JP2011154343A - Photosensitive resin composition, overcoating layer for color filter and photosensitive resin adhesive - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide: a photosensitive resin composition having such properties as high translucency, heat resistance, acid resistance, alkali resistance and thermal discoloration resistance; an overcoating layer for a color filter; and a photosensitive resin adhesive. <P>SOLUTION: The photosensitive resin composition comprises (A) a graft acrylic alkali-soluble resin adhesive having carboxylic acid groups and olefin units into which acryloyloxy groups have been introduced by epoxy groups, (B) a compound containing a photopolymerizable ethylenically unsaturated group, (C) a photoinitiator, (D) an organic acid anhydride, (E) a compound containing at least two epoxy groups in the molecule, and (F) an organic solution. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

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

  Generally speaking, a method for manufacturing a color filter for a liquid crystal display panel is to first form a large number of black matrices on a glass substrate, and then sequentially arrange red, green and blue between adjacent black matrices. The color layer is formed as a pixel, and a color appears when a light ray passes through the pixel.

  In addition, after the fabrication of the color filter is completed, a transparent electrode is then formed to cover the black matrix and the color layer. Normally, an overcoating layer is formed between the color filter and the transparent electrode to flatten the surface of the color filter, helping to manufacture the transparent electrode, and to prevent the color filter from being affected by subsequent processes. To do. Generally speaking, the above-described protective film must have high light transmittance, adhesion, heat resistance, acid resistance, and alkali resistance.

US Pat. No. 6,582,862 US Patent No. 7097959 International Publication No. 2006/129924 Pamphlet

  In some literatures, related technologies for color filter protective films have been proposed, for example, patent documents such as US 6582862, US 7097959, and WO 2006/129924. In these documents, a negative type photoresist in which the protective film of the color filter includes an alkali-soluble resin binder, a photopolymerization compound, a photopolymerization initiator, and a solvent. It is disclosed that it is a negative photoresist 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 the composition used for the protective film of the color filter and improvement of its characteristics are one of the important issues for industrial development.

  Accordingly, an object of the present invention is to provide a photosensitive resin composition having characteristics such as high translucency, heat resistance, acid resistance, alkali resistance and heat discoloration.

  Another object of the present invention is to provide a color filter protective film capable of effectively protecting the color filter.

  Still another object of the present invention is to provide a photosensitive resin pressure-sensitive adhesive having characteristics such as high light transmittance, heat resistance, acid resistance, alkali resistance and heat discoloration.

そのうち、x = 1〜10モルパーセント、y = 29〜59モルパーセント、a + b =40〜60モルパーセント、a = 5〜40モルパーセント、b = 5〜25モルパーセント、Rがベンジル基、フェニル基、CNまたはC（O）OR2であり、そのうち、R2がC1〜C15の直鎖または環状アルキル基、フェニル基、ベンジル基またはアリル基であり、R₁がHまたはC1〜C4のアルキル基である。 This invention includes (A) an alkali-soluble resin adhesive, (B) a compound containing a photopolymerizable ethylenically unsaturated group, (C) a photopolymerizable initiator, (D) an organic acid anhydride, and (E) in the molecule. A photosensitive resin composition comprising a compound containing at least two epoxy groups and (F) an organic solution is provided. (A) The alkali resin-soluble pressure-sensitive adhesive is a polymer represented by the structural formula (1),

Among them, x = 1-10 mole percent, y = 29-59 mole percent, a + b = 40-60 mole percent, a = 5-40 mole percent, b = 5-25 mole percent, R is benzyl group, phenyl group, CN or C (O) oR @ 2, of which a straight-chain or cyclic alkyl group of R2 is C1 to C15, a phenyl group, a benzyl group or an allyl group, R ₁ is an alkyl group of H or C1~C4 is there.

  In the photosensitive resin composition according to the embodiment of the present invention, the weight average molecular weight of the alkali-soluble resin pressure-sensitive adhesive (A) is in the range of, for example, 3000 to 300000.

  In the photosensitive resin composition according to the embodiment of the present invention, the solid content of the (A) alkali-soluble resin pressure-sensitive adhesive is in the range of, for example, 10 to 50%.

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

  In the photosensitive resin composition according to the embodiment of the present invention, based on (A) 100 parts by weight of the alkali-soluble resin pressure-sensitive adhesive, the content of the compound containing (B) a photopolymerizable ethylenically unsaturated group is, for example, 1 to The range is between 250 parts by weight.

  The photosensitive resin composition according to the embodiment of the present invention is based on (A) 100 parts by weight of the alkali-soluble resin pressure-sensitive adhesive, and the content of (C) the photopolymerizable initiator is, for example, between 0.1 and 100 parts by weight. It is a range.

  The photosensitive resin composition according to the embodiment of the present invention is based on (A) 100 parts by weight of the alkali-soluble resin adhesive, and (D) the content of the organic acid anhydride is, for example, in the range of 0.1 to 100 parts by weight. It is.

  In the photosensitive resin composition according to the embodiment of the present invention, based on (A) 100 parts by weight of the alkali-soluble resin pressure-sensitive adhesive, (E) the content of the compound containing at least two epoxy groups in the molecule is, for example, 0.1. The range is between ~ 100 parts by weight.

  In the photosensitive resin composition according to the embodiment of the present invention, based on (A) 100 parts by weight of the alkali-soluble resin pressure-sensitive adhesive, (F) the content of the organic solution is in the range of, for example, 10 to 2500 parts by weight. .

  In the photosensitive resin composition according to the embodiment of the present invention, the viscosity of the photosensitive resin composition is in the range of 1 to 200 cps.

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

  The present invention further provides (A) a photosensitive resin adhesive containing an alkali-soluble resin adhesive.

Action

  Based on the above, the photosensitive resin composition of the present invention has characteristics such as high translucency, heat resistance, acid resistance, alkali resistance, and heat discoloration, so the photosensitive resin composition of the present invention is polymerized. Thus, the color filter protective film can effectively protect the color filter and improve the functional effect of the element.

  In other words, the alkali-soluble resin pressure-sensitive adhesive of the present invention has succeeded in synthesizing a high ratio of functional group a and functional group b, and can acquire superior heat resistance and alkali resistance. The photosensitive resin composition has characteristics such as high light transmittance, heat resistance, acid resistance, alkali resistance and heat discoloration, and is a protective film for a color filter obtained by polymerizing the photosensitive resin composition of the present invention. Can effectively protect the color filter. The photosensitive resin adhesive provided with the alkali-soluble resin adhesive of the present invention also has characteristics such as high translucency, heat resistance, acid resistance, alkali resistance and heat discoloration.

  Hereinafter, embodiments for carrying out the present invention will be described based on chemical structural formulas.

  This invention submits the photosensitive resin composition. Since this photosensitive resin composition has characteristics such as high light transmittance, heat resistance, acid resistance, alkali resistance and heat discoloration, a protective film for a color filter obtained by polymerizing this photosensitive resin composition is effective. The color filter can be protected.

  This invention also submits the photosensitive resin adhesive containing the following (A) alkali-soluble resin adhesive.

  The photosensitive resin composition of the present invention comprises (A) an alkali resin-soluble adhesive, (B) a compound containing a photopolymerizable ethylenically unsaturated group, (C) a photopolymerizable initiator, and (D) an organic acid anhydride. And (E) a compound containing at least two epoxy groups in the molecule and (F) an organic solution. In addition, in the adhesive or at the time of preparing the photoresist, it is preferable that propylene glycol methyl ether acetate (PGMEA), 3-methoxybutyl acetate (3-methoxy butyl asetate = MBA) ), A solvent such as 3-ethoxy ethyl propinate (EEPA).

そのうち、x = 1〜10モルパーセント、y = 29〜59モルパーセント、a + b =40〜60モルパーセント、a = 5〜40モルパーセント、b = 5〜25モルパーセント、Rがベンジル基、フェニル基、CNまたはC（O）OR2であり、そのうち、R2がC1〜C15の直鎖または環状アルキル基、フェニル基、ベンジル基またはアリル基であり、R₁がHまたはC1〜C4のアルキル基である。（Ａ）アルカリ可溶性樹脂粘着剤の重量平均分子量は、例えば3000〜300000の間の範囲であり；固形分含有量は、例えば10〜50％であり；酸価は、例えば10〜400mgKOH/gの間の範囲である。 (A) Alkaline resin soluble adhesive:
(A) The alkali resin-soluble adhesive is a solution composed of a polymer represented by the structural formula (1) and a solvent such as PGMEA, MBA, and EEPROM.

Among them, x = 1-10 mole percent, y = 29-59 mole percent, a + b = 40-60 mole percent, a = 5-40 mole percent, b = 5-25 mole percent, R is benzyl group, phenyl group, CN or C (O) oR @ 2, of which a straight-chain or cyclic alkyl group of R2 is C1 to C15, a phenyl group, a benzyl group or an allyl group, R ₁ is an alkyl group of H or C1~C4 is there. (A) The weight average molecular weight of the alkali-soluble resin pressure-sensitive adhesive is, for example, in the range of 3000 to 300000; the solid content is, for example, 10 to 50%; and the acid value is, for example, 10 to 400 mgKOH / g. The range between.

(B) Compound containing photopolymerizable ethylenically unsaturated group:
(A) Based on 100 parts by weight of the alkali-soluble resin pressure-sensitive adhesive, the content of the compound containing (B) a photopolymerizable ethylenically unsaturated group is, for example, in the range of 1 to 250 parts by weight, preferably 20 to The range is between 60 parts by weight.

  (B) The compound containing a photopolymerizable ethylenically unsaturated group is an ethylenically unsaturated compound containing at least one ethylenically unsaturated group. (B) The compound containing a photopolymerization type ethylenically unsaturated group is, for example, ethylene glycol dimethacrylate (ethylene glycol di (meth) acrylate), polyethylene glycol dimethacrylate having 2 to 14 ethyleneoxide groups (ethyleneoxide group) ( polyethylene glycol di (meth) acrylate), trimethylol propane di (meth) acrylate, trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate ) acryrlate), pentaerythritol tetra (meth) acryrlate, propylene glycol di (meth) acrylate having 2 to 14 propylene oxide groups, dipentaerystol pen Methyl acrylate (dipentaerythritol penta (meth) acrylate), dipentaerythritol hexa (meth) acrylate (DPHA), trimethylolpropane triglycidyl ether acyclic acid additive (trimethylolpropanetrigylcidylether acrylic acid additives), bisphenol A diacid Bisphenol A diglycidylether acrylic acid additives, β-hydroxyethyl (meth) acrylate of phthalate diesters, β of toluene diisocyanate additive -A polymeric compound having an ethylenically unsaturated bond or β-hydroxyethyl (meth) acrylate of toluene diisocyanate additives, Polymeric compounds having a sum bond include ditrimethylol propanetetraacrylate, tris (2-acryloxyethyl) isocyanurate, and ethoxylated pentaerylthritoltetraacrylate. ) (EO 4 mol), pentaerythritol tetraacrylate (EO 35 mol), ethoxylated trimethlolpropanetriacrylate (EO 9 mol), trimethylolpropane tetraacrylate (EO 9 mol) 3 mol), propoxylated pentaerylthritoltetraacrylate (EO 4 mol), nonaethylene glycol diacrylate , Dipentaerythritol acrylate-modified caprolactone and trimethylolpropanepropoxylate triacrylate, preferably dipentaerystole heximesa acrylate (Dipentaerythritol hexa (meth) acrylate = DPHA).

(C) Photopolymerizable initiator:
(A) Based on 100 parts by weight of the alkali-soluble resin pressure-sensitive adhesive, the content of (C) the photopolymerizable initiator is, for example, in the range of 0.1 to 100 parts by weight, preferably between 0.5 to 10 parts by weight. It is a range.

  (C) The photopolymerizable initiator is, for example, a phosphine oxide compound, a carbonyl compound, an aminocarbonyl compound, a triazine compound, or an oxime compound, and It can be used in combination with a co-photoinitiator. The co-photopolymerizable initiator is an amine compound, an alkoxy compound (alloxyanthracene) compound, or a thioxanthone compound.

  Examples of phosphine oxide compounds include arylphosphine oxide, acylphosphine oxide, bisacylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide. (2,4,6-trimethylbenzoyl-diphenylphosphine oxide = TPO), 2,6-diethylbenzoyl-diphenylphosphine oxide, 2,6-dimethoxytrimethylbenzoyl-diphenylphosphine oxide ( 2,6-dimethoxybenzoyl-diphenylphosphine oxide), 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide (2,3 , 5,6-tetramethylbenzoyl-diphenylphosphine oxide), benzoyldi (2,6-dimethylpheny) l) 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 )).

  Series compounds such as carbonyl compounds, aminocarbonyl compounds, triazine compounds, and oxime compounds include, for example, acetophenone, benzophenone, bihenylketone, 1-hydroxy-1-cyclohexane ( 1-hydoroxy-1-benzoylcyclohexane (I-184)), benzoyldimethylketal 2,2-dimethoxy-1,2-diphenylethane-1-ketone (benzoyldimethylketal2,2-dimethoxy-1,2-diethane-1-one) (I-651)), 1-benzyl-1-dimethylamino-1- (4-morpholine-benzoyl) propane (I-136) 2-morpholyl-2- (4-methylmercapto) benzoylpropane (I-907), ethylantraquinone, 4-benzoyl-4-methyl Diphenyl sulfide (4-benzoyl-4-methyld iphenylsulfide), 2-hydroxy-2-benzoylpropane, 2-hydroxy-2- (4-isopropyl) benzoylpropane (2-hydoroxy-2- (isopropropyl) 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-morpholine-isobutyroyl) carbazole) (9-n-butyl-3,6-bis (2-morpholine-isobutyloyl) carbzole), 10-butyl-2-chloroacydone, 2- [2- (4-methoxy-phenyl) -vinyl] -4,6-bis-trichloromethyl- [1,3,5 ] Triazine (2- [2- (4-methoxy-phenyl) -vinyl] -4,6-bis-tr ichloromethyl- [1,3,5] triazine), 2- (4-methoxy-naphthalene-1-group)]-4,6-bis-trichloromethyl- [1,3,5] triazine (2- (4- methoxy-naphtahlene-1-yl) -4,6-bis-trichloromethyl- [1,3,5] triazine), 2-benzo [1,3] dioxol-5-group-4,6-bis-trichloromethyl- [1,3,5] triazine (2-benzo [1,3] dioxole-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-naphthyl-4,6-bis (trichloromethyl) -s-triazine (2-naphthyl-4,6-bis (trichloromethyl) -s-triazine) .

  Amino compounds include, for example, triethanolamine, methyldiethanolamine, triisopropylamine, 4-dimethylaminomethyl benzoate, 4-dimethylaminoethyl benzoate (4 -dimethylaminoethyl benzoate), 4-dimethylaminoisoamyl benzoate, 2-methylaminoethyl benzoate, 4-dimethylamino-2-ethylhexyl benzoate (4-dimethylamino-2-benzoate) ethylhexyl benzoate), N, N-methylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (4,4'-bis (dimetylamino) benzophenone), 4,4'-bis ( Diethylamino) benzophenone (4,4'-bis (dietylamino) benzophenone) or 4,4'-bis (ethylmethylamino) benzo It is phenone (4,4'-bis (ethylmethylamino) benzophenone).

  Alkoxyanthracene compounds include, for example, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene (2- ethyl-9,10-dimethoxyanthracene) or 2-ethyl-9,10-diethoxyanthracene.

  Examples of thioxanthone compounds include 2-isopropylthioxanthone (2-isoproplythioxanthone), 4-isopropylthioxanthone (4-isoproplythioxanthone = IPTX), 2,4-diethylthioxanthone (2,4-diethyl isoproplythioxanthone = DETX), 2,4- It is trichlorothioxanthone (2,4-trichlorothioxanthone) or 1-chloro-4-proxythioxanthone.

(D) Organic acid anhydride:
(A) Based on 100 parts by weight of the alkali-soluble resin pressure-sensitive adhesive, the content of (D) the organic acid anhydride is, for example, in the range of 0.1 to 100 parts by weight.

  (D) The organic acid anhydride is, for example, maleic anhydride (MA), itaconic anhydride, tetrahydrophthalic anhydride, citaraconic anhydride or Mesaconic anhydride, preferably maleic anhydride. The above organic acid anhydrides can be used alone or in combination of several kinds.

(E) Compound containing at least two epoxy groups in the molecule:
(A) Based on 100 parts by weight of the alkali-soluble resin pressure-sensitive adhesive, (E) the content of the compound containing at least two epoxy groups in the molecule is, for example, in the range of 0.1 to 100 parts by weight, preferably , In the range between 2 and 10 parts by weight.

  (E) Compounds containing at least two epoxy groups in the molecule include, for example, bisphenol A type epoxy resin compounds, bisphenol S type epoxy resin compounds, and fluorene-9-bisphenol. Diglycidyl ether (fluorene-9-bisphenol diglycidyl Ether = FBDE), bisphenol A type epoxy resin (for example, product name: Epikote 824,1001,1002, manufactured by Shell Epoxy) 1004), an epoxy resin obtained by the reaction of alcoholic hydroxyl of bisphenol A type epoxy resin and epichlorohydrin (for example: Nippon Kayaku Co., Ltd., trade name NER-1302, epoxy equivalent 323) , Softening point 76 ° C), bisphenol F type epoxy resin (for example, manufactured by Yuka Shell Epoxy, Epoxyte 807, 4001, 4002, 4004, etc.), epoxy resin obtained by the reaction of alcoholic hydroxyl of bisphenol F type resin and epichlorohydrin (for example: Nippon Kayaku Co., Ltd., trade name NER) -7406, epoxy equivalent 350, softening point 66 ° C), biphenyl glycidly ether (for example, Epikote YX4000, manufactured by Yuka Shell Epoxy Co., Ltd.), phenol novolac type epoxy resin ( For example: Nippon Kayaku Co., Ltd., trade name EPPN-201; Yuka Shell Epoxy Co., Ltd., product Epikote 152,154,157S65,157S70; Dow Chemical Co., Ltd., trade name DEN-438), Cresol biphenyl novolac type epoxy resin (cresol novolac type epoxy resin (for example, trade name EOCN-102S, 1020,104S, manufactured by Nippon Kayaku Co., Ltd.), triglycidyl isocyanulate ) (Eg: Nissan Chemical Co., Ltd., trade name TEPIC), triphenol methane type epoxy resin (eg: Nippon Kayaku Co., Ltd., trade name: EPPN-501,502,503), fluorene type epoxy resin (fluorene type epoxy resin) (eg: Nippon Steel Chemical Co., Ltd., trade name ESF-300), alicyclic epoxy resin (eg: Daicel Chemical Industries, trade name: Celloxide 2021P, EHPE), epoxidized polybutadiene (epxidized) polybutadiene) (for example: trade name Eplead PB3600, manufactured by Daicel Chemical Industries, Ltd.), of which fluorene-9-bisphenol diglycidyl ether is preferable. The above compounds containing at least two epoxy groups in the molecule can be used alone or in combination of several kinds.

(F) Organic solution:
(A) Based on 100 parts by weight of the alkali-soluble resin pressure-sensitive adhesive, the content of the organic solution (F) is, for example, in the range of 10 to 2500 parts by weight, and preferably in the range of 80 to 250 parts by weight. It is.

  (F) The organic solution is, for example, PGMEA, MBA or EEPROM. The above organic solutions can be used alone or in combination of several kinds.

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

  In embodiments, a coupling agent may be further added to increase adhesion between the photosensitive resin composition and the color filter, and to increase adhesion between the photosensitive resin composition and the transparent electrode. Based on 100 parts by weight of the photosensitive resin composition, the amount of binder used is in the range of 0.01 to 30 parts by weight, and preferably in the range of 0.5 to 3 parts by weight. The binder is, for example, a silicon compound containing an epoxy group or an amino group, such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (β- (3,4-epoxycyclohexyl) ethy trimethoxysilane), β- (3,4-epoxycyclohexyl) ethyltriethoxysilane (β- (3,4-epoxycyclohexyl) ethy triethoxysilane), γ-glycidoxypropyl trimethoxysilane (GTS), γ-glycid Γ-glycidoxypropyl dimethoxysilane, γ-glycidoxypropyl dimethoxy (ethoxy) silane, γ-glycidoxypropyl dimethoxysilane (γ-glycidoxypropyl dimethoxysilane) (methoxy) silane), γ-glycidoxypropyl dimethly (ethoxy) silane), 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, N- (2-aminoethyl) -3 -Aminopropyldimethoxymethylsilane (N- (2-amonoethyl) -3-aminopropyldimethoxymethylsilane), (3-aminopropyl) trimethoxysilane ((3-aminopropyl) trimethoxysilane), (3-aminopropyl) trimexisilane ((3 -aminopropyl) triethoxysilane), (N, N-diethyl-3-aminopropyl) trimethoxysilane (N, N-diethyl-3-aminopropyl) trimethoxysilane) or N-β (aminoethyl) γ-aminopropyltrimexisilane (N-β (aminopropyl) γ-trimethoxysilane). The above-mentioned binders can be used alone or in combination of several kinds.

  In embodiments, additional surfactants can be added. Based on 100 parts by weight of the photosensitive resin composition, the content of the surfactant is, for example, in the range of 0.01-30 parts by weight, and preferably in the range of 0.5-3 parts by weight. Surfactants include, for example, polyoxyethylene alkyl ethers (for example, polyoxyethylene lauryl ether), polyoxyethylene stearyl ether, polyoxyethylene oleyl ether. (Polyoxyethylene oleyl ether), polyoxyethylene aryl ethers (for example, polyoxyethylene octyl phenyl ether), polyoxyethylene nonyl phenyl ether, polyethylene glycol Polyalkylene glycol dialkyl ethers (eg, polyoxyethylene glycol dilaurate), polyoxyethylene glycol dilaurate Polyoxyethylene glycol distearate, organosiloxane polymer (for example, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.)) or (meth) acriylic acid polymer (for example, Polyflow No. 75,90 , 95 (manufactured by Koeisha Yushi Chemical Co., Ltd.)), Megafac F171, F172, F173, F475 (Dainippon Chemical & Ink Co., Ltd. = manufactured by DIC Corporation), Florand FC430, TC431 (Sumitomo 3M Co., Ltd.) Asahi Gard G710, Serflon S382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-1068 (manufactured by Asahi Glass Co., Ltd.) It can be used alone or in combination of several kinds.

  In the embodiment, other additives such as a defoaming agent, a leveling agent, a thermal polymerization inhibitor, and the like can be added.

  The production of 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) a photopolymerizable initiator, D) An organic acid anhydride, (E) a compound containing at least two epoxy groups in the molecule, and (F) an organic solution are uniformly mixed in a stirrer, and the viscosity is in the range of 1 to 200 cps. Preferably, the solution is in the range between 3 and 25 cps.

The photosensitive resin composition of the present invention can be applied onto a substrate by a method such as spin coating, cast coating, and cast-spin coating. After application, prebake at 80 ° C. for 2 minutes to remove the solution. Then, the whole surface exposure is 200 mJ / cm ² . After development, post-baking is performed at 230 ° C. for 20 minutes to form a photosensitive resin layer having a thickness of 1 to 1.5 μm, which is used as a protective film for the color filter. The substrate described above is, for example, a salt-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 in a solid-state imaging device. Etc.

  The structural formula (1) of the present invention will be described by way of an example of the synthesis of the structural formula (2A) of the following (A) alkali-soluble resin pressure-sensitive adhesive, but is not limited thereto. Among them, the functional group a control includes the functional group h, the functional group b control includes the functional group I, the functional group x control includes the functional group c, and the functional group y control includes d, e. , f, g are included.

そのうち、c=1モルパーセント；d=19モルパーセント；e=3モルパーセント；f=2モルパーセント；g=30モルパーセント；h=15モルパーセント；I=30モルパーセント；h+1=45モルパーセント、40〜60モルパーセントの範囲内である。 (A) Synthesis example of structural formula (2A) of alkali-soluble resin adhesive

Of which: c = 1 mole percent; d = 19 mole percent; e = 3 mole percent; f = 2 mole percent; g = 30 mole percent; h = 15 mole percent; I = 30 mole percent; h + 1 = 45 moles Percent, in the range of 40-60 mole percent.

  The detailed synthesis steps of this synthesis example are described below:

  9 g 2,2'-azobisisobutyronitride (AIBN), 630 g PGMEA solution and 10 g chain transfer agent (α-methyl styrene dimer) dimer)) and dissolve with stirring. 50.2 g of dicyclopentanylmethacrylate, 46.4 g of methacrylic acid, 4.5 g of allylmethacrylate, 1.6 g of metacyclonitride and 37.5 g of styrene (Styrene) and 2.9 g of 2,2-dimethyl-1,3-propylene glycol diacrylate, add nitrogen gas, and stir. Heat to ℃ and react for 2.5 hours. Next, 0.3 g of AIBN is dissolved in 10 g of PGMEA and added dropwise to the reaction flask for 10 minutes, and the reaction is continued for 12 hours. Then stop nitrogen gas, 51.2g glycidy methacrylate, 2.5g catalyst (1-methlimidazole and 0.15g inhibitor (4-methoxyphenole) and The resin solution of the resulting product has a solid content of 27.2 wt%, a viscosity of 110 cps / 25 ° C., an acid value of 57.3 mg KOH / g, a weight average The molecular weight is 111867.

そのうち、c=1モルパーセント；d=19モルパーセント；e=3モルパーセント；f=2モルパーセント；g=30モルパーセント；h=15モルパーセント；I=30モルパーセントである。2.7重量部のDPHAと0.5重量部のFBDEと0.25重量部のMAと0.2重量部のI-907と0.5重量部のIPTXと0.02重量部の密着剤GPSと4重量部の溶剤PGMEAをともに溶解混合させ、調製してカラーフィルター用の感光性樹脂組成物（表１）を得た。この感光性樹脂組成物を以下の各種測定評価方式を利用して評価し、得られた結果を表２に示す。 <Example 1>
Use 10 parts by weight of (A) alkali-soluble resin adhesive having the following structural formula (2A)

Of these, c = 1 mole percent; d = 19 mole percent; e = 3 mole percent; f = 2 mole percent; g = 30 mole percent; h = 15 mole percent; I = 30 mole percent. 2.7 parts by weight DPHA, 0.5 parts by weight FBDE, 0.25 parts by weight MA, 0.2 parts by weight I-907, 0.5 parts by weight IPTX, 0.02 parts by weight adhesive GPS and 4 parts by weight solvent PGMEA are dissolved and mixed together. And a photosensitive resin composition for a color filter (Table 1) was obtained. This photosensitive resin composition was evaluated using the following various measurement evaluation methods, and the results obtained are shown in Table 2.

そのうち、c=1.4モルパーセント；d=23.5モルパーセント；e=3.8モルパーセント；f=2.6モルパーセント；g=38.7モルパーセント；h=15モルパーセントである。2.7重量部のDPHAと0.5重量部のFBDEと0.25重量部のMAと0.2重量部のI-907と0.5重量部のIPTXと0.020.5重量部の密着剤GPSと4重量部の溶剤TGMEAをともに攪拌溶解混合し、調製してカラーフィルター用の感光性樹脂組成物（表１）を得た。 <Comparative Example 1>
10 parts by weight of (A) alkali-soluble resin adhesive having the following structural formula (2R) is used

Of these, c = 1.4 mole percent; d = 23.5 mole percent; e = 3.8 mole percent; f = 2.6 mole percent; g = 38.7 mole percent; h = 15 mole percent. 2.7 parts by weight DPHA, 0.5 parts by weight FBDE, 0.25 parts by weight MA, 0.2 parts by weight I-907, 0.5 parts by weight IPTX, 0.020.5 parts by weight adhesive GPS and 4 parts by weight solvent TGMEA The mixture was stirred, dissolved and mixed to obtain a photosensitive resin composition for color filters (Table 1).

  This photosensitive resin composition was evaluated using the following various measurement evaluation methods, and the results obtained are shown in Table 2.

Evaluation method:
1. Heat resistance The photosensitive resin layer on the glass substrate obtained by the production was oven-treated at 250 ° C. for 60 minutes, and the membrane pressure change before and after the treatment was measured by profilter Tencor α-step 500.
○: Membrane pressure change <6%
X: Membrane pressure change ≧ 6%

2. Alkali Resistance The photosensitive resin layer on the glass substrate obtained by soaking was immersed in 10% NaOH at 25 ° C. ± 2 ° C. for 3 hours, and the change in membrane pressure before and after the treatment was measured with profilter Tencor α-step 500.
○: Change in membrane pressure <1%
X: membrane pressure change ≧ 3%

3. Acid resistance The photosensitive resin layer on the glass substrate obtained by soaking was immersed in 10% HCl at 25 ° C. ± 2 ° C. for 3 hours, and the change in membrane pressure before and after the treatment was measured with profilter Tencor α-step 500.
○: Change in membrane pressure <1%
X: membrane pressure change ≧ 3%

4). Solvent resistance The photosensitive resin layer on the glass substrate obtained by soaking was immersed in NMP for 3 hours at 25 ° C. ± 2 ° C., and the change in membrane pressure before and after the treatment was measured with profilter Tencor α-step 500.
○: Change in membrane pressure <1%
X: membrane pressure change ≧ 3%

5. Transmissivity The transmittance of the photosensitive resin layer on the glass substrate obtained by the production was measured with light having a wavelength of 380 to 800 nm.
○: Transmissivity> 97%
X: Transmissivity <97%

6). Heat-resistant color change The photosensitive resin layer on the glass substrate obtained by the manufacturing was oven-treated at 250 ° C. for 60 minutes, and the change in light transmittance was measured with light having a wavelength of 380 to 800 nm.
○: Light transmittance change 5% or less △: Light transmittance change 5% to 10%
X: Change in transmissivity of 10% or more

7). Adhesiveness The photosensitive resin layer on the glass substrate obtained by the production was cross-cut, and the film layer was peeled off by using an adhesive tape.
○: Residual photoresist film is 98% or more X: Residual photoresist film is less than 98%

  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 that those skilled in the art can easily understand. Therefore, the scope of patent protection should be defined based on the scope of claims and the equivalent area.

Claims (14)

A polymer represented by the structural formula (1),

(Wherein x = 1-10 mole percent, y = 29-59 mole percent, a + b = 40-60 mole percent, a = 5-40 mole percent, b = 5-25 mole percent, R is a benzyl group, phenyl, CN or C (O) oR @ 2, of which a straight-chain or cyclic alkyl group of R2 is C1 to C15, a phenyl group, a benzyl group or an allyl group, an alkyl group of R ₁ is H or C1~C4 Is)
(A) an alkali-soluble resin adhesive;
(B) a compound containing a photopolymerizable ethylenically unsaturated group;
(C) a photopolymerizable initiator;
(D) an organic acid anhydride;
(E) a compound containing at least two epoxy groups in the molecule;
(F) A photosensitive resin composition comprising an organic solution.   (A) The photosensitive resin composition of Claim 1 whose weight average molecular weights of an alkali-soluble resin adhesive are the range between 3000-300000.   (A) The photosensitive resin composition according to claim 1, wherein the solid content of the alkali-soluble resin pressure-sensitive adhesive is in the range of 10 to 50%.   (A) The photosensitive resin composition according to claim 1, wherein the acid value of the alkali-soluble resin pressure-sensitive adhesive is in the range of 10 to 400 mgKOH / g.   The content of (B) a compound containing a photopolymerizable ethylenically unsaturated group is in the range of 1 to 250 parts by weight based on 100 parts by weight of (A) alkali-soluble resin pressure-sensitive adhesive. Photosensitive resin composition. (A) Based on 100 parts by weight of the alkali-soluble resin pressure-sensitive adhesive, the content of (C) the photopolymerizable initiator is 0.1
The photosensitive resin composition of Claim 1 which is the range between -100 weight part.   The photosensitive resin composition according to claim 1, wherein the content of (D) the organic acid anhydride is in the range of 0.1 to 100 parts by weight based on 100 parts by weight of the (A) alkali-soluble resin pressure-sensitive adhesive.   The content of the compound containing (A) at least two epoxy groups in the molecule based on 100 parts by weight of (A) the alkali-soluble resin pressure-sensitive adhesive is in the range of 0.1 to 100 parts by weight. Photosensitive resin composition.   The photosensitive resin composition according to claim 1, wherein the content of the organic solution (F) is in the range of 10 to 2500 parts by weight based on 100 parts by weight of the (A) alkali-soluble resin adhesive.   The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition has a viscosity in the range of 1 to 200 cps.   The protective film of the color filter formed by superposing | polymerizing the photosensitive resin composition as described in any one of Claim 1 to 10. A polymer represented by the structural formula (1),

(Wherein x = 1-10 mole percent, y = 29-59 mole percent, a + b = 40-60 mole percent, a = 5-40 mole percent, b = 5-25 mole percent, R is a benzyl group, phenyl, CN or C (O) oR @ 2, of which a straight-chain or cyclic alkyl group of R2 is C1 to C15, a phenyl group, a benzyl group or an allyl group, an alkyl group of R ₁ is H or C1~C4 Is)
(A) an alkali-soluble resin adhesive;
(B) a compound containing a photopolymerizable ethylenically unsaturated group;
(C) a photopolymerizable initiator;
(D) an organic acid anhydride;
(E) a compound containing at least two epoxy groups in the molecule;
(F) The photosensitive resin adhesive containing organic solution.   (A) The photosensitive resin adhesive of Claim 12 whose weight average molecular weights of an alkali-soluble resin adhesive are the range between 3000-300000.   (A) The photosensitive resin pressure-sensitive adhesive according to claim 12, wherein the acid value of the alkali-soluble resin pressure-sensitive adhesive is in the range of 10 to 400 mgKOH / g.