171, F172, F173, F475 (manufactured by Dainippon Ink & Chemicals, Inc.), Florard FC430, FC431 (manufactured by Sumitomo 3M Limited), Asahi Gard G710, Serflon S382, SC-101 SC-102, SC-103, Sc-104, SC-105, SC-1068 (manufactured by Asahi Glass Co., Ltd.)). The above-mentioned surfactants may be used alone or in combination of several kinds.

  In embodiments, other additives such as, for example, a defoamer, leveling agent, thermal polymerization inhibitor agent may be further added.

  The preparation of the photosensitive resin composition of the present invention mainly includes the above-mentioned (A) alkali-soluble resin pressure-sensitive adhesive, (B) a compound containing a photopolymerizable ethylenically unsaturated group, and (C) a photopolymerization initiator. (D) an organic acid anhydride, (E) a compound having at least two epoxy groups in the molecule, and (F) an organic solvent having a viscosity of between 1 and 200 cps, more preferably between 3 and 25 cps. Mix uniformly in a stirrer until it is in solution.

The photosensitive resin composition of the present invention can be applied onto a substrate by a method such as spin coating, cast coating, or cast-spin coating. After application, the solvent is removed by pre-baking at 80 ° C. for 2 minutes. Thereafter, the entire surface is exposed at 200 mJ / cm ² . After the development, the film is post-cured at 230 ° C. for 20 minutes to form a 1-1.5 μm photosensitive resin layer, which can be used as a color filter protective film. The substrate described above is, for example, alkali-free glass, soda-lime glass, hard glass (Pyrex (registered trademark) glass), quartz glass, or a photoelectric conversion device substrate (for example, a silicon substrate) used for a solid-state imaging device. Etc.
(A) Synthesis method of alkali-soluble resin adhesive:

Method 1:
Fluorene diacrylate having the following structural formula I is ethylenically unsaturated compound (a1) having an acid group, and other ethylenically unsaturated compounds that can be copolymerized with (a1) and fluorenediacrylate. By copolymerizing with the compound (a2), a compound having the following structural formula II is obtained. Thereafter, the ethylenically unsaturated simple substance (a4) containing an epoxy group is grafted by an esterification reaction.
The reaction equation is as follows:

Method 2:
An ethylenically unsaturated compound (a1) having an acid group and another ethylenically unsaturated compound (a2) that can be copolymerized with (a1) are copolymerized to obtain a compound having the following structural formula III . Thereafter, the fluorene (a3) containing an epoxy group is crosslinked by an esterification reaction to form a compound having the following structural formula II. Then, the ethylenically unsaturated simple substance (a4) containing an epoxy group is grafted.
The reaction equation is as follows:

（Ａ）アルカリ可溶性樹脂粘着剤Ａ１の合成例： Method three:
An ethylenically unsaturated compound (a1) having an acid group and another ethylenically unsaturated compound (a2) that can be copolymerized with (a1) are copolymerized to obtain a compound having the following structural formula III . Thereafter, crosslinking and grafting are simultaneously performed on the fluorene (a3) containing an epoxy group and the ethylenically unsaturated simple substance (a4) containing an epoxy group by an esterification reaction.
The reaction equation is as follows:

(A) Synthesis example of alkali-soluble resin adhesive A1:

Synthesis Example 1 (Method 1):
Add 180 g DGDE solvent and 290 g PGMEA solvent into the reaction bottle, inject nitrogen, stir and heat to 100 ° C. Separately, 6.8 g of 2,2-azobisisobutyronitrile (AIBN) was dissolved in 100 g of DGDE, then 57.2 g of dicyclopentanylmethacrylate, 53. 3 g of methacrylic acid, 5.2 g of allyl methacrylate, 1.85 g of methacrylonitrile, 43 g of styrene, 16 g of full orange acrylate (50% PGMEA solution) The mixture is mixed and dropped into a reaction bottle, and all the reactants are dropped into a reaction bottle at 100 ° C. within one and a half hours. Subsequently, 0.3 g of AIBN is dissolved in a solution of 5 g / 5 g of DGDE / PGMEA and dropped into the reaction bottle within 10 minutes, followed by reaction for 3 hours. Thereafter, the temperature of the reaction bottle was lowered to 80 ° C., nitrogen was stopped, 58.7 g glycidyl methacrylate, 2.7 g catalyst agent (1-methylimidazole) and 0.165 g An inhibitor (4-methoxyphenol) is added and stirred in air for 19 hours. The obtained product had a solid component of the resin solution of 26.7 wt. %, Viscosity is 106 cps / 25 ° C., acid value is 47.1 mg KOH / g, and weight average molecular weight is 17939.
(A) Synthesis example of alkali-soluble resin adhesive A2:

Synthesis Example 2 (Method 2):
Add 368 g MBA solvent and 92 g PGMEA solvent into the reaction bottle, pour nitrogen, stir and heat to 100 ° C. Separately, 6 g of AIBN was dissolved in a mixed solution of 88 g / 22 g of MBA / PGMEA, and then 50.2 g of dicyclopentanyl methacrylate, 47.5 g of methacrylic acid, 4.5 g of allyl methacrylate, 1.6 g of methacrylate. Ronitrile and 37.5 g of styrene were mixed and dropped into the reaction bottle, and all the reactants were dropped into the reaction bottle at 100 ° C. within 1 hour and a half. React. Subsequently, 0.3 g of AIBN is dissolved in 10 g of the MBA solution and dropped into the reaction bottle within 10 minutes, and the reaction is continued for 3 hours. Thereafter, 5.6 g of fluorene bisepoxy and 0.14 g of a catalyst agent (1-methylimidazole) were added and reacted for 14 hours, the temperature of the reaction bottle was lowered to 80 ° C., nitrogen was stopped, and 51.2 g of glycidyl Methacrylate, 2.5 g catalyst (1-methylimidazole) and 0.14 g inhibitor (4-methoxyphenol) are added and allowed to react in air for 19 hours. The obtained product had a solid component of 25.1 wt. %, Viscosity is 119 cps / 25 ° C., acid value is 64.5 mgKOH / g, and weight average molecular weight is 18265.
(A) Synthesis example of alkali-soluble resin adhesive A2:

Synthesis Example 3 (Method 3):
Add 235 g of DGDE solvent and 235 g of PGMEA solvent into the reaction bottle, pour nitrogen, stir and heat to 100 ° C. Separately, 8 g of AIBN was dissolved in a mixed solution of 55 g / 55 g of DGDE / PGMEA, and then 48 g of dicyclopentanyl methacrylate, 49 g of methacrylic acid, 4.5 g of allyl methacrylate, 1.6 g of methacrylonitrile, 37 .8 g of styrene is mixed and dropped into the reaction bottle, and all the reactants are dropped into the reaction bottle at 100 ° C. within one and a half hours. Subsequently, 0.4 g of AIBN is dissolved in a solution of 5 g / 5 g of DGDE / PGMEA and dropped into the reaction bottle within 10 minutes, and the reaction is continued for 3 hours. The temperature of the reaction bottle was then lowered to 80 ° C. to stop the nitrogen, 22.3 g fluorene bisepoxy, 2.03 g catalyst PPh3 and 43.1 g glycidyl methacrylate, 2.0 g catalyst (1-methyl Imidazole) and 0.15 g inhibitor (4-methoxyphenol) are added and stirred in air and allowed to react for 18 hours. The obtained product had a solid component of the resin solution of 25.9 wt. %, Viscosity is 229 cps / 25 ° C., acid value is 61 mg KOH / g, and weight average molecular weight is 11180.
(A) Synthesis comparative example of alkali-soluble resin pressure-sensitive adhesive T (crosslinking without using fluorene):

  Add 235 g of DGDE solvent and 235 g of PGMEA solvent into the reaction bottle, pour nitrogen, stir and heat to 100 ° C. Separately, 6 g of AIBN was dissolved in a mixed solution of 55 g / 55 g of DGDE / PGMEA, and then 48 g of dicyclopentanyl methacrylate, 49 g of methacrylic acid, 4.5 g of allyl methacrylate, 1.6 g of methacrylonitrile, 37 .8 g of styrene is mixed and dropped into the reaction bottle, and all the reactants are dropped into the reaction bottle at 100 ° C. within one and a half hours. Subsequently, 0.4 g of AIBN is dissolved in a solution of 5 g / 5 g of DGDE / PGMEA and dropped into the reaction bottle within 10 minutes, and the reaction is continued for 3 hours. Thereafter, the temperature of the reaction bottle is lowered to 80 ° C., 51.6 g of glycidyl methacrylate, 2.5 g of a catalyst (1-methylimidazole) and 0.15 g of an inhibitor (4-methoxyphenol) are added, and air is added. Stir in and allow to react for 18 hours. The obtained product had a solid component of 22 wt. %, A viscosity of 19 cps / 25 ° C., an acid value of 78.7 mgKOH / g, and a weight average molecular weight of 11,000.

評価方法： (A) Alkali-soluble resin adhesives A1, A2, A3, and T obtained by Synthesis Examples 1 to 4 using 10 parts by weight were converted into 2.7 parts by weight DPHA, 0.5 parts by weight FBDE, 0.25 Stir, dissolve and mix with parts by weight MA, 0.2 parts by weight I-907, 0.5 parts by weight IPTX, 0.02 parts by weight coupling agent GTS, and 4 parts by weight solvent PGMEA. Then, a photosensitive resin composition for a color filter is prepared (Table 1). The photosensitive resin composition was evaluated using the following various measurement evaluation methods, and the results are shown in Table 2. The prescriptions of other synthesis examples and synthesis comparative examples are also described in Table 1, and the results are shown in Table 2.

Evaluation methods:

1. Heat resistance The photosensitive resin layer on the obtained glass substrate is treated in an oven at 250 ° C. for 60 minutes, and the change in film thickness before and after the treatment is measured with a surface shape measuring apparatus Tencor α-step 500.
○: Change in thickness ≤ 5%
×: Thickness change> 5%

2. Alkali resistance The photosensitive resin layer on the obtained glass substrate is immersed in 10% NaOH for 3 hours at 25 ° C ± 2 ° C, and the change in film thickness before and after treatment is measured with a surface shape measuring device Tencor α-step 500. taking measurement.
○: Change in thickness <1%
×: Thickness change ≧ 1%

3. Acid resistance The photosensitive resin layer on the obtained glass substrate is immersed in 10% HCl for 3 hours at 25 ° C ± 2 ° C, and the change in film thickness before and after treatment is measured with a surface shape measuring device Tencor α-step 500. taking measurement.
○: Change in thickness <1%
×: Thickness change ≧ 1%

4. Solvent resistance The resulting photosensitive resin layer on the glass substrate is immersed in 10% NMP for 3 hours at 25 ° C ± 2 ° C, and the film thickness changes before and after the treatment with the surface shape measuring device Tencor α-step 500. Measure.
○: Change in thickness <1%
×: Thickness change ≧ 1%

5. Light transmittance A change in light transmittance of the photosensitive resin layer on the obtained glass substrate is measured with light having a wavelength of 380 to 800 nm.
○: Light transmittance> 97%
×: Light transmittance ≦ 97%

Six, heat-resistant discoloration property The photosensitive resin layer on the obtained glass substrate is processed in an oven at 250 ° C. for 60 minutes, and the change in light transmittance is measured with light having a wavelength of 380 to 800 nm.
○: Change in light transmittance 5% or less Δ: Change in light transmittance 5% to 10%
×: Change in light transmittance of 10% or more

  As described above, the photosensitive resin composition of the present invention has characteristics such as higher light transmittance, heat resistance, acid resistance, alkali resistance and heat discoloration, and polymerizes this photosensitive resin composition. The color filter can be effectively protected by the color filter protective film formed as described above.

  As described above, the present invention has been disclosed by the embodiments. However, the present invention is not intended to limit the present invention, and is within the scope of the technical idea of the present invention so as to be easily understood by those skilled in the art. Therefore, the scope of patent protection should be defined based on the scope of claims and the equivalent area.

Claims (11)

Having a polymer represented by Chemical Formula 1,

a is 1 to 10 mole percentage, b is 30 to 60 mole percentage, c is 5 to 30 mole percentage, d is 5 to 50 mole percentage, R is benzyl group, phenyl group, CN or C (O) OR ₂ , of which linear or cyclic alkyl group of R ₂ is C1 to C15, a phenyl group, a benzyl group or an allyl group, R ₁ is H, C1 -C4 alkyl group (a) an alkali-soluble resin adhesive,
(B) a compound containing a photopolymerizable ethylenically unsaturated group;
(C) a photopolymerization initiator;
(D) an organic acid anhydride;
(E) a compound having at least two epoxy groups in the molecule;
(F) The photosensitive resin composition containing an organic solvent.   The photosensitive resin composition according to claim 1, wherein the weight average molecular weight of the (A) alkali-soluble resin pressure-sensitive adhesive is between 3,000 and 100,000.   The photosensitive resin composition according to claim 1, wherein the solid component of the (A) alkali-soluble resin pressure-sensitive adhesive is between 10% and 50%.   The photosensitive resin composition according to claim 1, wherein the acid value of the (A) alkali-soluble resin pressure-sensitive adhesive is between 10 and 400 mgKOH / g.   When the (A) alkali-soluble resin pressure-sensitive adhesive is 100 parts by weight, the content of the compound (B) containing a photopolymerizable ethylenically unsaturated group is between 1 and 250 parts by weight. 1. The photosensitive resin composition according to 1.   The photosensitive resin composition according to claim 1, wherein when (A) the alkali-soluble resin pressure-sensitive adhesive is 100 parts by weight, the content of the (C) photopolymerization initiator is between 0.1 and 100 parts by weight. object.   The photosensitive resin composition according to claim 1, wherein when (A) the alkali-soluble resin pressure-sensitive adhesive is 100 parts by weight, the content of the (D) organic acid anhydride is between 0.1 and 100 parts by weight. object.   When (A) the alkali-soluble resin pressure-sensitive adhesive is 100 parts by weight, the content of the compound (E) having at least two epoxy groups in the molecule is between 0.1 and 100 parts by weight. Item 2. A photosensitive resin composition according to Item 1.   2. The photosensitive resin composition according to claim 1, wherein when (A) the alkali-soluble resin pressure-sensitive adhesive is 100 parts by weight, the content of the (F) organic solvent is between 10 and 2,500 parts by weight.   The photosensitive resin composition of Claim 1 whose adhesiveness of the said photosensitive resin composition is between 1-200 cps.   The protective film of the color filter formed by superposing | polymerizing the photosensitive resin composition of any one of Claim 1 to 10.