TW201115266A - Photo-sensitivity resin composition and overcoating layer of color filter - Google Patents

Abstract

A photo-sensitivity resin composition is provided. The photo-sensitivity resin composition comprises (A) photoreaction alkali-soluble resin adhesive, (B) photopolymerization compound containing ethylenically unsaturated group, (C) photo-initiator, (D) organic acid anhydride, (E) compound containing at least two epoxy groups in one molecule, and (F) organic solvent. (A) photoreaction alkali-soluble resin adhesive contains a polymer as shown in formula (1), wherein a=1 to 10 mol%; b=30 to 60 mol%; c=5 to 30 mol%; d=5 to 50 mol%; R is benzyl, phenyl, CN or C(O)OR2, wherein R2 is C1 to C15 straight chain or cyclic alkyl, phenyl, benzyl, allyl; R1 is H or C1 to C4 alkyl.

Description

201115266 DX071103 31287twf.doc/n VI. Description of the Invention: [Technical Field] The present invention relates to a protective film of a photosensitive resin composition and a color filter, and has a high A photosensitive resin composition having properties such as light transmittance, richness, acid resistance, alkali resistance, and heat discoloration resistance, and a protective film of a color filter. [Prior Art] Generally, a color filter of a liquid crystal display panel is formed by forming a plurality of black matrices on a glass substrate, and then sequentially forming red between adjacent black matrices. The green and blue color layers act as pixels, so that when the light passes through the pixels, the color appears. In addition, after the color filter is completed, a transparent electrode is formed to cover the black matrix and the color layer. Generally, an overcoating layer is formed between the color light-emitting sheet and the transparent electrode to make the surface of the color filter flat, to facilitate the manufacture of the transparent electrode, and to protect the color filter. Affected by subsequent processes. In general, the above-mentioned 5 vine film must have good transparency, adhesion, heat resistance, acid resistance and durability. In some documents, related techniques relating to protective films for color filters have been proposed, such as US 6,582,862, US 7,097,759, WO 2006/129924, and the like. In the above documents, it is disclosed that the protective film of the color filter is a negative resist composition, which includes an alkali dissolvable resin binder, photopolymerization 201115266 DX071103 31287twf.doc / photopolymerization compound, photopolymerization initiator and solvent. However, the composition proposed in these documents is inferior in characteristics such as economy, acid resistance, and thermal discoloration. White Therefore, the development of the composition of the protective film for color filters and the improvement of its characteristics have become one of the important topics in the development of the industry. SUMMARY OF THE INVENTION The present invention provides a photosensitive resin composition which has characteristics such as high light transmittance, heat resistance, acid resistance, alkali resistance and heat discoloration resistance. The present invention further provides a protective film for a color filter which can effectively protect a color light guide sheet. The present invention provides a photosensitive resin composition comprising (A) an alkali-soluble resin binder, (B) a photopolymerizable ethylenically unsaturated group-containing compound, (C) a photoinitiator, an (in) organic acid anhydride, (E) a compound containing at least two %oxy groups in the molecule and (F) an organic solvent. (A) The alkali-soluble resin binder contains the polymer represented by the formula (1), 201115266 DX071103 31287twf.doc/n

C - - '不丫

a base, phenyl, CN or c(o) 〇 R2, wherein R 2 is a linear or cyclic alkyl group of α to C15, a strepyl group, a phenyl fluorenyl group or an allyl group; I is hydrazine, C1 to C4. base. According to the photosensitive resin composition of the embodiment of the present invention, the above (A) can be examined; and the weight average molecular weight of the gluten resin binder is, for example, between 3 Å and 100,000. According to the photosensitive resin composition of the embodiment of the invention, the solid content of the above (A) alkali-soluble resin binder is, for example, between 1 〇 and 5 〇%. According to the photosensitive resin composition of the embodiment of the present invention, the acid value of the above-mentioned 201115266 DX071103 31287twf.doc/n (A) alkali-soluble resin binder is, for example, between 10 and 400 mgKOH/g. For example, the sensory resin composition according to the embodiment of the present invention is based on (A) the bathable resin binder is _ parts by weight, and (9) the content of the photopolymerizable ethylenically unsaturated group-containing compound is, for example, 1 to 1 part by weight. The photosensitive resin composition according to the embodiment of the present invention is based on (A) alkali solubility_gluing age-parts by weight (the content of the fluorene starting group is, for example, between 0.1 and 100 parts by weight. According to an embodiment of the present invention The photosensitive resin composition is based on (A) a soluble resin binder of 1 〇〇 by weight, and (D) an organic acid anhydride content of, for example, 0.1 to 100 parts by weight. The photosensitive resin composition is contained in an amount of 1 part by weight based on (A) the alkali-soluble resin binder, and the content of the compound containing at least 2% of an oxygen group in the molecule is, for example, 〇1 to 1 part by weight. The photosensitive resin composition according to the embodiment of the present invention is based on (A) an alkali-soluble resin binder of 1 part by weight, and (F) an organic solvent content of, for example, between 10 and 2500 parts by weight. According to the photosensitive resin composition of the embodiment of the present invention, the photosensitive resin composition has a viscosity of, for example, between 1 and 2 cpps. The present invention further provides a protective film for a color filter. It is made of the above photosensitive resin The photosensitive resin composition of the present invention is composed of the photosensitive resin of the present invention based on the above characteristics of the photosensitive resin composition of the present invention having high light transmittance, heat resistance, acid resistance, alkali resistance and heat discoloration resistance. The color filter of polymer polymerization 201115266 DX071103 31287twf. The protective film of doc/n can effectively protect the color filter to further improve the component performance. The above features and advantages of the present invention can be more clearly understood. The following is a detailed description of the following examples, and is described in detail below with reference to the accompanying drawings. [Embodiment] The present invention provides a photosensitive resin composition which has high transparency, heat resistance, acid resistance and resistance. The protective film of the color filter obtained by polymerizing the photosensitive resin composition can effectively protect the color filter. The photosensitive resin composition of the present invention includes (A). The soluble resin is bonded to the guest, (B) the photopolymerizable ethylenically unsaturated group-containing compound, (q photoinitiator, (D) organic acid anhydride, and (E) molecule contains at least 2 (E) alkali-soluble resin binder: (A) The alkali-soluble resin binder is a solution containing the polymer represented by the formula (1). σ 201115266 DX071103 31287twf. Doc/n

Wherein a is a percentage of 1 to 10 moles; b is a percentage of 30 to 60 moles; a percentage of 5 to 30 moles; d is a percentage of 5 to 50 moles; and R is a clumpy base, a stupid base, CN or C (0) And R2, wherein R2 is a C1 to C15 straight bond or a cyclic alkyl group, a phenyl group, a benzenef group or an allyl group; and R1 is an anthracene, a C1 to C4 alkyl group. The weight average molecular weight of the (A) alkali-soluble resin binder is, for example, between 3 〇〇〇 and 300,000, preferably between loooo 〜; the solid content is, for example, between 10 and 50%, preferably between 2 〇 〜 Between 27%; the acid value is, for example, between 10 and 400 mg KOH/g, preferably between 2 〇 and 1 〇〇 mgKOH/g. In the above, the solvent used for the general suspension is, for example, benzene, 201115266 DX071103 31287twf.doc/n toluene, xylene, methanol, ethanol. , ethylene glycol monopropyl ether, diethylene glycol dimethyl ether (DGDE), diethylene glycol methyl ether (MEC), decyloxypropionic acid vinegar ( Methyl methoxypropionate), ethyl ethoxypropionate (EEP), ethyllactate, tetrahydrofuran (THF), ethylene glycol monomethyl ether, ethanol (ethylene glycol monoethyl ether), methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethanol glycol Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate (PGME) A), propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, 3-methoxy butyl acetate (MBA), thiol isoform Methyl isobutyl ketone, methyl ether ketone, acetone, cyclohexanone, dimethylformamide (DMF), N,N-dimethylacetamidine N, N-dimethylacetamide (DMAc), N-methyl ketone ratio (N-methyl_2-pyrrolidone 'NMP), γ-butyrolactone. (B) Photopolymerizable ethylenically unsaturated group-containing compound 11 201115266 DX071103 31287twf.doc/n Based on (A) alkali-soluble resin binder, 1 part by weight, (B) photopolymerizable ethylenically unsaturated group The content of the compound is, for example, between 1 and 250 parts by weight, preferably between 20 and 60 parts by weight. (B) The photopolymerizable ethylenically unsaturated group-containing compound is an ethylenically unsaturated compound having at least one ethylenically unsaturated group. (B) The photopolymerizable ethylenically unsaturated group-containing compound is, for example, ethylene glycol di(meth)acrylate, having a polymerization of 2 to 14 ethylene oxide groups. Polyethylene glycol di(meth)acrylate, trimethylol propane di(meth)acrylate, trimethylolpropionate dimercaptopropionate Trimethylol propane tri(meth)acrylate), pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 2-14 Propylene glycol propyleneglycol di(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexamethylene acrylate Dipentaerythritol hexa(meth)acrylate, DPHA), trimethylolpropanetriglycidylether acrylic acid additive (double discretion) Bisphenol A diglycidylether acrylic acid additive (phthalate diesters of β-hydroxyethyl (meth)acrylate), phthalate diesters of β-hydroxyethyl (meth)acrylate Toluene diisoocyanate additive (toluene diisocyanate desirable of 厶-hydroxyethyl (meth)acrylate) or having an ethylenically unsaturated bond (to 12:15,2011,266, DX071103, 31287 twf.doc/n) (ethylenically unsaturated bond) a polymerizable compound in which a polymerizable compound having an ethylenically unsaturated bond is selected from ditrimethylol propanetetraacrylate, ethoxylated Tris(2-acryloxyethyl)isocyanurate, ethoxylated pentaerylthritoltetraacrylate (EO 4 mol), pentaerythritol tetraacrylate (pentaerythritoltetraacrylate) (EO 35 mol), eth〇Xylated trimethylolpropanetriacrylate (EO 9 mo l), ethoxylated trihydroxymercaptopropane triacrylate (E〇3mol), propoxylated triphenylmercaptopropane, propexylated pentaerythritoltetraacrylate (PO 4 mol), nonaethylene glycol Nonaethylene glycol diacrylate, dipentaerythritol hexaacrylate-modified caprolactone and trimethyl〇lpropanepropoxylate triacrylate The group formed is preferably dipentaerythritol hexamethylene acrylate. (C) Photoinitiator: based on (A) the soluble resin binder is 1 part by weight, and (c) the photoinitiator is, for example, between 〇1 and 1 part by weight, preferably Between 0.5 and 10 parts by weight. 13 201115266 DX071103 31287twf.doc/n (C) The photoinitiator 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-photogenic initiator is, for example, an amine compound, an alkoxyantharcene compound or a thioxanthone compound. The phosphine oxide-based compound is, for example, an arylphosphine oxide, an acylphosphine oxide, a bisacylphosphine oxide, or a 2,4,6-trimethylbenzoinyl-diphenylphosphine oxide. 2,4,6-trimethylbenzoyldiphenylphosphine oxide, TPO), 2,6-diethylbenzoyldiphenylphosphine oxide, 2,6-dimercaptobenzoyl- 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5,6-tetradecyl Benzoyldi(2,6-dimethylphenyl)phosphonate, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, bis(2,4,6-trimethylphenylhydrazino)phenylphosphine oxide (bis(2,4,6-trimethylbenzoyl)phenylphosphine(I-819)) or bis(2,6-nonylphenylphenyl)-2,4,4-trimethylphenylphosphine oxide 14 201115266 DX071103 31287t Wf.doc/n (bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide)) ° series of compounds, amine compounds, triazine compounds, lanthanide compounds, etc. For example, acetophenone, benzophenone, biphenylketone, 1-hydroxy-1-benzoylcyclohexane (1-) 184)), benzyl dimethylacetate 2,2-dimethoxy-1,2-diphenylethane-1 -one (1-651) , 1-benzyl-1-didecyl tertiary amine-1-(4- morphine-benzoyl)propane (1 -benzyl-1 -dimethylamino-1 -(4-morpholino-benzoyl)propane (1 -369)), 2-morphol-2-(4-methylmercapto)benzoylpropane (1-907), ethylantjiraquinone, 4-benzoyl-4-methyldiphenylsidfide, benzoinbutylether, 2-pyridyl-2-benzopyrene 2-hydroxy-2-benzoylpropane), 2-amino-2-(4-isopropyl)benzil-acrylic (2-hydroxy-2-(4-is) Opropyl)benzoylpropane), 4-butylbenzoic acid trigaster (4-151117 this 1^〇>^1^111〇1*〇11^]1 sister 6), 4-phenoxybenzoquinone 4-phenoxybenzoyldichloromethane, benzoylmethylformate, 1,7-bis(9-acridinyl) heptane, 9-n-butyl-3,6-bis(2-morphine-isobutyl) °^.(9-n-butyl-3,6-bis(2-morpholino-isobutyloyl)carbazole)' 10-butyl 2-chloroacrydone (10-butyl-2_chloroacrydone), 2-[2-(4•methoxy 15 201115266 DX071103 31287twf.doc/n phenyl-phenyl)-vinyl]-4,6-bis-trichloroanthracene -[1,3,5]triazine(2-[2-(4-methoxy-phenyl)-vinyl]-4,6-bis-trichloromethyl-[l,3,5]tr iazine), 2-( 4-methoxy-naphthalen-1-yl)_4,6-bis-trichloromethyl^3,5]triazine (2-(4-methoxy-naphthalen-1 -yl)-4,6-bis- Trichloromethyl-[ 1,3,5]tri 〇2^), 2-nonylbenzene [1,3]dioxetene-5-yl-4,6-bis-trichloromethyl-[1,3 ,5] triazine (2-benzo[l,3]dioxol-5-yl-4,6-bis-trichloromethyl-[l,3,5]triazine), 2-methyl-4,6-bis (three Chloromethyl)-s-triazine (2-methyl-4,6-bis(trichloromet) Hyl)_s-triazine), 2-phenyl-4,6-bis(trichloromethyl)-s-triazine (2-phenyl-4,6-bis(trichloromethyl)-s-triazine) or 2-naphthalene Ester-4,6-bis(trimethylmethyl)-S-triazine (2-naphthyl-4,6-bis(trichloromethyl)-s-triazine). The amine compound is, for example, triethanolamine, methyldiethanolamine (11^1;11)4(11611^11〇1&111丨1^), triisopropanolamine (11 also (^1:(^) >43111丨1^), 4-dimethylaminomethyl benzoate, 4-dimethylaminoethyl benzoate, 4-dimethylaminoethyl benzoate 4-methylaminoisoamylbenzoate, 2-methylaminoethyl benzoate, 4-diaminoamino-2-carboxylate 4-dimethylamino-2-ethylhexyl benzoate, N,N-methyl-p-anilide (]^,>^-11^]1}41)3 plus 〇111丨( 111^), 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzol Ketone (4,4'-bis(diethylammo)benzophenone) or 4,4'-bis(ethylmethylamino)benzophenone. 16 201115266 DX071103 31287twf. The doc/n alkoxy lanthanide compound is, for example, 9,10-dimethoxyanthracene, 9 10_1,10-diethoxyanthracene, 2-ethyl 9,10-dimethoxyanthracene or 2-ethyl 9,10, diethoxyanthracene (2-ethyl-9,10-diethoxyanthracene) ° ° The compound of the tonate is, for example, 2-isopropyl. It is 2-isopropylthioxanthone, 4-isopropyl, and beta-butanone (4- Isopropylthioxanthone, IPTX), 2,4-diethylthioxanthone 'DETX, 2,4-trichlorothioxanthone or 1-chloro-4-propanol Based on ridicule (1 -chloro-4-propoxythioxanthone). (D) Organic acid anhydride: based on (A) the alkali-soluble resin binder is 1 part by weight, and the content of the (D) organic acid anhydride is, for example, between 0.1 and 100 parts by weight, preferably between 2 and 5 parts by weight. . (D) The organic acid Sf is, for example, a maleic anhydride, a itaconic anhydride, a tetrahydrophthalic anhydride, a citraconic anhydride or a mesaconic acid Sf. (mesaconic anhydride), wherein maleic anhydride is preferred. The above organic acid anhydrides may be used singly or in combination of several kinds. (E) A compound containing at least two epoxy groups in the molecule: based on (A) a soluble resin binder of 1 part by weight, a molecule of 17 201115266 DX071103 31287twf.doc/n containing at least 2 epoxy groups The content of the compound is, for example, between 〇 parts by weight, preferably between 2 and 10 parts by weight. (E) A compound having at least two epoxy groups in the molecule is, for example, a bisphenol A type epoxy compound, a bisphenol S type epoxy compound, 芴-9-bisphenol Fluorine-9-bisphenoldiglycidyl Ether (FBDE), bisphenol A type epoxy resin (for example: oiled Shell Epoxy company's trade name Epikote 828, 1001, 1002, 1004 Etc.), an epoxy resin obtained by reacting an alcoholic hydroxyl group with an epichlorohydrin (for example: 曰本化制药公司's trade name NER- 1302 'epoxy equivalent 323, softening point 76. bisphenol F type epoxy resin (for example: oily shell Epoxy company, trade name Epikote 8〇7, 4001, 4002, 4004 Etc., an epoxy resin obtained by reacting an alcoholic hydroxyl group of an bisphenol F-type epoxy resin with an epichlorohydrin (for example, manufactured by Nippon Kayaku Co., Ltd., trade name NER-7406, epoxy Equivalent 350, softening point 66. bismuth, diphenyl Biphenyl glycidyl ether (for example: oiled Shell Epoxy a coat, ηπ is named Epikote YX4000), phenol novolac type epoxy resin (for example: Nippon Kayaku Co., Ltd.) System, the product name is EPPN-201; oiled by Shell Epoxy company, the trade name is Epikote 152, 154, 157S65, 157S70; Dow Chemical Company, trade name is DEN-438), 曱 (本) acid running ring Oxygen resin (cres〇in〇v〇iac ep0Xy resin) (for example, manufactured by Sakamoto Chemical Co., Ltd., trade name: E〇CN-1〇2S, 1〇2〇, 104S), triglycidyl isocyanurate (triglycidyl is〇cyanurate) (Example 18 201115266 DX071103 31287twf.doc/n such as: manufactured by Seiko Chemical Co., Ltd., trade name TEPIC), trisphenol methane type epoxy resin (eg: Japanese chemical) The company's product name is EPPN-5 (H, 502, 503), 苟 type epoxy resin (flu_e _ 61? Qing 1^11) (for example: manufactured by Xinyi Iron Chemical Co., Ltd., trade name is 矽17_3〇〇) , alicyclic epoxy resin (for example: Daicel Chemical Industry Co., Ltd., trade name

Celloxide P, or epoxidized polybutanene (4) two (four) polybutachene (for example: Daicel Chemical Industry Co., Ltd., trade name EP〇leadPB3_ ' which is preferably gauze diglycidyl ^ in the above molecule The compound containing at least 2 epoxy groups may be used alone or in combination of several kinds. (F) Organic solvent: Based on (A) the test can be converted to _ 丨 (9) The solvent content is, for example, 10 to 2 times ± () Organic as ~250 parts by weight. 2 between lake rereading, preferably between

The organic solvent is, for example, stupid, toluene, xylene, decyl alcohol, ethanol early (tetra), diethylene glycol dimer, diethylene glycol (tetra) = vinegar, ethyl, ethyl vinegar, lactic acid ethyl acetate, g base, money agent Acid §, ethyl cellosolve acetic acid f field I, - ethanol monoethyl ether, diethanol monobutyl bond, C - = acetic acid cool, propylene glycol ethyl acetate acetate, C22: 1 = 1 A:, c Dimethylmethyl ugly is called methylpyrrolidone and γ-butyrolactone. The above organic, and the agent may be used singly or in combination of several kinds. In addition, as a protective film for a color filter, the photosensitive resin composition of the present invention is mainly composed of (A) an alkali-soluble resin binder and (B) a photopolymerizable type. A compound having an ethylenically unsaturated group, (a photoinitiator, (D) an organic acid anhydride, or a compound having at least two epoxy groups in the (E) molecule is a main component. Of course, depending on actual needs, the following may be added as necessary In one embodiment, a adhesion aid (c〇upUng agent) may be further added to improve the adhesion between the photosensitive resin composition and the color filter, and to enhance the photosensitive resin composition. The adhesion to the transparent electrode is 1 part by weight based on the photosensitive resin composition, and the adhesion aid may be used in an amount of from 0.01 to 30 parts by weight, preferably from 0.5 to 3 parts by weight. The adhesion promoter is, for example, an epoxy group-containing or amino group-containing hydrazine compound, which is, for example, 10,000-(3,4-epoxycyclohexane)ethyltrimethoxydecane (P-(3,4-epoxycyclohexyl). )ethyl trimethoxysilane), /3 - (3,4-epoxycyclohexene) P-(3,4-epoxycyclohexyl)ethyl triethoxysilane, γ-glycidoxypropyl trimethoxysilane (GTS), γ-glycidyl propyl sulfonate Γ-glycidoxypropyl methyldimethoxysilane, γ-glycidoxypropyl methyldiethoxysilane, γ-glycidil dimethoxy ethoxy ethoxylate Γ-glycidoxypropyl dimethoxy(ethoxy)silane), γ-glycidoxypropyl dimethyl(methoxy)silane, γ-glycidyl dimethyl ethoxylate Γ-glycidoxypropyl dimethyl(ethoxy)silane), 3,4-epoxybutyltriene 20 201115266 DX071103 31287twf.doc/n 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethylsilane 3,4-epoxybutyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane, (3_ Aminopropyl)trimethoxysilanium (3-aminopropyl)trimethoxysiIane, (3-aminopropyltriazole) (3-aminopropyl) triethoxysilane, (N,N-diethyl-3-aminopropyl)trimethoxysilane or hydrazine -β(aminoethyl)γ-aminopropylphosphonium trimethoxysilane (Np(aminoethyl)Y-aminopr〇pyl trimethoxysilane). The above-mentioned adhesion aids may be used singly or in combination of several kinds. In a real example, a surfactant may be further added. The surfactant may be used in an amount of from 0.01 to 30 parts by weight, preferably from 0.5 to 3 parts by weight, based on 100 parts by weight of the photosensitive resin composition. The surfactant is, for example, a polyoxyethylene ether ether ❻〇 lyoxy alkyl alkyl ethers (for example, polyoxyethylene laurel laurel _ (^ 〇 〇; ^ pull 1 to 161 ^ 1 & 111716 such as 1:), polyoxyethylene stearin (polyoxyethylene stearyl ether), polyoxyethylene oleyl ether, polyoxyethylene aryl ethers (eg polyoxyethylene octylphenyl ether ^p〇iy〇Xyethyiene 〇C|yi phenyl) Ether), 壬 纷 纷 纷 〇 y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ^p〇iyethyiene giyC〇i dilaurate), polyethylene glycol distearate & 〇iyethyiene giyC〇i distearate)), organic oxy-oxygenated polymer p〇iymer) (eg 21 201115266 DX071103 31287twf.doc/ n KP341 (manufactured by Shin-Etsu Chemical Industry Co. Ltd.)) or (meth)acrylic acid polymer (for example, p〇iyflow N〇. 75, 90, 95 (by Kyoei-Sha) Yushi Kagaku Kogyo Co., Ltd.), Megafac F171, F172, F173, F475 ( Dainippon Chemicals ana Ink Co" Ltd.), Florard FC430, FC431 (manufactured by 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.)). The above surfactants may be used singly or in combination of several kinds. In an embodiment, other additives such as a deformer, a leveling agent 'thermal polymerization in Wbitor agent' and the like may be further added. The photosensitive resin composition of the present invention is mainly prepared by the above (A) soluble resin binder, (B) photopolymerizable ethylenically unsaturated group-containing compound, (C) photoinitiator, and (D) organic An acid anhydride, a compound containing at least two epoxy groups in the (E) molecule, and (F) an organic solvent uniformly mixed into a solution state in a stirrer, whose viscosity is between 1 and 200 cps, preferably between 3 and 25 CpS. between. The photosensitive resin composition of the present invention can be applied onto a substrate by spin coating, cast coating, cast-spin coating or the like. After coating, prebake at 80 C for 2 minutes to remove the solvent. Then, the full exposure is 200 mJ/cm2. After development, it is baked at 23 Torr for 2 minutes to form a photosensitive resin layer of 1 to 1.5 μm, and can be used as a protective film for a color filter. The substrate described above is, for example, an alkali-free glass, a soda-lime glass, a hard glass (Pyrus glass), a quartz glass, or a photoelectric conversion device for the 201115266 DX071103 31287twf.doc/n solid-state viewing device for a liquid crystal display device. A substrate (such as a germanium substrate) or the like. (A) Synthetic method for testing soluble resin binder: Method 1:

: There are two kinds of dilute acid vinegar (diacryiate) of the lower jaw j, the mouth structure I, the ethylenically unsaturated compound (ai) having a t group, and other copolymerizable with (al) and (4) (10) The ethylenically unsaturated compound (IV) is copolymerized, and the compound of the lower (four) configuration formula H is then grafted with a second saturated monomer (a4). The reaction equation is as follows.

(a2) 23 201115266 DX071103 31287twf.doc/n

Rn

24 201115266 DX071103 31287twf.doc/n

Method 2: A compound having the following structural formula III is synthesized by copolymerization of an ethylenically unsaturated compound (al) having an acid group and other ethylenically unsaturated compound (a2) copolymerizable with (al). Then, an epoxy group-containing ruthenium (a3) is bridged to form a compound having the following structural formula II by an esterification reaction. Thereafter, it is grafted with an epoxy group-containing ethylenically unsaturated monomer (a4). The reaction equation is as follows:

201115266 DX071103 31287twf.doc/n

Structural Formula II 201115266 DX071103 31287twf.doc/n

Method 3: A compound having the following structural formula is synthesized by copolymerization of an ethylenically unsaturated compound (al) having an acid group and other ethylenically unsaturated compound (a2) copolymerizable with (al). Thereafter, the epoxy group-containing cerium (a3) and the epoxy group-containing ethylenically unsaturated monomer (a4) are bridged and grafted simultaneously by an esterification reaction. The reaction equation is as follows: 27 201115266 DX071103 31287twf.doc/n

Ri

\ OH +

Ri

(al) (a2)

Structural formula III

28 201115266 DX071103 31287twf.doc/n (A) Synthesis example of alkali-soluble resin binder A1: Synthesis example 1 (method 1): 180 g of DGDE solvent and 290 g of PGMEA solvent were added to the reaction flask, and nitrogen gas was introduced thereto. And stir to heat to l ° ° c. In addition, 6.8 g of 2,2-azobisisobutyronitrile (AIBN) was dissolved in 110 g of DGDE' and then 57.2 g of dicyclopentanylmethacrylate '53.3 g Methacrylic acid, 5.2 grams of allylmethacrylate, 1.85 grams of methacrylonitriie, 43 grams of styrene, 16 grams of acrylic acid vinegar (50 The mixture of the PGMEA solution was dropped into the reaction flask, and the reaction mixture was completely dropped into a reaction vessel of 1 ° C for 1.5 hours to continue the stirring reaction for 1 hour. Next, 0.3 g of AIBN was dissolved in a solution of 5 g/5 g of DGDE/PGMEA, and the reaction bottle was dropped into the reaction bottle over 1 minute, and the reaction was continued for 3 hours. Thereafter, the temperature of the reaction flask was lowered back to 80 C ' and the nitrogen was stopped and 58.7 g of glycidyl methacrylate, 2.7 g of catalyst (1-methylimidazole) and hydrazine were added. A 165 g inhibitor (4-methoxyphenol) was stirred in air for 19 hours. The obtained product resin solution had a solid content of 26.7 wt.%; a viscosity of 10 cp 6 cps / 25 ° C; an acid value of 47.1 mg KOH / g; and a weight average molecular weight of 17939. (A) Synthesis Example of Soluble Resin Glue A2: Synthesis Example 2 (Method 2): 368 g of MBA solvent and 92 g of 29 201115266 DX071103 31287twf.doc/n PGMEA solvent were added to the reaction flask, and nitrogen gas was introduced. And stir to heat to l ° ° C. In addition, 6 g of AIBN was dissolved in a mixed solution of MBA/PGMEA of 88 g / 22 g, followed by 50.2 g of dicyclopentanyl methacrylate, 47.5 g of methacrylic acid, and 4.5 g of allyl methacrylate. 1.6 g of mercapto acrylonitrile and 37.5 g of styrene were mixed into the reaction flask, and the reactant was completely dropped into a reaction flask at 100 ° C for 1.5 hours, and the reaction was further stirred for 1 hour after the completion of the dropwise addition. Next, 0.3 g of AIBN was dissolved in 10 g of the MBA solution, dropped into the reaction flask in 1 minute, and the reaction was continued for 3 hours. Thereafter, 5.6 g of fluorene bisepoxy and 0.14 g of catalyst (1_mercaptopurine) were added for 14 hours. The reaction flask temperature was lowered back to 80 C, and the nitrogen was stopped and 51, 2 g was added. Glycidyl methacrylate, 2.5 g of a catalyst (i-methyl π sitting) and 0.14 g of an inhibitor (4-decyloxybenzene) were turbulent in air for 19 hours. The product resin solution thus obtained had a solid content of 25.1 vvt.%; a viscosity of 119 cps/25 ° C'·acid value of 64.5 mgKOH/g; and a weight average molecular weight of 18,265. (A) Synthesis Example of Soluble Resin Glue A3: Synthesis Example 3 (Method 3): 235 g of DGDE solvent and 235 g of PGMEA solvent were added to the reaction flask, and nitrogen gas was passed through and the mixture was heated to just. c. In addition, 8 g of AIBN was dissolved in a mixed solution of 55 g/55 g of DGDE/PGMEA 'again with 48 g of methyl propyl-bicyclopentan, 49 g of methyl acetoacetate, 4.5 g of methacrylic acid. Allocating g, 16 g of methyl acrylonitrile, gram-like styrene and styrene mixed in a human reaction flask, the reactants were completely dropped into the reactor within 30 hours. 30 201115266 DX071103 31287twf.doc/n °C reaction bottle The reaction was continued for 1 hour after the completion of the dropwise addition. Next, 4 g of AIBN was dissolved in a solution of 5 g/5 g of DGDE/PGMEA and dropped into the reaction flask in 1 minute to continue the reaction for 3 hours. After that, the temperature of the reaction flask was lowered back to 80 ° C ' and the nitrogen was stopped and 22.3 g of bis(a) bismuth oxide, 2.03 g of catalyst pph3, and 43 g of glycidol methacrylate, 2.0 g of catalyst were added (1_曱基咪 saliva) and 15 g of inhibitor (4-methoxybenzene)' were stirred in air for 18 hours. The resulting product resin solution had a solids content of 25.9 wt.% and a viscosity of 229%/25. (:; acid value is 61 mgKOH/g; weight average molecular weight is ηι8〇. (A) Synthesis of colloidal resin binder τ (for example without truss bridge):

2: 35 g of DGDE solvent and 235 g of PGMEA solvent were added to the reaction flask, and nitrogen gas was passed through and stirred and heated to 1 〇〇c>c. In addition, 6 grams of AIBN was dissolved in DGDE/PGMEA at 55 g/55 g of mixed solution 31 201115266 DX071103 31287twf.doc/n liquid 'again with 48 grams of dicyclopentanyl methacrylate, 49 grams of methacrylic acid, 4'5g of allyl methacrylate, 1.6g of decyl acrylonitrile, π gram of styrene were mixed into the reaction flask, and the reaction was completely dropped into the 100 C reaction bottle within 1.5 hours. 'Turn off the reaction and continue to stir the reaction for 1 hour. Next, 0.4 g of AIBN was dissolved in a solution of 5 g/5 g of DGDE/PGMEA, and dropped into the reaction flask within 10 minutes' and the reaction was continued for 3 hours. Thereafter, the temperature of the reaction flask was lowered back to 80 ° C. '51.6 g of mercapto propylene warm glycidol, 25 g of catalyst (1-methyl 11 m hydrazine) and 0.15 g of inhibitor (4-methoxyl) Benzene was stirred in air for 18 hours. The obtained product resin solution had a solid content 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. 10 parts by weight of the (A) alkali-soluble resin binders Al, A2, A3' T and 2.7 parts by weight of DPHA, 0.5 parts by weight of FBDE, 0.25 parts by weight of MA, 0.2 parts by weight of 1 obtained by Synthesis Examples 1 to 4 were used. -907, 0.5 parts by weight of IPTX, 0.02 parts by weight of the adhesion aid GTS, and 4 parts by weight of the solvent PGMEA were stirred and mixed to prepare a photosensitive resin for color filter, and the composition (Table 1) ). The photosensitive resin composition was evaluated by various measurement evaluation methods described below. The results obtained are shown in Table 1. Further, the formulations of the other synthesis examples and the synthesis comparative examples are also shown in Table 1, and the results obtained are shown in Table 2. 32 201115266 DX071103 31287twf.doc/n Table 1 Composition Resin Adhesive (g) DPHA (g) FBDE (g) MA (g) Photoinitiator (g) GTS (g) Solvent (g) Formulation 1 Resin Adhesive A1 (Synthesis Example 1) 10 2.7 0.5 0.25 1-907 (0.2) IPTX (0.05) 0.02 PGMEA (4) Formulation 2 Resin Adhesive A2 (Synthesis Example 2) 10 2.7 0.5 0.25 1-907 (0.2) IPTX (0.05) 0.02 PGMEA(4) Formulation 3 Resin Adhesive A3 (Synthesis Example 3) 10 2.7 0.5 0.25 1-907 (0.2) ΙΡΤΧ (0.05) 0.02 PGMEA (4) Formulation 4 Resin Glue T (Synthetic Comparative Example) 10 2.7 0.5 0.25 1-907(0.2) ΙΡΤΧ(0.05) 0.02 PGMEA(4)

Evaluation method: 1. Heat resistance The photosensitive resin layer on the obtained glass substrate was subjected to an oven treatment at 250 ° C for 60 minutes, and the film thickness change before and after the treatment was measured by a profiler Tencor a - step 500. 〇: thickness change of $5% X: thickness change > 5% -, verifyability The photosensitive resin layer on the obtained glass substrate was 25 ° C ± 2 . The underarm & foam was immersed in 10% NaOH for 3 hours, and the film thickness change before and after the treatment was measured by profller Tencor α-step 500. 〇: thickness variation <1% 33 201115266 DX071103 31287twf.doc/n X : thickness variation ^1% III. Acid resistance Soak the photosensitive resin layer on the prepared glass substrate at 25 ° C ± 2 ° C The film thickness changes before and after treatment were measured in 10% HC1 for 3 hours and profiler Tencor a-step 500. 〇: thickness change < 1% X: thickness change 21% 4. Solvent resistance The photosensitive resin layer on the obtained glass substrate was 25. 〇±2. 〇下> was bubbled in NMP for 3 hours, and the film thickness change before and after treatment was measured by profiler Tencor a-step 500. 〇: thickness change < 1% X: thickness change 21% 5. Transmittance The photosensitive resin layer on the obtained glass substrate was measured for light transmittance at a wavelength of 380 to 800 nm. 〇: light transmittance > 97% X: light transmittance: $97% 6. Heat-resistant discoloration The photosensitive resin layer on the obtained glass substrate was treated in an oven at 250T for 60 minutes, and light having a wavelength of 380 to 800 nm. The measured light transmittance was changed to 201115266 DXU/H03 31287twf.doc/n. 〇: The light transmittance changes by 5% or less △: The light transmittance changes by 5% to 10% X: The light transmittance changes by 10% or more. Table 2 Evaluation results Heat resistance, alkali resistance, acid resistance, solvent resistance, light resistance, heat resistance Color-changing formula 1 〇〇〇.〇〇〇 Formulation 2 〇〇〇〇〇〇 Formulation 3 〇〇〇〇〇〇 Formulation 4 XX 〇〇〇〇 示 示 , , , , , 感光 感光 感光 感光 感光 感光 感光 感光The protective film of the color filter in which the photosensitive resin composition is polymerized by the high transmittance, heat resistance, acid resistance, alkali resistance, and heat discoloration resistance can effectively protect the color filter.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the scope of the invention, and the scope of the patent application is defined by the appended claims. [Simple description of the diagram] Benefits [Main component symbol description] Benefit 35

Claims (1)

201115266 DX071103 31287twf.doc/n VII. Patent Application Range 1. 1. A photosensitive resin composition comprising: (A) a soluble resin binder containing a polymer represented by the formula (1), Co2h Wherein a is from 1 to 10 mole percent; b is from 30 to 60 mole percent; C is from 5 to 30 mole percent; d is from 5 to 50 mole percent; and R is phenylhydrazine, phenyl, CN or C ( 0) 0R2, wherein R2 is a linear or cyclic alkyl group of C1 to C15, a phenyl group, a phenylhydrazine group or an allyl group; R! is a fluorene group of fluorene, C1 to C4; (Β) a photopolymerizable type containing B a compound having a dilute unsaturated group; 36 201115266 /1103 31287twf.doc/n (c) a photoinitiator; (D) an organic acid anhydride; (E) a compound having at least two epoxy groups in the molecule; and (F) Organic solvents. 2. The photosensitive resin composition as described in claim 1 wherein (A) the soluble resin binder has a weight average molecular weight of from 3,000 to 100,000. 3. The light-emitting resin composition according to claim 1, wherein the (A) alkali-soluble resin binder has a solid content of between 1 〇 and 5 〇 0 / 。. 4. The photosensitive resin composition as described in claim 1 wherein (A) the acid value of the soluble resin binder is between 1 〇 4 〇〇 mgKOH/g. 5. The photosensitive resin composition according to claim 1, wherein the (A) soluble resin binder is 1 part by weight, and (b) the photopolymerizable ethylenically unsaturated group-containing compound The content is between parts by weight. 6. The photosensitive resin composition according to claim 1, wherein the (A) alkali-soluble resin binder is 1 part by weight, and (c) the photoinitiator is in a range of 〇. 〖〇() between parts by weight. 7. The photosensitive resin composition according to the invention of claim 2, wherein (D) the alkali-soluble resin binder is 1 part by weight, and (D) the content of the organic acid anhydride is 〇.1 to 1〇 〇 between parts by weight. 8. The photosensitive resin composition of claim 1, wherein the (A) molecule contains at least 1 part by weight of the soluble resin binder, and the (E) molecule contains at least The content of the two epoxy group-containing compounds is between 0.1 and 100 parts by weight. 9. The photosensitive resin composition according to claim 1, wherein the (A) alkali-soluble resin binder is 1 part by weight, and (F) the organic solvent is contained in an amount of 10 to 2500 parts by weight. between. 10. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition has a viscosity of between 1 and 2 Å CpS. A protective film of a color light-receiving sheet, which is obtained by polymerizing a photosensitive resin composition according to any one of claims 1 to 10. 38 201115266 DX071103 31287twf.doc/n West, designated representative figure = (1) The designated representative figure of this case: None (2) Simple description of the component symbol of this representative figure: No. 5. If there is a chemical formula in this case, please reveal the best display. Chemical formula of the inventive feature: Formula (1) 4