TWI461478B - Photo-sensitivity resin composition, overcoating layer of color filter and photo-sensitivity resin adhesive - Google Patents

Description

Photosensitive resin composition, protective film for color filter, and photosensitive resin Glue

The invention relates to a photosensitive resin composition, a protective film of a color filter and a photosensitive resin adhesive, and particularly relates to a light transmittance, heat resistance, acid resistance, alkali resistance and heat resistance. A photosensitive resin composition having characteristics such as discoloration, a protective film of a color filter, and a photosensitive resin binder.

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, green, and blue colors between adjacent black matrices. The color layer acts as a pixel, so that when the light passes through the pixel, it will appear.

In addition, after the color filter is completed, a transparent electrode is then formed to cover the black matrix and the color layer. Generally, an overcoating layer is formed between the color filter 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 protective film must have high light transmittance, adhesion, heat resistance, acid resistance and alkali resistance.

In some documents, related art relating to a protective film for a color filter has been proposed, such as US 6,582,862, US Pat. No. 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 including alkali soluble. Alkali dissolvable resin binder, photopolymerization compound, photopolymerization initiator and solvent. However, the compositions proposed in these documents are inferior in properties such as alkali resistance, acid resistance, and heat discoloration resistance.

Therefore, the development of the composition of the protective film for a color filter and the improvement of its characteristics have become one of the important topics in the development of the industry.

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 filter.

The present invention provides a photosensitive resin adhesive which has characteristics of high light transmittance, heat resistance, acid resistance, alkali resistance and heat discoloration resistance.

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, (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 binder contains the polymer represented by the structural formula (1), Wherein x=1~10 mole percentage; y=29~59 mole percentage; a+b=40~60 mole percentage; a=15~40 mole percentage; b=5~30 mole percentage; R is Benzyl, phenyl, CN or C(O)OR2, wherein R2 is a C1 to C15 linear or cyclic alkyl group, a phenyl group, a benzyl group or an allyl group; and R ₁ is H or a C1 to C4 group. alkyl.

According to the photosensitive resin composition of the embodiment of the invention, the weight average molecular weight of the above (A) alkali-soluble resin binder is, for example, between 3,000 and 300,000.

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 10 and 50%.

According to the photosensitive resin composition of the embodiment of the invention, the acid value of the (A) alkali-soluble resin binder is, for example, between 10 and 400 mgKOH/g.

The photosensitive resin composition according to the embodiment of the invention is based on 100 parts by weight of the (A) alkali-soluble resin binder, and the content of the (B) photopolymerizable ethylenically unsaturated group-containing compound is, for example, from 1 to 250. Between parts by weight.

The photosensitive resin composition according to the embodiment of the present invention is contained in an amount of, for example, 100 parts by weight based on (A) the alkali-soluble resin binder, and (C) the photoinitiator is, for example, between 0.1 and 100 parts by weight.

The photosensitive resin composition according to the embodiment of the present invention has a content of (D) an organic acid anhydride of, for example, 0.1 to 100 parts by weight based on 100 parts by weight of the (A) alkali-soluble resin binder.

The photosensitive resin composition according to the embodiment of the present invention has a content of at least two epoxy groups in the molecule (E), for example, between 0.1 and 100, based on 100 parts by weight of the (A) alkali-soluble resin binder. Between parts by weight.

The photosensitive resin composition according to the embodiment of the present invention has a content of (F) an organic solvent of, for example, 10 to 2500 parts by weight based on 100 parts by weight of the (A) alkali-soluble resin binder.

According to the photosensitive resin composition of the embodiment of the invention, the photosensitive resin composition has a viscosity of, for example, between 1 and 200 cps.

The present invention further provides a protective film for a color filter which is obtained by polymerizing the above-mentioned photosensitive resin composition.

The present invention further proposes a photosensitive resin binder comprising the above (A) alkali-soluble resin binder.

In view of the above, since the photosensitive resin composition of the present invention has characteristics such as high light transmittance, heat resistance, acid resistance, alkali resistance, and heat discoloration resistance, the color of the photosensitive resin composition of the present invention is polymerized. Filter The protective film effectively protects the color filter to further enhance component performance.

The above described features and advantages of the present invention will be more apparent from the following description.

The present invention proposes a photosensitive resin composition which has high light transmittance, heat resistance, acid resistance, alkali resistance and heat discoloration resistance, and thus colors obtained by polymerizing the photosensitive resin composition The protective film of the filter can effectively protect the color filter.

The present invention further provides a photosensitive resin binder comprising the following (A) alkali-soluble resin binder.

The photosensitive resin composition of the present invention comprises (A) an alkali-soluble resin binder, (B) a photopolymerizable ethylenically unsaturated group-containing compound, (C) a photoinitiator, (D) an organic acid anhydride, (E) A compound having at least two epoxy groups in the molecule and (F) an organic solvent. In addition, it is preferred to use propylene glycol methyl ether acetate (PGMEA) or 3-methoxy butyl methacrylate in the adhesive or in the photoresist formulation. Acetate, MBA), 3-ethoxy ethyl propionate (EEPA) and other solvents.

(A) Alkali-soluble resin binder:

(A) the alkali-soluble resin binder is a solution composed of a polymer represented by the structural formula (1) and a solvent such as PGMEA, MBA, or EEPA. Wherein x=1~10 mole percentage; y=29~59 mole percentage; a+b=40~60 mole percentage; a=15~40 mole percentage; b=5~30 mole percentage; R is Benzyl, phenyl, CN or C(O)OR2, wherein R2 is a C1 to C15 linear or cyclic alkyl group, a phenyl group, a benzyl group or an allyl group; and R ₁ is H or a C1 to C4 group. alkyl. The weight average molecular weight of the (A) alkali-soluble resin binder is, for example, between 3,000 and 300,000; the solid content is, for example, between 10 and 50%; and the acid value is, for example, between 10 and 400 mgKOH/g.

(B) Photopolymerizable ethylenically unsaturated group-containing compound

The content of the (B) photopolymerizable ethylenically unsaturated group-containing compound is, for example, between 1 and 250 parts by weight, preferably between 20 and 60 parts by weight, based on 100 parts by weight of the (A) alkali-soluble resin binder. Between the shares.

(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, which has a polymerization of 2 to 14 ethylene oxide groups. Polyethylene glycol di(meth)acrylate, trimethylol propane di(meth)acrylate, trimethylol propane tri(meth) Acetate), pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, having 2-14 propylene oxide groups ( Propyleneoxide group) propyleneglycol di(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth) Acrylate, DPHA), trimethylolpropanetriglycidylether acrylic acid additive, bisphenol A diglycidyl ether acrylic acid additive phenol A diglycidylether acrylic acid additives), phthalate esters of (meth) acrylic acid - β - hydroxyethyl methacrylate (phthalate diesters of β -hydroxyethyl (meth ) acrylate), tolylene hydrogen ester additive (A yl) acrylic acid - β - hydroxyethyl methacrylate (toluene diisocyanate additives of β -hydroxyethyl ( meth) acrylate) or a compound having a polymerizable (polymeric compound) ethylenically unsaturated bond (ethylenically unsaturated bond), wherein having an ethylenically unsaturated bond The polymerizable compound is selected from the group consisting of ditrimethylol propanetetraacrylate, tris(2-acryloxyethyl)isocyanurate, and ethoxylated pentaerythritol Ethoxylated pentaerylthritoltetraacrylate (EO 4mol), pentaerythritoltetraacrylate (EO 35mol), ethoxylated trimethylolpropanetriacrylate (EO 9mol), Ethoxytrimethylolpropane triacrylate (EO 3mol), propoxytrimethylolpropane triacrylate (propx Citricated pentaerythritoltetraacrylate) (PO 4 mol), nonaethylene glycol diacrylate, dipentaerythritol hexaacrylate-modified caprolactone and trimethylolpropane propoxy triacrylate A group consisting of trimethylolpropanepropoxylate triacrylate, preferably dipentaerythritol hexamethacrylate.

(C) Photoinitiator:

The content of the (C) photoinitiator is, for example, between 0.1 and 100 parts by weight, preferably between 0.5 and 10 parts by weight, based on 100 parts by weight of the (A) alkali-soluble resin binder.

(C) The photoinitiator is, for example, a phosphine oxide compound, a carbonyl compound, an aminocarbonyl compound, a triazine compound or an oxime compound, and versus A co-photoinitiator is used together. 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, 2,4,6-trimethylbenzimidyl-diphenylphosphine oxide ( 2,6,6-trimethylbenzoyldiphenylphosphine oxide, TPO), 2,6-diethylbenzoyldiphenylphosphine oxide, 2,6-dimethylbenzylidene 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5,6-tetramethyl Benzoyldi(2,6-dimethylphenyl)phosphonate, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide (bis(2,4,6-trimethylbenzoyl)phenylphosphine(I-819)) or bis(2,6-methoxybenzhydryl)-2,4,4-trimethylphenylphosphine oxide (bis) 2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide)).

Carbonyl compound, amine carbonyl compound, triazine compound A series of compounds such as lanthanide compounds, such as acetophenone, benzophenone, biphenylketone, 1-hydroxy-1-cyclohexyl phenyl ketone (1-hydroxy-) 1-benzoylcyclohexane (I-184)), benzyl acetone 2,2-dimethoxy-1,2-diphenylethane-1-one (benzyldimethylketal 2,2-dimethoxy-1,2-diphenylethane-1- One(I-651)), 1-benzyl-1-dimethyl-tert-amine-1-(4-morpholin-benzamide)propane (1-benzyl-1-dimethylamino-1-(4-morpholino- Benzoyl)propane (I-369)), 2-morpholyl-2-(4-methylmercapto)benzoylpropane (I-907), ethyl An (ethylanthraquinone), 4-benzoyl-4-methyldiphenylsulfide, benzoinbutylether, 2-hydroxy-2-phenyl 2-hydroxy-2-benzoylpropane, 2-hydroxy-2-(4-isopropyl)benzoylpropane, 4-butyl benzoyl 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzhydrazide Zoylmethylformate), 1,7-bis(9-acridinyl)heptane, 9-n-butyl-3,6-bis(2-morpholine-iso Butyr) 9-n-butyl-3,6-bis(2-morpholino-isobutyloyl)carbazole, 10-butyl-2-chloroacrydone (10-butyl-2-chloroacrydone), 2-[2- (4-methoxy-phenyl)-vinyl]-4,6-bis-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-toluene[1,3]dioxol-5- 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-naphthyl ester-4,6-bis(trichloromethyl) )-s-triazine (2-naphthyl-4,6-bis(trichloromethyl)-s-triazine).

The amine compound is, for example, triethanolamine, methyldiethanolamine, triisopropylamine, 4-dimethylaminomethyl benzoate, 4- 4-dimethylaminoethyl benzoate, 4-methylaminoisoamyl benzoate, 2-methylaminoethyl benzoate 2-methylaminoethyl benzoate, 4-dimethylamino-2-ethylhexyl benzoate, N,N-methyl-p-toluidine (N, N -methylparatoluidine), 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone Ketone (4,4'-bis(diethylamino)benzophenone) or 4,4'-bis(ethylmethylamino)benzophenone.

The alkoxy ruthenium compound is, for example, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl 9,10 -dimethoxy oxime (2-ethyl-9,10-dimethoxyanthracene) or 2-ethyl 9,10-diethoxyanthracene.

The thioxantane compounds are, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone (IPTX), 2,4-diethylthioxanthone (2,4). -diethylthioxanthone, DETX), 2,4-trichlorothioxanthone or 1-chloro-4-propoxythioxanthone.

(D) Organic acid anhydride:

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, based on 100 parts by weight of the (A) alkali-soluble resin binder.

(D) The organic acid anhydride is, for example, maleic anhydride (MA), itaconic anhydride, tetrahydrophthalic anhydride, citraconic anhydride or 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 having at least two epoxy groups in the molecule:

The content of the compound having at least two epoxy groups in the (E) molecule is, for example, between 0.1 and 100 parts by weight, preferably between 2 and 10 parts by weight, based on 100 parts by weight of the (A) alkali-soluble resin binder. Between the shares.

(E) a compound having at least two epoxy groups in the molecule, for example, bisphenol A Bisphenol A type epoxy compound, bisphenol S type epoxy compound, fluorene-9-bisphenol diglycidyl Ether (FBDE), bisphenol Bisphenol A type epoxy resin (for example: oiled Shell Epoxy, trade name: Epikote 828, 1001, 1002, 1004, etc.), alcoholic hydroxyl group of bisphenol A epoxy resin (alcoholic hydroxyl) An epoxy resin obtained by reacting with epichlorohydrin (for example, manufactured by Nippon Kayaku Co., Ltd., trade name: NER-1302, epoxy equivalent 323, softening point 76 ° C), bisphenol F type epoxy resin (bisphenol F type epoxy resin) (for example, oiled by Shell Epoxy, trade name: Epikote 807, 4001, 4002, 4004, etc.), alcoholic hydroxyl of bisphenol F epoxy resin and epoxy chloride Epoxy resin obtained by reaction of epichlorohydrin (for example, manufactured by Nippon Kayaku Co., Ltd., trade name: NER-7406, epoxy equivalent 350, softening point 66 ° C), biphenyl glycidyl ether (biphenyl glycidyl ether) For example: oiled Shell Epoxy company, the product name is Epikote YX 4000), phenol novolac type epoxy resin (for example, manufactured by Nippon Kayaku Co., Ltd., trade name EPPN-201; manufactured by Oiled Shell Epoxy Co., Ltd. under the trade name Epikote 152, 154, 157S65 157S70; manufactured by The Dow Chemical Company, trade name DEN-438), cresol novolac type epoxy resin (for example, manufactured by Nippon Kayaku Co., Ltd., trade name EOCN-102S, 1020) , 104S), triglycidyl isocyanurate (for example: manufactured by Nissan Chemical Co., Ltd., trade name TEPIC), trisphenol methane type epoxy resin (for example: Nippon Kayaku) Company-made, trade name EPPN-501, 502, 503), fluorene type Epoxy resin) (for example, manufactured by Nippon Steel Chemical Co., Ltd. under the trade name ESF-300), alicyclic epoxy resin (for example, manufactured by Daicel Chemical Industry Co., Ltd. under the trade name Celloxide 2021P, EHPE) or epoxidized polybutane An epoxidized polybutadiene (for example, manufactured by Daicel Chemical Industry Co., Ltd. under the trade name of Epolead PB3600), preferably yttrium-9-bisphenol diglycidyl ether. The compound containing at least two epoxy groups in the above molecule may be used singly or in combination of several kinds.

(F) Organic solvents:

The content of the (F) organic solvent is, for example, between 10 and 2,500 parts by weight, preferably between 80 and 250 parts by weight, based on 100 parts by weight of the (A) alkali-soluble resin binder.

(F) The organic solvent is, for example, PGMEA, MBA or EEPA. The above organic solvents may be used singly or in combination of several kinds.

Further, as a protective film for a color filter, the photosensitive resin composition of the present invention is mainly (A) an alkali-soluble resin binder, (B) a photopolymerizable ethylenically unsaturated group-containing compound, and (C) light. The initiator, (D) an organic acid anhydride, and a compound having at least two epoxy groups in the (E) molecule are main components. Of course, depending on the actual needs, the following additives can be added as necessary.

In one embodiment, a adhesion agent may be further added to improve adhesion between the photosensitive resin composition and the color filter, and to improve adhesion between the photosensitive resin composition and the transparent electrode. degree. 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, based on 100 parts by weight of the photosensitive resin composition. The adhesion promoter is, for example, an epoxy group-containing or amino group-containing hydrazine compound, which is, for example, β- (3,4-epoxycyclohexane)ethyltrimethoxydecane (β-(3,4-epoxycyclohexyl)ethyl). trimethoxysilane), β - (3,4- epoxycyclohexane) ethyl triethoxysilane Silane (β- (3,4-epoxycyclohexyl) ethyl triethoxysilane), γ- trimethoxy silane-oxide (γ-glycidoxypropyl Trimethoxysilane, GTS), γ-glycidoxypropyl methyldimethoxysilane, γ-glycidoxypropyl methyldiethoxysilane, γ-propylene oxide Γ-glycidoxypropyl dimethoxy(ethoxy)silane, γ-glycidoxypropyl dimethyl(methoxy)silane, γ-propylene oxide dimethyl ethoxylate Γ-glycidoxypropyl dimethyl(ethoxy)silane, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxydecane (3,4) -epoxybutyltriethoxysilane), N-(2-Aminoethyl)-3-aminopropyldimethoxydimethylsilane (N-(2-aminoethyl)-3-aminopro Pyldimethoxymethylsilane), (3-aminopropyl)trimethoxysilane, (3-aminopropyltriethoxysilane), (N,N-diethyl) N-N-diethyl-3-aminopropyltrimethoxysilane or N-β(aminoethyl)γ-aminopropyltrimethoxydecane) (N-β( Aminoethyl) γ-aminopropyl trimethoxysilane). The above-mentioned adhesion aids may be used singly or in combination of several kinds.

In an embodiment, 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 surfactants are, for example, polyoxyethylene alkyl ethers (for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether). )), polyoxyethylene aryl ethers (such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether), polyethylene glycol Polyethylene glycol dialkyl esters (for example, polyethylene glycol dilaurate, polyethylene glycol distearate), organooxane polymer (organosiloxane) Polymer) (for example, KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.)) or (meth)acrylic acid polymer (for example, Polyflow No. 75, 90, 95 (by Kyoei- Sha Yushi Kagaku Kogyo Co., Ltd.), Megafac F171, F172, F173, F475 (manufactured by Dainippon Chemicals ana Ink Co., Ltd.), Florard FC430, FC431 (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, and a thermal polymerization inhibitor may be further added. Polymerization inhibitor agent).

The photosensitive resin composition of the present invention is mainly prepared by the above (A) alkali-soluble resin binder, (B) photopolymerizable ethylenically unsaturated group-containing compound, (C) photoinitiator, and (D) organic An acid anhydride, a compound having at least two epoxy groups in the (E) molecule, and (F) an organic solvent uniformly mixed into a solution state in a stirrer, the viscosity of which is between 1 and 200 cps, preferably between 3 and 25 cps. .

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, it was prebaked at 80 ° C for 2 minutes to remove the solvent. Then, the full exposure was 200 mJ/cm ² . After development, it was baked at 230 ° C for 20 minutes to form a photosensitive resin layer of 1 to 1.5 μm, and was 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 (Pyles glass), a quartz glass, or a photoelectric conversion device substrate (for example, a germanium substrate) used for a solid-state imaging device.

The structural formula (1) of the present invention will be described by taking a synthesis example of the following (A) alkali-soluble resin binder structural formula (2A) as an example, but is not limited thereto. Wherein the functional group a control comprises a functional group h, the functional group b control comprises a functional group i, the functional group x control comprises a functional group c, and the functional group y control comprises d, e, f, g.

(A) Alkali-soluble resin binder is a synthesis example of structural formula (2A)

Wherein c = 1 mole percentage; d = 19 mole percentage; e = 3 mole percentage; f = 2 mole percentage; g = 30 mole percentage; h = 15 mole percentage; i = 30 mole percentage. h+i=45% of the mole, in the range of 40 to 60 moles.

The detailed synthetic procedure for this synthesis is illustrated as follows: 9 grams of 2,2-azobisisobutyronitrile (AIBN), 630 grams of PGMEA solvent and 10 grams of chain transfer were added to the reaction flask. agents (alpha] -methylstyrene dimer (α -methyl styrene dimer)), and stirred to dissolve. Then, 50.2 g of dicyclopentanylmethacrylate, 46.4 g of methacrylic acid, 4.5 g of allylmethacrylate, and 1.6 g of methacrylonitrile were added. 37.5 g of styrene, 2.9 g of 2,2-dimethyl-1,3-propane glycoldiacrylate, and nitrogen gas The mixture was heated to 80 ° C with stirring to carry out a reaction for 2.5 hours. Next, 0.3 g of AIBN was dissolved in 10 g of PGMEA, and dropped into the reaction flask over 10 minutes to continue the reaction for 12 hours. Thereafter, the nitrogen gas was stopped, and 51.2 g of glycidyl methacrylate, 2.5 g of a catalyst (1-methylimidazole) and 0.15 g of an inhibitor (4-methoxybenzene) were added. 4-methoxyphenol)), and the mixture was stirred in air for 19 hours. The obtained product resin solution had a solid content of 27.2 wt.%; a viscosity of 110 cps/25 ° C; an acid value of 57.3 mgKOH/g; and a weight average molecular weight of 11,867.

Example 1

10 parts by weight of (A) alkali-soluble resin binder having the following structural formula (2A), Wherein c = 1 mole percentage; d = 19 mole percentage; e = 3 mole percentage; f = 2 mole percentage; g = 30 mole percentage; h = 15 mole percentage; i = 30 mole percentage. 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 I-907, 0.5 parts by weight of IPTX, 0.02 parts by weight of adhesion promoter GTS, and 4 parts by weight of solvent PGMEA together The mixture was stirred and dissolved to prepare a photosensitive resin composition for a color filter (Table 1). The photosensitive resin composition was evaluated by the following various measurement evaluation methods, and the results are shown in Table 2.

Comparative example 1

10 parts by weight of (A) alkali-soluble resin binder having the following structural formula (2R), Wherein c = 1.4 mole percentage; d = 23.5 mole percentage; e = 3.8 mole percentage; f = 2.6 mole percentage; g = 38.7 mole percentage; h = 15 mole percentage; I = 15 mole percentage. 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 I-907, 0.5 parts by weight of IPTX, 0.02 parts by weight of adhesion promoter GTS, and 4 parts by weight of solvent PGMEA together The mixture was stirred and dissolved to prepare a photosensitive resin composition for a color filter (Table 1). The photosensitive resin composition was evaluated by the following various measurement evaluation methods, and the results are shown in Table 2.

Evaluation method: First, heat resistance

The photosensitive resin layer on the obtained glass substrate was oven-treated at 250 ° C for 60 minutes, and the film thickness change before and after the treatment was measured by profiler Tencor α -step 500.

○: thickness change <6%

X: thickness change ≧ 6%

Second, alkali resistance

The photosensitive resin layer on the obtained glass substrate was immersed in 10% NaOH at 25 ° C ± 2 ° C for 3 hours, and the film thickness change before and after the treatment was measured by profiler Tencor α -step 500.

○: thickness change <1%

X: thickness change ≧3%

Third, acid resistance

The photosensitive resin layer on the obtained glass substrate was immersed in 10% HCl for 3 hours at 25 ° C ± 2 ° C, and the film thickness change before and after the treatment was measured by profiler Tencor α -step 500.

○: thickness change <1%

X: thickness change ≧3%

Fourth, solvent resistance

The photosensitive resin layer on the obtained glass substrate was immersed in NMP at 25 ° C ± 2 ° C for 3 hours, and the film thickness change before and after the treatment was measured by profiler Tencor α -step 500.

○: thickness change <1%

X: thickness change ≧3%

Fourth, the transmittance

The photosensitive resin layer on the obtained glass substrate was measured for light transmittance at a wavelength of 380 to 800 nm.

○: light transmittance >97%

X: light transmittance <97%

Five, heat discoloration

The photosensitive resin layer on the obtained glass substrate was oven-treated at 250 ° C for 60 minutes, and the light transmittance was measured by light having a wavelength of 380 to 800 nm.

○: The light transmittance is changed by 5% or less

△: light transmittance changes by 5% to 10%

X: Light transmittance changes by more than 10%

Sixth, adhesion

The photosensitive resin layer on the obtained glass substrate was cross-cut and tested by peeling off the film layer by adhesive tape.

○: Residual photoresist film exceeds 98%

X: Residual photoresist film is less than 98%

In summary, the alkali-soluble resin binder of the present invention successfully synthesizes a higher proportion of functional groups h and i, and can obtain better heat resistance and alkali resistance, so that the photosensitive resin composition of the present invention has a high The protective film of the color filter in which the photosensitive resin composition is polymerized by the characteristics of light transmittance, heat resistance, acid resistance, alkali resistance, and heat discoloration resistance can effectively protect the color filter. Further, the photosensitive resin binder having the alkali-soluble resin binder of the present invention also has characteristics such as high light transmittance, heat resistance, acid resistance, alkali resistance, and heat discoloration resistance.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the invention, and any one of ordinary skill in the art can make some modifications and refinements without departing from the spirit and scope of the invention. this The scope of the invention is defined by the scope of the appended claims.

Claims (9)

A photosensitive resin composition comprising: (A) an alkali-soluble resin binder containing a polymer represented by the structural formula (1), Wherein x=1~10 mole percentage; y=29~59 mole percentage; a+b=40~60 mole percentage; a=15~40 mole percentage; b=5~30 mole percentage; R is Benzyl, phenyl, CN or C(O)OR2, wherein R2 is a C1 to C15 linear or cyclic alkyl group, a phenyl group, a benzyl group or an allyl group; and R ₁ is H or a C1 to C4 group. (B) a photopolymerizable ethylenically unsaturated group-containing compound; (C) a photoinitiator; (D) an organic acid anhydride; (E) a compound having at least two epoxy groups in the molecule; An organic solvent, (F) an organic solvent is propylene glycol methyl ether acetate, 3-methoxyacetic acid butyl ester, 3-ethoxypropionic acid ethyl ester or a combination thereof, wherein (A) the alkali-soluble resin binder has an average weight The molecular weight is between 3,000 and 300,000. The acid value of the (A) alkali-soluble resin binder is between 10 and 400 mgKOH/g, and the viscosity of the photosensitive resin composition is between 1 and 200 cps. The photosensitive resin composition according to claim 1, wherein the (A) alkali-soluble resin binder has a solid content of 10 to 50%. The photosensitive resin composition according to claim 1, wherein the (B) alkali-soluble resin binder is 100 parts by weight, and the content of the (B) photopolymerizable ethylenically unsaturated group-containing compound is 1 ~250 parts by weight. The photosensitive resin composition according to claim 1, wherein the (A) alkali-soluble resin binder is contained in an amount of from 0.1 to 100 parts by weight based on 100 parts by weight of the (A) alkali-soluble resin binder. The photosensitive resin composition according to claim 1, wherein the (A) alkali-soluble resin binder is contained in an amount of from 0.1 to 100 parts by weight based on 100 parts by weight of the (A) alkali-soluble resin binder. The photosensitive resin composition according to claim 1, wherein the content of the compound having at least two epoxy groups in the (E) molecule is 0.1 based on 100 parts by weight of the (A) alkali-soluble resin binder. ~100 parts by weight. The photosensitive resin composition according to claim 1, wherein the (A) alkali-soluble resin binder is contained in an amount of from 10 to 2,500 parts by weight based on 100 parts by weight of the (A) alkali-soluble resin binder. A protective film of a color filter obtained by polymerizing a photosensitive resin composition according to any one of claims 1 to 7. A photosensitive resin binder comprising: (A) an alkali-soluble resin binder containing a polymer represented by the formula (1), Wherein x=1~10 mole percentage; y=29~59 mole percentage; a+b=40~60 mole percentage; a=15~40 mole percentage; b=5~30 mole percentage; R is Benzyl, phenyl, CN or C(O)OR2, wherein R2 is a C1 to C15 linear or cyclic alkyl group, a phenyl group, a benzyl group or an allyl group; and R ₁ is H or a C1 to C4 group. (B) a photopolymerizable ethylenically unsaturated group-containing compound; (C) a photoinitiator; (D) an organic acid anhydride; (E) a compound having at least two epoxy groups in the molecule; An organic solvent, (F) an organic solvent is propylene glycol methyl ether acetate, 3-methoxyacetic acid butyl ester, 3-ethoxypropionic acid ethyl ester or a combination thereof, wherein (A) the alkali-soluble resin binder has an average weight The molecular weight is between 3,000 and 300,000, and the acid value of the (A) alkali-soluble resin binder is between 10 and 400 mg KOH/g.