TWI286563B - Resin composition and protective film - Google Patents

Abstract

A resin composition comprises (A) a copolymer of an epoxy-containing unsaturated compound and an unsaturated compound of a different alkenic series; (B) a reaction product of a hydroxy-containing epoxy resin and an alkoxysilane; and (C) a cationic polymeric compound different from the components (A) and (B). The resin composition can form an optical device protective film having high planarity, surface hardness, excellent thermal resistance, pressure withstanding, acid resistance, alkaline resistance, anti-sputtering, etc.

Description

1286563 (1) Technical Field of the Invention The present invention relates to a curable resin composition, a method of forming a protective film, and a protective film. In particular, a curable resin composition suitable for use as a material for forming a protective film for a liquid crystal display element (LCD), such as a color smear and a CCD for use in a liquid crystal display device (LCD), A method of forming a protective film using the composition, and a protective film formed of the composition. [Prior Art] A radioactive device such as an LCD or a CCD is subjected to an immersion treatment using a display element such as a solvent, an acid or an alkali solution in the production process. When the wiring electrode layer is formed by sputtering, the surface of the element is locally exposed to a high temperature. Therefore, in order to prevent deterioration or damage of the element by such processing, a protective film having a film having resistance to such treatment is provided on the surface. Such a protective film must have a substrate or a lower layer to be formed with the protective film and a high adhesion to the layer to be formed on the protective film. The film itself is smooth and strong, and has transparency, heat resistance and It has high light resistance and does not cause deterioration of coloring, yellowing, whitening, etc., and various physical properties such as water resistance, solvent resistance, acid resistance and alkali resistance. The thermosetting composition containing a polymer having a glycidyl group disclosed in Japanese Laid-Open Patent Publication No. Hei 5/7 84 5 3 is known to be used for forming a protective film for a physical property. Things. Moreover, when such a protective film is used as a color liquid crystal display device or a color filter of a 12866563 (2) charge coupled device, it is generally required to flatten the height difference caused by the color filter formed on the substrate. conditions of. Further, in the color liquid crystal display device, for example, a STN (SUper Twisted Nematic) method or a TFT (Thin Film Transister) color liquid crystal display device, the cell gap of the liquid crystal layer is uniformly maintained ( In the case of cell gap, a panel is generally attached after the bead-like spacer is spread on the protective film. Then, the sealing material is thermocompression bonded to seal the liquid crystal cell. However, due to the heat and pressure applied at the time, the protective film of the portion where the bead is present may be dented, causing a problem of cell gap confusion. In particular, when manufacturing a color liquid crystal display device of the STN type, the precision of the adhesion between the color filter and the opposite substrate must be strictly enforced, and the protective film needs to have an extremely high level of flatness and heat resistance. performance. Further, in recent years, a method of forming a wiring electrode (indium tin oxide, ITO) on a protective film of a color filter by sputtering and sputtering ITO with a strong acid or a strong alkali is also employed. . As a result, the protective film is locally exposed to high temperatures during sputtering or treated with various chemicals. Therefore, the protective film is also required to be resistant to such treatment, and in order to prevent the ITO from being peeled off from the protective film during the treatment of the drug, it is necessary to have adhesion to the wiring electrode. In the formation of such a protective film, it is convenient to use a thermosetting composition having the advantage of being able to form a protective film having excellent hardness in a simple manner, but it has not been developed so far. It conforms to -6 - 1286563 (3) Transparency and the like as a general protective property of a protective film, and is compatible with the protective film of various properties as described above, and is excellent in storage stability as a composition. SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances. SUMMARY OF THE INVENTION An object of the present invention is to provide a cured film having high flatness on a substrate even if the surface is poor in flatness, and is suitable for forming a surface hardness, heat resistance, pressure resistance, and acid resistance. A resin composition of a protective film for an optical device which is excellent in various resistances such as alkali resistance and sputter resistance. Another object of the present invention is to provide a method for forming a protective film using the above composition of the present invention. Still another object of the present invention is to provide a protective film formed of the above composition. Still other objects and advantages of the present invention will be apparent from the following description. According to the present invention, the above objects and advantages of the present invention, first, can be achieved by a resin composition characterized by containing [A] (al) an epoxy group-containing unsaturated compound, and (a2) and ( Al) a copolymer of an olefin-based unsaturated compound having a different composition (hereinafter referred to as a copolymer [A].) [B] (b) a reactant of a hydroxyl group-containing epoxy resin and (b2) alkoxydecane, and [ C] Cationic polymerizable compound which is different from [A] component and [B] component (5) 1286563 BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. First, the resin composition of the present invention will be described. Copolymer [A] The copolymer [A] used in the present invention is a copolymer of (al) an epoxy group-containing unsaturated compound and (a2) an (al) component different from the (al) component. . The above (a1) an epoxy group-containing unsaturated compound is a compound having an epoxy group and a polymerizable carbon-carbon double bond in one molecule. Specifically, acrylic acid glycidic acid, glycidyl methacrylate, α-ethyl methacrylate, glycidyl n-propyl acrylate, glycidyl α-n-butyl acrylate, acrylic acid-3 can be exemplified. , 4-epoxybutyl acrylate, _3,4-epoxybutyl methacrylate, -6,7-epoxyheptyl acrylate, -6,7-epoxyheptyl methacrylate, α Ethyl acrylate-6,7-epoxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like. Among them, from the viewpoint of copolymerization reactivity and improvement in heat resistance and hardness of the obtained protective film, it is preferred to use glycidyl methacrylate or methacrylic acid-6,7-epoxyglycol. Ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like. These (a 1) unsaturated compounds containing an epoxy group may be used alone or in combination of two or more. The above-mentioned olefinic unsaturated compound which is different from the component (a 2 )( a 1), -9 - 1286563, and the allylic propyl carbaryl ester of the propyl group and the acetylated acid The acid group is suspected of having a propyl group and the methyl group is oxo. The ring is an example (6 has a 'n-butyl acrylate, a second butyl methacrylate, a third butyl methacrylate, etc. Alkyl acrylate; alkyl acrylate such as methyl acrylate or isopropyl acrylate; cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, cyclohexyl methacrylate, trimethyl methacrylate [ 5.2.1.02,6]癸-8-yl (in the technical field, known as dicyclopentanyl methacrylate), dicyclopentanyloxyethyl methacrylate, isobornyl a methacrylic acid cyclic alkyl ester such as methacrylate; cyclohexyl acrylate, 2-methylcyclohexyl acrylate, cyclohexyl acrylate, tricyclo[5·2·1.02'6]癸-8·yl (In the technical field, it is called dicyclopentanyl acrylate as a customary name), dicyclopentane oxyethyl acrylate a cyclic alkyl alkanoate such as isobornyl acrylate; aryl methacrylate such as phenyl methacrylate or benzyl methacrylate; acrylic acid such as phenyl acrylate or benzyl acrylate An aryl ester; a dicarboxylic acid ester such as diethyl maleate, diethyl fumarate or diethyl itaconate; a gj5 derivative such as a guanidine; a phenylmaleimide; Benzyl maleimide, cyclohexylmaleimide, N-succinimide, 3-maleimide benzoate, N-succinimide-4-maleimide Butyrate, Ν-amber quinone imine-6-maleimide caproate, Ν-amber quinone imine-3-maleimide propionate, Ν-(9-acridinyl a dicarboxy quinone imine derivative such as maleimide; a hydroxyalkyl ester such as 2-hydroxyethyl-10- 1286563 (7) methacrylate or 2-hydroxypropyl methacrylate; Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-ethoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, dichloroethylene, Acrylamide, methacrylic acid Amine, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1, 3-butadiene, etc. Among them, copolymerization reactivity and prepared protective film From the viewpoint of heat resistance, styrene, tert-butyl methacrylate, dicyclopentanyl methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, 1, 3 - are preferred. Butadiene, phenylmaleimide, cyclohexylmaleimide, etc. These compounds (a2) may be used singly or in combination. Specific examples of the copolymer [A] may, for example, be benzene. Ethylene/glycidyl methacrylate copolymer, styrene/glycidyl acrylate copolymer, tricyclo[5 ·2.1 ·02,6]decane-8-yl ester/glycidylmethyl methacrylate Acrylate copolymer, tricyclo[5.2.1.02'6]decane-8-yl ester/glycidyl acrylate copolymer, styrene/cyclohexylmaleimide/glycidyl methacrylate Ester copolymer, styrene/phenyl maleimide/glycidyl methacrylate copolymer, styrene/methacrylic acid tricyclic [5.2.1.02 ,6]decane-8-yl ester/shrinkage-11 - 1286563 (8) glyceryl methacrylate copolymer, styrene/methacrylic acid-6,7-epoxyheptyl ester copolymer, A Tricyclo[5·2·l·02'6]decane-8-yl acrylate/methacrylic acid-6,7·epoxyheptyl ester copolymer, phenylethyl/cyclohexylmaleimide /Methylpropionic acid-6,7-epoxyheptyl ester copolymer. Among them, preferred are styrene/glycidyl methacrylate copolymer, tricyclo[5.2.1.02,6]decane·8-yl ester/glycidyl methacrylate copolymer. , styrene/cyclohexylmaleimide/glycidyl methacrylate copolymer, styrene/methacrylic acid tricyclo [5.2.1.0''6]decane-8-yl ester/glycidylmethyl Acrylate copolymer and the like. The copolymer [Α] may be used alone or in combination of two or more. The copolymer [Α] is preferably from 1 to 90 parts by weight, more preferably from 40 to 90 parts by weight, per 100 parts by weight of the copolymer [Α], of the constituent unit derived from the compound (a 1). The copolymer [A] is preferably a weight average molecular weight (hereinafter, simply referred to as "]\^" in terms of polyethylene, and is preferably 3,000 to 100,000, more preferably 3,000 to 50,000, particularly preferably 3,000 戋 20,000. The copolymer [A] can be obtained by, for example, radical polymerization of the above (a1) epoxy group-containing unsaturated compound and (a2) olefin-based unsaturated compound in the presence of a suitable solvent and a polymerization initiator. And to synthesize. The solvent which can be used for the synthesis of the copolymer [A] may, for example, be an alcohol such as methanol or ethanol; -12·1286563 Ο) an acid such as tetrazo-D-fu, etc., ethylene glycol-methyl ether Glycol ethers such as ethylene glycol-diethyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate; diethanol monomethyl ether; Diethylene glycol such as ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethanol diethyl ether, diethylene glycol ethyl methyl ether; propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol dibutyl ether a propylene glycol monoether ether such as propylene glycol monoether ether; propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate; propylene glycol methyl ether propionate; a propylene glycol alkyl ether such as propylene glycol diethyl ether propionate, propylene glycol propyl ether propionate or propylene glycol butyl ether propionate; an aromatic hydrocarbon such as toluene or xylene; methyl ethyl ketone, cyclohexanone, 4 - ketones such as hydroxy-4-methyl-2.pentanone, methyl isoamyl ketone, etc.; and methyl acetate, ethyl acetate Ester, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, hydroxyl Ethyl acetate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, 3 - butyl hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, ethoxylate Methyl acetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate-13- ( 10) 1286563, butyl oxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, 2 -ethyl methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2 -propyl ethoxypropionate, butyl 2-ethoxypropionate, 2- Methyl oxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, 3-methyl Ethyl oxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-B Propyl oxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, 3-propane Esters such as butyl oxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate . The solvent may be used alone or in combination of two or more. Among them, preferred are diethylene glycols and propylene glycol alkyl acetates, and particularly preferred are ethylene glycol ethyl methyl ether, propylene glycol methyl ether acetate, and propylene glycol diethyl ether acetate. The initiator which can be used in the production of the copolymer [A] can be generally used as a radical polymerization initiator, and may be exemplified by 2,2 azoisobutyronitrile, 2,2 / · An azo compound such as nitrogen bis(2,4.dimethyl pentanenitrile), 2,2,-azobis(4-methoxy-2,4-dimethylvaleronitrile); benzamidine peroxide , an organic peroxide such as peroxidized lauryl hydrazine, tributyltrimethylacetate peroxide, 1,1 bis(tetrabutylperoxy peroxide) cyclohexane; and hydrogen peroxide. When a peroxide is used as a radical polymerization initiator, the peroxide can act together with a reducing agent as a redox type -14-1286563 (11) initiator. [B] (bl) a reaction product between a hydroxyl group-containing epoxy resin and (b2) alkoxydecane. The [B] component used in the present invention is (bl) a hydroxyl group-containing epoxy resin and (b 2 a reaction product between alkoxydecanes. (bl) The epoxy resin containing a hydroxyl group may, for example, be a bisphenol type epoxy resin, a lacquer type epoxy resin, a glycidyl ester type epoxy resin, a glycidylamine type epoxy resin, or a linear aliphatic group. Epoxy resin and alicyclic epoxy resin, and bis-amine epoxy resin. Among them, a bisphenol type epoxy resin and a lacquer type epoxy resin are preferably used. The bisphenol type epoxy resin can be obtained by a reaction between a bisphenol and a halogenated epoxide such as epichlorohydrin or ?-methylepichlorohydrin. The bisphenols may, for example, be aldehydes or ketones of phenol or 2,6-dihalogenated benzene with formaldehyde, acetaldehyde, acetone, methyl phenyl ketone, cyclohexanone or diphenyl ketone. The reaction product, the oxidation product formed by the peroxyacid of the dihydroxyphenyl sulfide, and the etherification reaction product between the hydroquinones and the like. Among these diketone type epoxy resins, in particular, as bisphenol, bisphenol type oxygen resin obtained by using bisphenol A, bisphenol S, bisphenol F or the like hydrogen additive is most widely used. And the best. Further, the bisphenol type epoxy resin has a hydroxyl group which can react with (b 2) alkoxy decane which will be described later. However, it is not necessary for all the molecules constituting the bisphenol type epoxy resin to have such a hydroxyl group, and it is preferable to have a hydroxyl group as a whole of the bisphenol type epoxy resin. For example, a bisphenol A type epoxy resin can be represented by the following formula (1), • 15 - 1286563 (12)

CHoCHCHjV

Ch3

0—CH

〇-ch2chch2V (1) (where m is an integer of 0 or more, and the average number of repeating units of m is 〇·1 to 34). However, if m is 1 or more, a considerable number of m may be included. These bisphenol type epoxy resins can be used, for example, as a phosphorus-modified bisphenol type epoxy resin by reacting with a phosphorus compound. The lacquer-type epoxy resin can be obtained, for example, by reacting a halogenated epoxide with a phenolphthalein-type resin or a cresol-type varnish-type resin. The glycidyl ester type epoxy resin can be obtained by reacting a polybasic acid such as citric acid with epichlorohydrin. The glycidylamine type epoxy resin can be obtained by reacting a polyamine such as diaminodiphenylmethane or isomeric cyanuric acid with epichlorohydrin. The above linear aliphatic epoxy resin and alicyclic epoxy resin can be obtained by treating, for example, an olefin with a peroxy acid such as peracetic acid. The above bisphenol type epoxy resin can be obtained by reacting, for example, a phenol with epichlorohydrin. -16- 1286563 (13) (b) The preferred oxime equivalent of the epoxy equivalent of the epoxy group-containing epoxy resin varies depending on the structure of the (bl) epoxy resin containing a hydroxyl group. It can be used according to the purpose. In general, when a (bl) component having a small epoxy equivalent is used, since the adhesion between the substrate and the substrate may be poor when the protective film is formed, the epoxy equivalent of the (bl) component is preferably prepared. 180 or more. On the other hand, when a (bl) component having a large epoxy equivalent is used, it may be gelled due to a reaction with (b 2) alkoxydecane described later, (bl) The epoxy equivalent of the component is preferably 5,000 or less. A more preferred epoxy equivalent is from 20 to 400. Further, in the above (b 2) alkoxydecane, a user in the sol-gel method can be generally used. For example, the formula: R^SUOR2)" (wherein, P represents an integer of 〇 or 1. R1 represents an alkyl group having 1 to 6 carbon atoms which can hold a functional group directly bonded to a carbon atom, and has a carbon number of 1 An aryl group to 6 or an unsaturated aliphatic residue having 2 to 6 carbon atoms, R 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and a compound represented by a plurality of R 2 may be the same or different. , or such partial condensates, and the like. The functional group of R1 described above may, for example, be a vinyl group, a mercapto group, an epoxy group or a glycidoxy group. Further, the "partial condensate" means a part obtained by condensing a part of an alkoxy group in the alkoxy decane represented by the above formula. Such a partial condensate can be obtained by subjecting the above alkoxydecane to hydrolysis in the presence of an acid or a base and water. Specific examples of such (b2) alkoxydecane include, for example, tetramethoxydecane, tetraethoxydecane, tetrapropoxydecane, and tetraisopropoxypurine-17-1286563 (14). Alkaneoxydecanes of alkane, tetrabutoxydecane; methyltrimethoxydecane, methyltriethoxydecane, methyltripropoxydecane, methyltributoxydecane, ethyltrimethoxy Base decane, ethyl triethoxy decane, n-propyl trimethoxy decane, n-propyl triethoxy decane, isopropyl trimethoxy decane, isopropyl triethoxy decane, vinyl trimethoxy Decane, vinyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, 3- Mercaptopropyltriethoxydecane, phenyltrimethoxydecane, phenyltriethoxydecane, 3,4-epoxycyclohexylethyltrimethoxydecane, 3,4-epoxycyclohexyl a trialkyloxydecane of ethyltriethoxydecane; or a partial condensate thereof or the like. Among them, it is preferable to have the following (2): ch3o·f • I-〇_och3 f Si——OCH3 (2) n 〇CH3 (wherein R3 is a methoxy group or a carbon number of 1 to 6 The alkyl group, and n is an integer of 1 or more, and the average number of repeating units of η is 1 to 7). a partial condensate of tetramethoxy decane or alkyltrimethoxy decane, -18- 1286563 (15) of a partial condensate of the tetramethoxy decane or alkyltrimethoxy decane The best is 260 to 2,000, preferably 260 to 890. a partial condensate of the tetramethoxynonane or alkyltrimethoxydecane, because in the reaction with the component (b1), together with methane, the unreacted (b2) component evaporates without flowing out of the system. For the sake of the outside, the reaction operation is also preferred. Further, since such a partial condensate does not possess the toxicity possessed by the corresponding early body, it is also suitable from this point of view. In the above formula (2), the enthalpy (η) of the average number of repeating units is preferably 11 or less and more preferably 7 or less. When the enthalpy exceeds 11%, the solubility in the epoxy resin and the organic solvent which are (b) hydroxy groups is insolubilized due to poor solubility, and the reactivity with the epoxy resin having a bl (b) is low. Propensity. The component [B] can be obtained by a dealcoholization condensation reaction between the above (bl) epoxy group-containing epoxy resin and (b2) alkoxydecane. (bl) The ratio of the use of the epoxy group-containing epoxy resin to the (b2) alkoxysilane, such as a ratio in which the alkoxy group can substantially remain in the obtained [B] component, is not particularly limited. Preferably, the weight (weight ratio) of the (b2) alkoxydecane equivalent weight / (bl) hydroxyl group-containing epoxy resin is in the range of 0.01 to 3. However, when (b) the epoxy resin containing a hydroxyl group is a high molecular weight resin having an epoxy equivalent of 400 or more, the viscosity of the solution may be increased or gelled due to the progress of the dealcoholization reaction, and the following may be This way you can avoid such an inappropriate situation. Preferably, 1 is such that the equivalent ratio is 1 or more or 1 or more in such a manner that (b) the hydroxyl group equivalent of the epoxy group-containing epoxy resin or the (b 2) alkoxydecane can be contained in a large amount. Particularly preferably, the above equivalent ratio is 0.8 to -19·1286563 (16) 1 or more or 1 or more. It is particularly preferable that the above equivalent ratio is Ο·8 or less or 1.2 or less. In particular, it is preferably adjusted to 1.2 or more. A method in which the dealcoholization reaction is stopped in the middle of the reaction, so as to prevent the viscosity increase and the gel method. For example, a method of changing the reaction system to a reflux system to adjust the amount of methanol distillation from the reaction system, or cooling the reaction system to terminate the reaction, or the like can be employed. The production of the above [Β] component can be carried out, for example, by feeding the above-mentioned respective components and performing a dealcoholization condensation reaction under the agitation of the alcohol formed by heating. The reaction temperature is preferably from 50 to 130 ° C, more preferably from 70 to 11 ° C, and the reaction time is preferably from 1 to 15 hours. This reaction is preferably carried out under substantially anhydrous conditions in order to prevent the (b 2) alkoxydecane from being condensed by itself. Further, this reaction can be carried out under reduced pressure in the range of (b 1) the epoxy group containing a hydroxyl group does not evaporate in the case of shortening reaction time. Further, in the case of performing the above-described dealcoholization condensation reaction, in order to promote the reaction, it is possible to use a known catalyst which does not open the oxirane ring. The catalyst may, for example, be lithium, sodium, potassium, rubidium, planer, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, bismuth, tin, lead, antimony, arsenic, antimony or cadmium. , manganese metal; oxides, organic acid salts, halides, alkoxides, etc. of such metals. Among them, organotin, organic acid tin, and specifically, dibutyltin laurate, tin octylate, and the like are preferable. Further, the above reaction can also be carried out in a solvent. The solvent is not particularly limited as long as it can dissolve (bl) an epoxy resin containing a hydroxyl group and (b2) an alkoxysilane, and does not react with such an organic solvent. : dimethylformamide, dimethylacetamide, tetrahydrofuran, -20-1286563 (17) Commercially available as a decane-modified epoxy resin containing an alkoxy group's name: Arakawa Chemical Industry Co., Ltd. Stock system, trade name: Kong Yilan Lang E-101, Ε·1〇2, Ε·201, Ε·202, Ε-211, Ε·212, etc. Among them, Arakawa Chemical Engineering Industrial Co., Ltd., trade name: 甫 甫 Ε Ε -201, Ε-202, Ε-212, because the protective film can have a high surface hardness, preferably . [C] a cationically polymerizable compound which is different from the [Α] component and the [Β] component, and the cationically polymerizable compound which is different from the [Α] component and the [Β] component used in the present invention may be used. For example, there are two or more compounds having an oxetanyl group, a 3,4-epoxycyclohexyl group or an epoxy group in the molecule. Specific examples of such a [C] cationically polymerizable compound may be exemplified below. The compound having two or more of the above oxetan groups in the molecule may, for example, be 3,7-bis(-oxetanyl)-5-oxa-decane, 3, -( 1,3-(2-methylene)propanediylbis(formaldehyde)bis(3.methyloxetane), 1,4-bis[(3-methyl-3-oxetane) Methoxy)methyl]benzene, 1,2-bis[(3-methyl-3-oxetanylmethoxy)methyl]ethane, 1, 3-bis[(3-A) ·3·oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-methyl-3-oxetanylmethyl)ether, dicyclopentyl bis[3- Methyl-3-oxetanylmethyl]ether, triethylene glycol bis(3-methyl-3-oxetanylmethyl)ether, tetraethylene glycol bis(3-methyl 3-oxetanylmethyl)ether, tricyclodecanediyldimethylenebis(3-ethyl-3-oxetanylmethyl)ether, trimethylolpropane ginseng (3-methyl-3-oxetanylmethyl)-21 - 1286563 (18) Ether, 1, bis(3-ethyl-3-oxetanylmethoxy)butane 1, bis(3-ethyl-3-oxetanylmethoxy)hexane, isovalerol ginseng (3·B Benzyl-3-oxetanylmethyl)ether, isovalerol 肆(3-ethyl-3-oxetanylmethyl)ether, polyethylene glycol bis(3·ethyl- 3-oxetanylmethyl)ether, diisopentylol, tert-(3-ethyl-3-oxetanylmethyl)ether, diisopentyltetraol (3-ethyl-) 3-oxetanylmethyl)ether, diisopentyltetrahydrofuran (3-ethyl-3-oxetanylmethyl)ether, diisopentyltetraol (3-ethyl-) a reaction product between oxetanylmethyl)ether and caprolactone, between diisopentyl alcohol (3-ethyl-3-oxetanylmethyl)ether and caprolactone Reaction product, bistrimethylolpropane oxime (3-ethyl-3-oxetanylmethyl)ether, bisphenol bismuth (3-ethyl-3-oxetanylmethyl) a reaction between ether and ethylene oxide, a reaction between bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether and propylene oxide, hydrogenated bisphenol A bis ( Reaction product of 3-ethyl-3-oxetanylmethyl)ether with ethylene oxide, hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) Reaction between ether and propylene oxide a reaction product of bisphenol F bis(3-ethyl-3-oxetanylmethyl)ether and ethylene oxide, etc. having 3,4-epoxycyclohexyl 2 in the molecule For the above compounds, 3,4-epoxycyclohexylmethyl-3", 4"-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl) -5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-ring Oxy-6-methylcyclohexylmethyl) adipate, 3,4·epoxy-6-methylcyclohexyl-3 / , 4^-epoxy-methylcyclohexanecarboxylate , methylene bis(3,4-epoxycyclohexane), dicyclopentadiene di-22- 1286563 (19) epoxide, ethylene glycol bis (3,4-epoxycyclohexyl) Methyl)ether, methylenebis(3,4-epoxycyclohexanecarboxylate), lactone modified 3,4-epoxycyclohexylmethyl-3/, epoxycyclohexane Carboxylic esters and the like. Examples of the compound having two or more of the above epoxy groups in the molecule include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, and hydrogenation. Bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl Diglycidyl ethers of various bisphenol compounds of benzyl ether, brominated bisphenol S diglycidyl ether; such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl a polyglycidyl ether of a polyol of a vinyl ether, glyceryl triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether; a polyglycol polyether polyglycidyl ether obtained by adding one or more epoxides to an aliphatic polyol such as ethylene glycol, propylene glycol or glycerin; a phenolphthalein type epoxy resin; Cresol lacquer type epoxy resin; polyphenol type epoxy resin; aliphatic long chain dibasic acid Glycidyl ethers; glycidyl esters of higher fatty acids; epoxidized soybean oil, epoxidized linseed oil, and the like. A commercially available product having two or more of the above epoxy groups may be a commercial product of a compound having two or more epoxy groups, and may be exemplified as bisphenol A. The epoxy resin of Epto can be 1001, the same 〇〇2, the same 1003, the same 1004, the same 1007, the same 1009, the same 1010, the same 828 (the above are all made by the oil-based Cheer Abbox (share) system) Etc. As a bisphenol F-type epoxy resin, Abby can be 807 (made by oily Scherr-Ebers), etc.; as a phenol varnish-type epoxy resin, Ebiket 152, 154, and 157S65 (The above are all oily Schell Abbox (share) system), EPPN201, and 20 2 (all of which are made by Nippon Chemical Co., Ltd.); EOCN102 as cresol varnish type epoxy resin, same as 103S, the same 104S, 1020, 1025, 1027 (all of which are made by Nippon Kayaku Co., Ltd.), Ebiket 180S 75 (oiled Cher Abbox), etc.; Bicote 1032H60, the same XY-4000 (all of which are oiled Cheer Abbox (manufactured by the company)); as a cyclic aliphatic epoxy resin CY-175, the same 177 Same as 179, Alarde CY-182, 192, 184 (above Chiba special chemicals (share) system), ERL-4234, same 4299, same 4221, same 4206 (all are UCC) , Xiao Dai Yin 509 (Showa Denko Co., Ltd.), Ebi-Cologne 200, the same 400 (above, Dainippon Ink (share) system, Ebikete 871, the same 872 (above are oily Xueer Aibox ( Co., Ltd.), EP-5 6 6 1 , same as 5662 (above, serranic coating), etc.; Eblet 1 〇0 MF as an aliphatic polyglycidyl ether (Kyoeisha Chemicals ( (E) system, Ebiol (manufactured by Nippon Oil & Fats Co., Ltd.), etc. The above cationically polymerizable compound may be used alone or in combination of 2 -24 - 1286563 (21) [C] cationic polymerizability Among the compounds, preferred are: a phenolphthalein lacquer type epoxy resin and a polyphenol type epoxy resin. [D] A curing agent is exemplified by the [D] curing agent used in the composition of the present invention. A polycarboxylic acid, a polycarboxylic acid anhydride, and a copolymer of an unsaturated polycarboxylic acid anhydride and an olefinic unsaturated compound. The acid is preferably a fatty acid polycarboxylic acid, an alicyclic polycarboxylic acid, and an aromatic polycarboxylic acid, and examples thereof include succinic acid, glutaric acid, adipic acid, butane tetracarboxylic acid, and maleic acid. An aliphatic polycarboxylic acid of itaconic acid; an alicyclic ring such as hexahydrofurfuric acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid or cyclopentanetetracarboxylic acid a polyvalent carboxylic acid; an aromatic polycarboxylic acid of citric acid, isophthalic acid, p-citric acid, trimellitic acid, pyromellitic acid, 1,2,5,8-naphthalenetetracarboxylic acid. Among these, an aromatic polyvalent carboxylic acid is particularly preferred from the viewpoints of the reactivity of the curable composition, the heat resistance of the formed cured film, and the like. The polyvalent carboxylic acid anhydride is preferably an aliphatic dicarboxylic acid anhydride, an alicyclic polycarboxylic dianhydride, an aromatic polycarboxylic acid anhydride, or an ester-containing acid anhydride. It may, for example, be an aliphatic such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecene succinic anhydride, propylene terephthalic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and salic anhydride. a dicarboxylic anhydride such as 1,2,3,4-butanetetracarboxylic anhydride, cyclopentane tetracarboxylic dianhydride, an alicyclic polycarboxylic dianhydride; such as phthalic anhydride, pyromellitic anhydride, trimellitic acid An aromatic polycarboxylic acid anhydride of an acid anhydride or diphenyl ketone tetracarboxylic anhydride; an ester anhydride-containing acid anhydride such as ethylene glycol trimellitate anhydride, -25-1286563 (22) glycerol paraben trimellitic anhydride. Among them, an aromatic polycarboxylic acid anhydride, particularly trimellitic anhydride, is particularly preferable because it can produce a cured film having high heat resistance. The unsaturated polycarboxylic acid anhydride used for the synthesis of the copolymer of the above unsaturated polycarboxylic acid anhydride and the olefinic unsaturated compound may, for example, be itaconic anhydride, citraconic anhydride, maleic anhydride, cis 1,2 At least one of an unsaturated polycarboxylic acid anhydride of 3,4-tetrahydrophthalic anhydride. Further, the olefin-based unsaturated compound used for the synthesis of the copolymer of the unsaturated polyvalent carboxylic acid anhydride and the olefin-based unsaturated compound may, for example, be styrene, p-methylstyrene or p-methoxystyrene. Methyl methacrylate, tert-butyl methacrylate, tricyclo[5·2·1·〇2'6]decane-8-yl ester, 2-methylcyclohexyl acrylate, phenyl At least one or more kinds of olefin-based unsaturated compounds of maleimide and cyclohexylmaleimide. The copolymerization ratio of the unsaturated polycarboxylic acid anhydride to the olefin-based unsaturated compound is preferably from 1 to 80 parts by weight, more preferably from 1 to 60 parts by weight, per 100 parts by weight of the copolymer of the unsaturated polycarboxylic acid anhydride. By using such a copolymer, a protective film excellent in flatness can be obtained. Preferred examples of the copolymer of the unsaturated polycarboxylic acid anhydride and the olefinic unsaturated compound include anhydrous maleic acid copolymer/styrene, citraconic anhydride/methacrylic acid tricyclic [5·2.1·02, 6] a decane-8-ester copolymer or the like. Further, the polystyrene-equivalent weight average molecular weight of the copolymer of the above unsaturated polycarboxylic acid anhydride and the olefin-based unsaturated compound is preferably from 500 to 50,000, more preferably from 500 to 10,000. By using a copolymer having such a molecular weight range of -26 to 1286563 (23), a protective film excellent in flatness can be obtained.

Copolymer [EJ] The copolymer [E] used in the present invention is an (el) unsaturated carboxylic anhydride and/or an unsaturated carboxylic anhydride, (e 2) an epoxy group-containing unsaturated compound, and (e3) and (el) a copolymer of an olefin-based unsaturated compound having a different composition than (e2). The copolymer [E] contains, per 100 parts by weight of the copolymer [E], the constituent unit derived from the compound (el), preferably 5 to 40 parts by weight, particularly preferably 10 to 30 parts by weight. The copolymer having a composition of 5 parts by weight or less tends to have heat resistance, chemical resistance, and surface hardness. On the other hand, when the composition unit exceeds 40 parts by weight of the copolymer, the storage stability may be lowered. The (el) unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride may, for example, be a monocarboxylic acid such as acrylic acid, methacrylic acid or crotonic acid; maleic acid, fumaric acid, citraconic acid or zhongkang; a dicarboxylic acid such as an acid or itaconic acid; and an anhydride of such a dicarboxylic acid. Among them, acrylic acid, methacrylic acid, maleic anhydride or the like is preferably used because of copolymerization reactivity, heat resistance, and easy availability. These compounds (el) may be used singly or in combination. The copolymer [E] contains, per 100 parts by weight of the copolymer [E], the constituent unit derived from the compound (e 2 ), preferably from 1 Torr to 7 Torr, particularly preferably from 20 to 60 parts by weight. When the composition unit is at most 1 part by weight, the obtained protective film has heat resistance and the surface hardness tends to be lowered. On the other hand, if it exceeds 70 parts by weight, the composition containing the copolymer is stored. -27- 1286563 (24) The tendency to maintain stability will be low. (e2) The epoxy group-containing unsaturated compound can be used in the same manner as exemplified as the compound (a1) used as the copolymer [A]. The copolymer [E], for the copolymer [E] per 1 part by weight 'containing the constituent unit derived from the compound (e3), preferably 10 to 70 parts by weight, particularly preferably 20 to 50 parts by weight . When the composition unit is at most 10 parts by weight, the storage stability of the composition containing the copolymer tends to be lowered, and on the other hand, if it exceeds 7 parts by weight, the heat resistance of the obtained protective film is obtained. The tendency of the surface hardness to decrease. (e 3 ) The olefin-based unsaturated compound other than (e 1 ) and (e 2 ) can be used in the same manner as exemplified as the compound (a2) used in the above copolymer [A]. Specific examples of the copolymer [E] used in the present invention can be exemplified by: styrene/trimethyl methacrylate t5·2·1·02'6]decane _8·yl ester/methacrylic acid shrinkage Glyceride Copolymer 'Phenyl benzene/Acrylic/Acrylic Tricyclo[5 ·2· ΙΟ2'6]decane _8·yl ester/glycidyl acrylate copolymer Benzene acetylene/methacrylic acid/phenylmalay醯iamine/methylpropionic acid glycidyl ester copolymer, styrene/acrylic acid/phenylmaleimide 7-propionic acid glycidyl ester copolymer, phenylethyl storage/methyl propylene acid/cyclohexyl Malesinamide/methyl propylene glycol glycidyl ester copolymer, butadiene/styrene/methacrylic acid/methacrylic acid tricyclic - 28 - 1286563 (25) [5·2·1·02'6 ] decane-8-yl ester/glycidyl methacrylate copolymer, butadiene/methacrylic acid/methacrylic acid tricyclic [5. 2. 1. 02,6]decane-8-yl ester/glycidyl methacrylate copolymer, styrene/methacrylic acid tricyclic [5. 2. 1. 02'6] decane-8-yl ester / methacrylic acid-6,7-epoxyheptyl ester copolymer. Styrene/acrylic acid/maleic anhydride/-6,7-epoxyheptyl ester methacrylate copolymer, tert-butyl methacrylate/acrylic acid/maleic anhydride/methacrylate-6,7-epoxy Hexaheptene copolymer, styrene/methacrylic acid/methyl methacrylate/glycidyl methacrylate copolymer, p-methoxystyrene/methacrylic acid/cyclohexyl acrylate/glycidyl methacrylate Copolymers, etc. The preferred ones are: styrene/methacrylic acid/methacrylic acid tricyclo [5. 2. 1 · 02'6] decane-8-yl ester / glycidyl methacrylate copolymer styrene / methacrylic acid / phenyl maleimide / glycidyl methacrylate copolymer, styrene / nail Acrylic acid/cyclohexylmaleimide/glycidyl methacrylate copolymer, butadiene/styrene/methacrylic acid/methacrylic acid tricyclo[5 ·2·1. 02,6]decane-8-yl ester/glycidyl methacrylate copolymer, butadiene/methacrylic acid/methacrylic acid tricyclo[5·2·l·02'6]decane-8- Base ester/glycidyl methacrylate copolymer ° -29 - 1286563 (26) The copolymer [E] has a polystyrene-equivalent weight average molecular weight of preferably 3,000 to 100,000, more preferably 3,000 to 50,000. It is 3,000 to 20,000. When a copolymer having a molecular weight in this range is used, a protective film excellent in flatness can be obtained. The copolymer [E] may be an (ep) unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride, (e2) an epoxy group-containing unsaturated compound in the presence of a suitable solvent and a polymerization initiator, and (e3) an olefin-based unsaturated compound different from the (el) component and the (e2) component, which is synthesized by, for example, radical polymerization, can be used as a solvent for synthesizing the copolymer [E] and a polymerization initiator. The same as those exemplified as the solvent and the polymerization initiator used in the production of the above copolymer [A] can be used. [F] a cationically polymerizable compound which is different from the [B] component and the [E] component, and the [F] and the cationically polymerizable compound which are different from the [B] component and the [E] component used in the present invention may be used. The same as those of the above-mentioned [C] component are used. [G] Compound which generates acid due to heat and/or radiation The component [G] used in the present invention is a radiation-initiating acid generator or a heat-initiating acid generator. The radiation-initiating acid generator may, for example, be a diaryl iodine salt, a triarylsulfonium salt or a diaryl hydroxy salt, and is suitable. Further, the thermally induced acid generator may, for example, be an onium salt (except for the above-mentioned triarylsulfonium salt -30-1286563 (27)), a benzothiazole key salt, an ammonium salt or a scale salt. Etc., among them, sulfonium salts (except for the above-mentioned triarylsulfonium salts) and benzothiazole iron are suitable. The above diaryliodonium salt may, for example, be diphenyliodopronium tetrafluoroborate, diphenyliodonium hexafluorophosphate, diphenyliodopyl hexafluoroarsenate or diphenyliodine. Tin trifluoromethanesulfonate, diphenyliodopyl trifluoroacetate, diphenyl p-toluenesulfonate, 4-methoxyphenylphenyl iodide tetrafluoroborate, 4-methoxybenzene Phenyl iodine gun hexafluorosulfonate, 4-methoxyphenyl phenyl iodonium hexafluoroarsenate, 4-methoxyphenyl phenyl iodide trifluoromethane sulfonate, 4 methoxy Phenylphenyl iodonate trifluoroacetate, 4-methoxyphenyl phenyl iodide trifluoroacetate, 4-methoxyphenyl phenyl iodide p-toluene sulfonate, double (4- Tributylphenyl)iodo-tetrafluoroborate, bis(4-t-butylphenyl)iodonium hexafluoroarsenate, bis(4-t-butylphenyl)iodotrifluoromethanesulfonic acid Salt, bis(4-tert-butylphenyl) iodine trifluoroacetate, bis(4_t-butylphenyl) iodine iron p-toluenesulfonate, and the like. Among them, diphenyliodonium iron hexafluorosulfonate is very suitable. The triarylsulfonium salt may, for example, be triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroarsenate or triphenylsulfonium trifluoromethanesulfonate. Salt, triphenylsulfonium trifluoroacetate, triphenylsulfonium p-toluenesulfonate, 4-methoxyphenyldiphenylphosphonium tetrafluoroborate, 4-methoxyphenyldiphenylphosphonium hexafluorophosphate Salt, 4-methoxyphenyldiphenylphosphonium hexafluoroarsenate, 4-methoxyphenyldiphenylphosphonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylphosphonium trifluoride Acetate, 4-methoxyphenyldiphenylphosphonium p-toluenesulfonate, 4-phenylphenylthiodiphenyltetrafluoroborate, 4-phenylphenylthiodi-31 - 1286563 (28) Phenyl hexafluorophosphate, 4-phenylphenylthiodiphenylhexafluoroarsenate, 4-phenylphenylthiodiphenyltrifluoromethanesulfonate, 4-phenylphenylthiodiphenyl Trifluoroacetate, 4-phenylphenylthiodiphenyl p-toluenesulfonate, and the like. Among them, triphenylsulfonium trifluoromethanesulfonate is very suitable. The diarylsulfonium salt may, for example, be an anisidine-cyclopentaacetate or an iron hexafluorodihydrochloride. As an acid generator which is very suitable for initiating a radioactive acid generator, it can be mentioned as a combined calcium carbide company of a diaryl iodine salt, trade name: UVI-6950, UVI-6970, UVI-6974, UVI- 6990, green chemical (share) system, trade name: MPI-103, BBI-103 and so on. In addition, as a triaryl sulfonium salt, it can be mentioned as: Asahi Chemical Industry Co., Ltd., trade name: Adka Oubundo SP-150, SP-151, SP-170, SP-171, Japan Soda (shares) ), trade name: ci-2481, CI-2624, CI-2639, CI-2064, green chemical (share) system, trade name: DTS-102, DTS-103, NAT-103, NDS-103, TPS- 103, MDS-103, Shado 瑪 company, trade name: CD-1010, CD-1011, CD-1012 and so on. Further, the diaryl iron salt is exemplified by Chiba Special Chemicals Co., Ltd., trade name: Ilga Qia 261, Nippon Chemical Co., Ltd., trade name: PCI-061T, PCI-062T, PCI-020T, PCI-022T, etc. Among them, the joint calcium carbide company, the trade name: UVI-697〇, UVI-6974, UVI-6990, Asahi Chemical Industry Co., Ltd., trade name: Adekaoubu 瑪 SP-170, 'SP- 171, manufactured by Sato, Ltd., trade name: CD-1012, green chemical (stock), trade name: MPI-103, since the obtained protective film has high surface hardness, it is preferable. -32- 1286563 (29) Among the above-mentioned thermally induced acid generators, specific examples of the onium salts (excluding the above-mentioned triarylsulfonium salts) include 4-ethyloxyphenyl dimethyl Hexafluoroantimonate, 4-ethenyloxyphenyldimethylhydrazine hexafluoroarsenate, dimethyl-4-(benzyloxycarbonyloxy)phenylphosphonium hexafluoroantimonate, dimethyl 4-(phenylhydroxy)phenylphosphonium hexafluoroantimonate, dimethyl-4-(benzoxyloxy)phenylphosphonium hexafluoroarsenate, dimethyl-3-chloro-4 - an alkyl phosphonium salt such as ethoxylated phenyl hydrazine hexafluoroantimonate; benzyl-4-hydroxyphenylmethyl hexafluoroantimonate, benzyl-4-hydroxyphenylmethyl hexafluorophosphate Phosphate, 4-acetoxyphenylbenzylmethyl hexafluoroantimonate, benzyl-4-methoxyphenylmethyl hexafluoroantimonate, benzyl-2-methyl-4 -Hydroxyphenylmethylhydrazine hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylphosphonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethyl a benzyl sulfonium salt such as hexafluorophosphate; dibenzyl-4-hydroxyphenyl hexafluoroantimonate, dibenzyl-4-hydroxyphenylphosphonium hexafluorophosphate, 4-ethoxypropoxybenzene base Dibenzyl hexafluoroantimonate, dibenzyl-4-methoxyphenylphosphonium hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylphosphonium hexafluoroarsenate, Benzyl-3-methyl-4-hydroxy-5-t-butylphenylphosphonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4-hydroxyphenylphosphonium hexafluorophosphate, etc. Dibenzyl sulfonium salt; p-chlorobenzyl-4-hydroxyphenylmethyl hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethyl hexafluoroantimonate, p-chlorobenzyl 4-hydroxyphenylmethyl sulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethyl hexafluoroantimonate, 3,5-dichlorobenzyl- 4-hydroxyphenylmethyl hexafluoroantimonate, o-chlorobenzyl-3-chloro-4-hydroxyphenylmethyl hexafluoro-33- 1286563 (30) substituted benzyl group铳 salt and so on. Among the more suitable ones are: 4-acetoxyphenyl dimethyl hydrazine hexafluoroarsenate, benzyl-4-hydroxyphenylmethyl hexafluoroantimonate, 4-ethenyloxyphenyl Benzylmethylphosphonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylphosphonium hexafluoroantimonate, 4-ethenyloxyphenyldibenzylphosphonium hexafluoroantimonate, and the like. The above benzothiazole salt may, for example, be 3-benzylbenzothiazole hexafluoroantimonate, 3-benzylbenzothiazole gun hexafluorophosphate or 3-benzylbenzothiazolium tetra Fluoroborate, 3-(p-methoxybenzyl)benzothiazolium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazole gun hexafluoroantimonate, 3-benzyl-5 -Benzylbenzothiazole salt such as chlorobenzothiazole key hexafluoroantimonate. Among them, 3-benzylbenzothiazole hexafluoroantimonate is suitable. An acid generator which is suitable as a heat-initiating acid generator, for example, as an alkyl sulfonium salt, can be obtained from: Asahi Kasei Co., Ltd., trade name: Adeka Obton cp-66, cp-77, etc. Sale. Further, as the benzyl sulfonium salt, Sanshin Chemical Industry Co., Ltd., trade names: SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-80L , SI-100L, SI-110L. Among them, since the obtained protective film has high surface hardness, it is preferably SI-80, SI-100, and SI-110. Composition Next, the composition of the present invention will be described. The composition of the present invention can be prepared by uniformly dissolving or dispersing the components -34- 1286563 (31) in a suitable solvent to be described later. The state of implementation of the composition of the present invention can be as follows. (1) The above-mentioned copolymers [A], [B], and [C] are essential components, and, if appropriate, a composition containing any of the additives described later (hereinafter referred to as "first composition"). 2 A composition containing a [D] curing agent in addition to the components of the above first composition. 3 The copolymer [E], [B] component, and [F] component are essential components, and, if appropriate, a composition containing any of the additives described later (hereinafter referred to as "second composition"). 4 In addition to the components of the second composition, the composition containing the "G" component (hereinafter referred to as "the third component.") The ratio of the components in the first composition is as follows. The 〇[B] component is used in an amount of 100 parts by weight, preferably 3 to 200 parts by weight, more preferably 5 to 100 parts by weight, particularly preferably 10 to 50 parts by weight, based on the copolymer [A]. If the amount is less than 3 parts by weight, the hardness of the resulting protective film may be insufficient, and on the other hand, such a enthalpy of more than 200 parts by weight may cause difficulty in the formation of the coating film. The component [C] contained in the first composition is used in an amount of preferably 3 to 100 parts by weight, more preferably 5 to 50 parts by weight, per 100 parts by weight of the copolymer [A]. When it is used in an amount used in this range, a protective film having sufficient strength can be obtained. The first composition described above is excellent in long-term stability. -35- 1286563 (32) The first composition described above is excellent in long-term stability. When the [D] curing agent is further added to the first composition, a protective film can be formed by a method described later. In addition to the requirements of adhesion, surface hardness, transparency, heat resistance, light resistance, solvent resistance, etc., the protective film formed in this manner does not dent due to the load in the state where heat is applied. And it is superior to the performance of flattening the height difference of the color filter formed on the substrate. The [D] curing agent which can be further added to the first composition is preferably used in a state of being dissolved in a suitable solvent. The concentration of the [D] curing agent in the solution is preferably from 5 to 50% by weight, more preferably from 10 to 40% by weight. The solvent which can be used herein can be the same as those exemplified as the solvent used in the production of the above copolymer [B]. The curing agent is added in an amount of preferably 20 to 60 parts by weight, more preferably 20 to 50 parts by weight per 100 parts by weight of the copolymer [A]. When used in an amount used in this range, the composition can exhibit good curing characteristics without affecting various physical properties of the resulting protective film. The composition in which the [D] curing agent is further added to the first composition is preferably supplied and used within 24 hours. The blending ratio of each component in the above second composition is as follows. The component [B] is used in an amount of 100 parts by weight, preferably 3 to 200 parts by weight, more preferably 5 to 100 parts by weight, particularly preferably 10 to 50 parts by weight, based on the copolymer [E]. When the amount is less than 3 parts by weight, the hardness of the obtained protective film may be insufficient, and on the other hand, if it exceeds 200 parts by weight, difficulty may occur in the formation of the coating film. The component [F] contained in the second composition is a copolymer of [E] 100 - 36 - 1286563 (33) by weight, preferably 3 to 100 parts by weight, more preferably 5 to 50 parts by weight. The amount is used. When used in this range, a protective film of sufficient hardness can be obtained. The second composition may further contain [G] a compound which generates an acid due to heat and/or radiation to form a third composition. The amount of the [G] component contained in the third composition is preferably 20 parts by weight or less, more preferably 0 parts by weight per 100 parts by weight of the copolymer [E]. 05 to 20 parts by weight, especially preferably 0. 1 to 10 parts by weight. When used in an amount used in this range, the composition can exhibit good curing characteristics without affecting various physical properties of the resulting protective film. The second or third composition can form a protective film by a method described later. In addition to the requirements of adhesion, surface hardness, transparency, heat resistance, light resistance, solvent resistance, etc., the protective film formed in this manner does not dent due to the load in the state where heat is applied and It is superior to the performance of flattening the height difference of the color filters formed on the substrate. Arbitrarily added components The composition of the present invention may be in various states as described above, and may contain other components than the above, as needed, without departing from the object of the present invention. Such other components may, for example, be surfactants, adhesion aids, etc. The above surfactants are added to enhance the applicability of the composition. Such a surfactant may, for example, be a fluorine-based surfactant; -37-1286563 (34) an anthrone-based surfactant; a polyethylene oxide alkyl ether or a polyethylene oxide aryl ether A nonionic surfactant such as a polyethylene oxide dialkyl ester. The polyethylene oxide alkyl ethers may, for example, be polyethylene oxide lauryl ether, polyethylene oxide stearyl ether or polyethylene oxide oleyl ether. The polyethylene oxide aryl ether may, for example, be polyethylene oxide octylphenyl ether or polyethylene oxide nonylphenyl ether. Further, the polyethylene oxide dialkyl esters may, for example, be polyethylene oxide dilaurate or polyethylene oxide distearate. Such a surfactant can be obtained, for example, from a fluorine-based surfactant: manufactured by BMCHIMIE Co., Ltd., trade name: BM-1000, BM-1100, manufactured by Dainippon Ink Chemical Industry Co., Ltd., trade name: Inorganic F142D With F172, with F173, with F-183, Sumitomo Suliem (share) system, trade name: Fu Le Latu FC-135, with FC-170C, with FC-430, with FC-431, Asahi Glass (share) system, trade name: Safran S-112, with S-1 13, with S-131, with S-141, with S-145, with S-382, with SC-101, with SC- 102, the same SC-103, the same SC-104, the same SC-105, the same SC-106, etc.; can be obtained from the ketone-based surfactant: Dongli ketone (stock) company, trade name: SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-5 7, DC-190, Shin-Etsu Chemical Co., Ltd., trade name: KP34 1, New Akita Chemicals Co., Ltd., products Name: Evert EF301, EF303, stone EF352, etc.; Can be obtained from other surfactants: Co., Ltd. Chemical Co., Ltd.'s product name: (meth)acrylic copolymer Pogliro NO. 57. Same as -38- 1286563 (35) Commercial products such as Ν〇·90. When the amount of the surfactant added is '100% by weight for the copolymer [Α] when the first composition is added, or when the second composition is added, the copolymer [Ε] is used. 100 parts by weight, preferably 5 parts by weight or less, more preferably 2 parts by weight or less. When the amount of the surfactant exceeds 5 parts by weight, film roughening of the coating film may easily occur during the coating process. The adhesion aid is added to enhance the adhesion between the formed protective film and the substrate. Such a bonding aid may, for example, be a functional decane coupling agent which is a reactive substituent such as a carboxyl group, a methacryl fluorenyl group, an isocyanate group or an epoxy group. Specifically, trimethoxymethanyl benzoic acid, r-methacryloxypropyltrimethoxydecane, vinyltriethoxydecane, vinyltrimethoxydecane, and r-isocyanate The base triethoxy decane, r-glycidoxypropyl three is composed of oxydecane, a point-(3, 4-3⁄4 oxy 5 hexyl) ethyl dimethoxy sand or the like. When the above-mentioned first composition is added, the adhesion aid is added to the copolymer [A] per 100 parts by weight or when the second composition is added, the copolymer [E] is added per 100 weight. The portion is preferably used in an amount of 30 parts by weight or less, more preferably 25 parts by weight or less. When the adhesion aid exceeds 30 parts by weight, the heat resistance of the obtained protective film may become insufficient. Solvent The composition of the present invention can be prepared by uniformly dissolving or dispersing the components in a preferably suitable solvent. The solvent which can be used is one which dissolves the components of -39-1286563 (36) or the dispersed composition, and does not react with each component. As such a solvent, the same as those exemplified as the solvent used in the production of the above copolymer [A] can be used. The amount of the solvent to be used is such that the content of the total solid component per 100 parts by weight of the composition of the present invention can be preferably from 1 to 50 parts by weight, more preferably from 5 to 40 parts by weight. Further, in combination with the above-mentioned solvent, a high-boiling solvent may be used, and a high-boiling solvent which can be used may, for example, be N-methylformamide, N,N-dimethylformamide or N- Methylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl azide, benzyl ether, dihexyl ether, acetone acetone, different Vorketone, caproic acid, caprylic acid, octanoicol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, r-butyrolactone, ethylene carbonate Ester, propylene carbonate, phenyl cellosolve acetate, and the like. The amount used in the case of using a high-boiling solvent is 1 part by weight based on the total amount of the solvent, preferably 90 parts by weight or less, more preferably 80 parts by weight or less. The composition prepared by the above method may also preferably have a pore diameter of 0. 2 to 3. 0 μιη, more preferably aperture 〇. 2 to 0. It is filtered by a Millipore filter of 5 μηη and used for use. Formation of Protective Film Next, a method of forming the protective film of the present invention using the composition of the present invention will be described. When the composition of the present invention is the first composition, the second composition or the third composition containing the thermally initiating acid generator as the [G] component, the composition of the -40-1286563 (37) is coated. The protective film is formed on the surface of the substrate by prebake to remove the solvent and form a coating film, followed by heat treatment. As the substrate, a substrate such as glass, quartz, rhodium, or resin can be used. The resin may, for example, be a ring-opening polymerization of polyethylene terephthalate, polybutylene terephthalate, polyether fluorene, polycarbonate, polyimine, and cyclic olefin. And the resin of its hydrogen additive. As the coating method, a suitable method such as a spray method, a roll coating method, a spin coating method, a strip coating method, or an ink jet method can be employed. The pre-baked conditions described above vary depending on the type of the components or the blending ratio, but may be, for example, at a temperature of from 1 to 15 minutes at 70 to 90 °C. The heat treatment after the formation of the coating film can be carried out using a suitable heating means such as a hot plate or an oven. The treatment temperature is preferably from about 15 Torr to about 250 deg., preferably from 5 to 30 minutes when using a heating plate as a heating device, and preferably from 30 to 90 minutes when using an oven. time. On the other hand, when the composition of the present invention contains the third component of the radiation-initiating acid generator as the component [G], the composition is coated on the surface of the substrate and pre-baked to remove the solvent. After the coating film is formed, the radiation is irradiated (exposure treatment) to form a protective film as a target. If necessary, heat treatment may be performed after the exposure treatment. At this time, a coating film was formed on the substrate in the same manner as described above. The radiation that can be used in the irradiation treatment of the above-mentioned radiation can be exemplified by visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, or the like. Among them, "extraordinary light" is ultraviolet light having a wavelength of 190 to 45 Onm. -41 · (38) 1286563 The exposure is preferably from 100 to 20,000 J/m2, more preferably from 1 to 10,000 J/m2, and particularly preferably from 1 to 5,000 J/m2. The film thickness of the protective film formed in this manner is preferably 〇. 丨 to 8 μηι ’ is preferably 0. 1 to 6 μ m, particularly preferably 0 · 1 to 4 μ m. Here, when the protective film of the present invention is formed on a substrate having a height difference of a color filter, the film thickness means the thickness from the uppermost portion of the color filter. The protective film of the present invention can be understood as follows, in addition to the requirements of adhesion, surface hardness, transparency, heat resistance, light resistance, solvent resistance, etc., while still applying heat It is not recessed by the load, and is applicable to a protective film for an optical device which is excellent in the flatness of the color filter formed on the substrate. [Embodiment] Hereinafter, the present invention will be described more specifically by way of Synthesis Examples and Examples, but the present invention is not limited by the following examples. Production of the copolymer [A] Hereinafter, the production examples of the copolymer [A] used in the present invention are described in Synthesis Examples 1 and 2. Synthesis Example 1 In a flask equipped with a cooling tube and a stirrer, 6 parts by weight of 2,2 / -azobisisobutyronitrile and 6 parts by weight of 2,4-diphenyl-4-methyl-1-pentene were fed. And 200 parts by weight of propylene glycol monomethyl ether acetate. Next, 80 parts by weight of glycidol-42- 1286563 (39)-based methacrylate and 20 parts by weight of styrene were fed, and after nitrogen gas replacement, stirring was started slowly. The solution temperature was raised to 95 ° C and maintained at this temperature for 4 hours to prepare a polymer solution containing the copolymer (A -1). The solid content of the obtained polymer solution was 33. 0% by weight. Further, the weight average molecular weight (Mw) of the copolymer (A-1) was 8,000. Synthesis Example 2 In a flask equipped with a cooling tube and a stirrer, 6 parts by weight of 2,2 azobisisobutyronitrile and 2,4·diphenyl-4-methyl-1-pentane 1 〇·〇 weight were fed. And 200 parts by weight of propylene glycol monomethyl ether acetate. Next, 50 parts by weight of glycidyl methacrylate and ternary methacrylate [5. 2. 1. 02,6] 50 parts by weight of decane-8-yl ester, and after nitrogen substitution, stirring was started slowly. The temperature of the solution was raised to 95 ° C, and this temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer (A-2). The solid concentration of the obtained polymer solution was 33. 0% by weight. Further, the copolymer (A-2) had a weight average molecular weight (Mw) of 6,000. Production of the copolymer [E] Hereinafter, the production examples of the copolymer [E] used in the present invention are described in Synthesis Examples 3 and 4. Synthesis Example 3 In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2 / -azo (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol methyl ethyl ether were fed. 43 - 1286563 (40) copies. Next, 25 parts by weight of styrene, 20 parts by weight of methacrylic acid > 45 parts by weight of glycidyl methacrylate and tricyclomethacrylate [5. 2. 1. 02,6] 10 parts by weight of decane-8-yl ester and subjected to nitrogen substitution, and the stirring was started slowly. The temperature of the solution was raised to 70 ° C, and this temperature was maintained for 5 hours to prepare a polymer solution containing the copolymer (E-1). The solid content of the obtained polymer solution was 33. 0% by weight. Further, the weight average molecular weight (Mw) of the copolymer (E-1) was 6,000. Synthesis Example 4 In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2 azo (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol methyl ethyl ether were fed. Next, after feeding 18 parts by weight of styrene, 20 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, and 22 parts by weight of cyclohexylmaleimide, and replacing with nitrogen, stirring was started slowly. The temperature of the solution was raised to 70 ° C ' and maintained at this temperature for 5 hours to prepare a polymer solution containing the copolymer (£ _ 2). The solid content of the obtained polymer solution was 33. 〇 Weight %. Further, the weight average molecular weight (Mw) of the copolymer (E-2) was 12,000. Preparation and Evaluation of First Composition Example 1 The solution containing the polymer (A-1) obtained in the above Synthesis Example 1 (corresponding to the amount of the copolymer (Al) in an amount of 100 parts by weight (solid content)) was added as [B] Ingredients of "King 甫 朗 E E-202" (trade name, Arakawa Optical Industry Co., Ltd.) 2 0 · 0 parts by weight, as a [C] component of bisphenol A lacquer type epoxy resin Ratio of 1286563 (41) Kete 157s65" (trade name, oily Scherr-Ebers (shares) 1 〇 〇 part by weight, as a bonding aid 7 - glycidoxypropyl trimethoxy decane 1 5 Parts by weight, and as a surfactant, SH28PA (Torayone) 1 part by weight, and then added propylene glycol monomethyl ether acetate in such a manner that the solid content can be 20%, and the pore diameter is 0. The 5 μηιη 米 利波亚 filter was filtered to prepare the first composition. Formation of a protective film. In the composition prepared as described above, 35 parts by weight of trimellitic anhydride was added as a component [D], and 65 parts by weight of ethylene glycol methyl ethyl ether was dissolved to prepare a protective film. A composition for formation. The components modulated here are colorless and transparent. After coating the above composition on a Si〇2 impregnated glass substrate using a spin coater, it was prebaked on a hot plate at 80 ° C for 5 minutes to form a coating film, which was then heat treated in an oven at 230 ° C. 60 minutes to form a film thickness 2.  Evaluation of Protective Film Protective Film of Ομιη1 Evaluation of Transparency 基板 A substrate having a protective film formed as described above, using a spectrophotometer (150-20 type double beam (manufactured by Hitachi, Ltd.)) to measure 400 The penetration rate to 800 nm. Table 1 shows the minimum 値 of the transmittance of 400 to 800 nm. When the ruthenium is above 95%, the transparency of the protective film is considered to be good. 45- 1286563 (42) 2 Evaluation of the heat-resistant dimensional stability The substrate having the protective film formed as described above is in the oven. The film was heated at 25 ° C for 1 hour and the film thickness before and after heating was measured. The heat resistance dimensional stability calculated by the following formula is shown in the table. When the enthalpy is above 95%, the heat resistance dimensional stability is considered to be good. Heat-resistant dimensional stability = (film thickness after heating) / film thickness before heating xl 〇〇 (%) 3 Evaluation of heat-resistant discoloration The substrate having the protective film formed as described above, at 250 ° in an oven The mixture was heated under C for 1 hour, and the transparency before and after heating was measured in the same manner as in the above 1. Table 1 shows the thermal discoloration resistance calculated by the following formula. Thermal discoloration resistance = penetration rate before heating (%) - transmittance after heating (%) 4 Determination of surface hardness The substrate having the protective film formed as described above according to JIS 1 (5400-1 990) 8. 4. 1 pencil scratch test to determine the surface hardness of the protective film. This is shown in Table 1. When the thickness is 4H or hard, the surface hardness is considered to be good. (5) Measurement of dynamic microhardness The substrate having the protective film formed as described above was subjected to Shimadzu dynamic microhardness tester DuH-201 (manufactured by Shimadzu Corporation), in accordance with the angle -46-1286563 (43) 1 1 5 ° triangular indenter (Herco must know type) of the bet test, according to the load: 0. 1 £ 〖, speed: 〇. 〇 1452 丨 / sec, hold time: 5 seconds 'temperature: 23 。. (: and the measurement conditions of 1 40 ° C, the dynamic microhardness of the protective film was measured. The results are shown in Table 1. 6 Evaluation of the adhesion property The substrate having the protective film formed as described above was subjected to a pressure cooker test ( 1201, humidity 100%, 4 hours), according to JIS K·5400-1 990 8. 5. 3 Adhesive square lattice adhesive tape method was used to evaluate the adhesion of the protective film (adhesion to Si〇2 (cerium oxide)). Table 1 shows the number of square lattices left in one square lattice. Further, as an evaluation of the adhesion of Cr (chromium), a Cr substrate was used except that the substrate was not impregnated with Si〇2, and the film thickness was formed in the same manner as described above. The protective film of Ομιη was evaluated in the same manner as the above-mentioned square adhesive tape method. The results are shown in Table 1. 7 Evaluation of planarization On a SiCh-impregnated glass substrate, a pigment-based color resist was applied using a spin coater (trade names "JCRRED689", "JCR GEEN 706", "CR8200B", all of which are Jay Ayers ( The system was prebaked on a hot plate at 90 ° C for 150 seconds to form a coating film. Then, the exposure machine Canon (PAA) was used to pass the pattern mask (Canon) In the system, the ghi line (intensity ratio of wavelength 436 nm, 405 nm, 365 nm = 2·7: 2·5: 4·8) is irradiated with an exposure amount of 2,000 J/m 2 in the i-line conversion, -47 - 1286563 (44) It was developed with 〇·05 % potassium hydroxide aqueous solution, rinsed with ultrapure water for 60 seconds, and then heat treated at 230 ° C for 30 minutes in an oven to form red, green and blue. 3 color band-shaped color filter (strip width 1 〇〇μηΊ). The unevenness of the surface of the substrate on which the color filter was formed was measured using a surface roughness meter "α - 斯贴补" (trade name: manufactured by Timor) The result is 1.  Ο μ m. Here, the measurement was carried out under the conditions of measurement length 2, Ο Ο Ο μ m, measurement range 2, Ο Ο Ο μ m, angle, and number of measurement points n = 5. That is, the measurement direction is made into the short axis direction of the stripe line in the red, green, and blue directions, and the direction of the long axis direction of the strip line of the same color of red, green, green, blue, and blue, It is measured in each direction by n = 5 (the total number of η is 10). Here, after coating the above protective film forming composition using a spin coater, it was prebaked on a hot plate at 90 ° C for 5 minutes, and then heat-treated at 230 ° C for 60 minutes in an oven to form a filter. The film thickness on the top of the color device is 2. Protective film of Ομιη. In the color filter formed as described above, a substrate was provided on the color filter, and the contact film thickness measuring device α-strip (manufactured by Timor Japan Co., Ltd.) was used to measure the unevenness of the surface of the protective film. Here, the measurement was carried out under the conditions of a measurement length of 2,000 μm, a measurement range of 2,000 μm, and measurement of the number of dots η = 5. That is, the measurement direction is made into the direction of the short line of the strip line in the red, green, and blue directions and the direction of the long axis of the same strip line of the same color of red, red, green, green, blue, and blue, and Each direction was measured by η = 5 (the total number of η was 10). In Table 1, the average 値 of 10 times of the height difference (nm) between the highest part and the bottom part of each measurement is shown. When the 値 is 300 nm or less, the flatness is considered to be good. -48- 1286563 (45) Examples 2 to 7 and Comparative Examples 1 and 2 The types and amounts of the components of the composition were determined as shown in Table 1, and were used without using propylene glycol monomethyl ether acetate. The composition described in Table 1 was prepared in the same manner as in Example 1 except that the solvent contained in Table 1 was blended. The composition was added as a component [D], and 35 parts by weight of trimellitic anhydride was dissolved in 65 parts by weight of diethylene glycol methyl ethyl ether to prepare a composition for forming a protective film. The appearance of the composition prepared here is shown in Table 1. Using the composition for forming a protective film prepared as described above, a protective film was formed in the same manner as in Example 1 and evaluated. The results are shown in Table 1. Here, the addition amount of each component in Table 1 is a part by weight, and "--" in the table means that no equivalent component is added. Further, the shortcomings of '[B] component, [C] component, and solvent are respectively indicated as follows. B-1 : 矽 改性 环氧树脂 环氧树脂 E 甫 甫 ( ( ( ( ( ( ( B B B B B B B B B B B B B B B B B B B B B B B B B B B B B (Product name: "Arakawa Chemical Industry Co., Ltd.") B-3: decane-modified epoxy resin "Kongyin Seika 01" (trade name: Arakawa Chemical Industry Co., Ltd.) B-4: decane modified epoxy Resin "Hole e 朗 e-212" (trade name 'Arakawa Chemical Industry Co., Ltd. 】) -49- 1286563 (46) Cl: bisphenol A lacquer type epoxy resin (oiled Cher Aiboikes) ), trade name: Ebicon 1 5 7 S 6 5 ) C-2 : bisphenol A epoxy resin (oiled Cher Abbox (stock) system, trade name: Ebikete 828) S -1 : Propylene glycol monomethyl ethyl acetate S-2 : diethylene glycol monomethyl ethyl acetate

•50- 1286563

Comparative Example CM 1 100 1 1 1 1 IT) 1 CM ώ Colorless and transparent C0 〇CO Ο) CO 寸 卜 卜 卜 — 100 195 τ — 100 1 1 I 1 1 LO 1 ώ Colorless and transparent G) 7 ο 7 CO Working size 7 CM 00 ΊΓ- 100 s 210 Example 1 100 1 1 1 s 1 to Ί—CM ώ ώ colorless transparent Ο) Ο) Ο) Ο) CO CO CM CO 00 CM 100 100 200 CO 100 1 1 1 1 so Ύ— 1 ώ colorless transparent Ο) Ο) Ο) σ> CO CO ο 00 CM 100 100 ! 190 in 1 100 1 § 1 瞧o 1 ώ Colorless transparent Ο) 7 Ο) Ο) CO CO CM CO Oi 100 100 195 inch 1 100 s 1 1 1 1 in T- CM ώ colorless transparent Ο) 〇Ο) σ> CO CO ο CO CM 100 100 180 CO 100 1 Zhan s 1 1 o T — ώ Colorless and transparent σ> Ο) Ο) Ο) CO work CD CM CO CM 100 100 200 CM 100 1 1 s 1 1 LO 1 CVI ώ colorless transparent Ο) Ο) σ> CO CO 荛O) C\J 100 100 200 i — 100 1 1 1 1 o 1 ώ Colorless and transparent Ο) Ο) Ο) σ> CO in σ> CM LO CM 100 100 190 LT— < A-2 ώ CM ώ CO ώ B-4 T— ό C- 2 Solvent solids (%) [D] Appearance transparency after addition of ingredients ( Heat resistance dimensional stability (%) Thermal discoloration (%) Pencil hardness 23〇C 140°c ω ο Flattening energy (nm) Copolymer [A] _ parts [c] Component dynamic microhardness adhesion - 51 - 1286563 (48) Preparation and evaluation of the second composition Example 8 A solution containing the copolymer (E-1) obtained in the above Synthesis Example 3 as the component [E] (corresponding to the copolymer (El) 100 weight In the amount of the (solid content), the product of the decane-modified epoxy resin of the [B] component, "Hole E 朗 E E E E E E E E E E E E E E E E E E E E E E E E E E E E E Ingredients of bisphenol A lacquer type epoxy resin (oiled by Shier Aiboikes Co., Ltd., trade name: Ebicon 157S65) 10.0 parts by weight, and SH-28PA as a surfactant (Dongli) 0.1 parts by weight of fluorenone (manufactured by oxime), propylene glycol monomethyl ether acetate was added in such a manner that the solid content concentration was 20.0 parts by weight, and then filtered using a Millipore filter having a pore size of 0.5 μm to prepare a second composition. . The appearance of the composition prepared here is colorless and transparent. Formation and Evaluation of Protective Film The composition prepared as described above was coated on a Si 02 impregnated glass substrate using a spin coater, and then prebaked on a hot plate at 8 CTC for 5 minutes to form a coating film, which was then baked. The furnace was heat-treated at 230 ° C for 60 minutes to form a protective film. Further, a protective film was formed on the substrate on which the color filter was formed in the same manner as in the method described in Example 1, in accordance with the above method. Evaluation was carried out in the same manner as in Example 1 using a substrate having such a protective film. The results are shown in Table 2. -52- (49) 1286563 Examples 9 and 10 and Comparative Examples 3 and 4 The types and amounts of the respective components of the composition were the same as those described in Table 2 except that propylene glycol monomethyl ether acetate was not used. The composition of the composition prepared in the same manner as in Example 8 except that the solvent described in Table 2 was used was shown in Table 2. Using the composition prepared as described above, a protective film was formed and evaluated in the same manner as in Example 8. The results are shown in Table 2. Preparation and evaluation of the third composition Example 1 1 A solution containing the copolymer (E-2) obtained in the above Synthesis Example 4 as the component [E] (corresponding to 1 part by weight of the copolymer (E-1) In the amount of (solid content), a decane-modified epoxy resin of the [B] component, "Kongsei Seika E-202" (trade name, manufactured by Arakawa Chemical Industry Co., Ltd.), 20.0 parts by weight was used as [F 15.0 parts by weight of trimethylolpropane ginseng (3-methyl-3-oxetanylmethyl)ether as the [G] component benzyl-2-methyl-4-hydroxyphenyl 2 parts by weight of hexafluoroantimonate and 'SH-28PA (manufactured by Toray ketone) as a surfactant) 1 part by weight 'adds B as a solid content concentration of 20.0% by weight The diol dimethyl ether was then filtered using a Millipore filter having a pore size of 5 μm to prepare a third composition. The appearance of the composition prepared here is shown in Table 2. Using the composition prepared as described above, a protective film was formed in the same manner as in Example 8 -53- 1286563 (50) and evaluated. The results are shown in Table 2. [Example 1] The composition was prepared in the same manner as in the same manner as in the above, except that the types and amounts of the components of the composition were the same as those described in Table 2. The appearance of the composition prepared here is shown in Table 2. The above composition solution was applied onto a 3丨〇2 impregnated glass substrate using a spin coater, and then prebaked on a hot plate at 80 ° C for 5 minutes to form a coating film. Next, using the exposure machine Canon PLA501F (manufactured by Canon), the ghi line (intensity ratio of wavelengths of 4 6 nm, 405 nm, and 3 65 nm = 2.7 : 2.5 : 4.8) was applied to the i-line. The conversion is irradiated with an exposure amount of 2,000 J/m 2 . It was further heated in an oven at 230 ° C for 60 minutes to form a protective film. Further, in the substrate on which the color filter was formed by the method described in the first embodiment, the processes of coating, prebaking, exposure, and heating were carried out in the same manner as described above to form a protective film. The substrate having such a protective film was used and evaluated in the same manner as in Example 6. The evaluation results are shown in Table 2. [Embodiment 1] In the same manner as in Example 12 except that the exposure amount was changed to 300 J/m2, the results shown in Table 2 were obtained. Here, in Table 2, the addition amount of each component is a part by weight, and ^" in the table means that no equivalent component is added. Further, the [B] component, the [F] component, the [G] component, and the abbreviation of the solvent '-54- 1286563 (51) are respectively shown below. --l _Sand Institute Modified Epoxy Resin "Hole E色朗E-202" (trade name, Arakawa Chemical Industry Co., Ltd.) Β - 2 · Sand Institute modified epoxy resin "孔甫色朗 ε _ 2 〇 1" (product name 'Arakawa Chemical Industry Co., Ltd.) Β-3 : decane-modified epoxy resin "Kong 甫 朗 E E-丨 01" (trade name, Arakawa Chemical Industry Co., Ltd.) F- 1 : bisphenol A lacquer type epoxy resin (made by oily Schell Abbox (trade name), trade name: Ebicon 157S65) F-2 : trimethylolpropane ginseng (3-methyl-3) -oxetanylmethyl)ether G-1: benzyl-2-methyl-4-hydroxyphenylmethylphosphonium hexafluoroantimonate G-2: triphenylsulfonium trifluoromethanesulfonate S-3: propylene glycol monomethyl ether acetate S-4: diethylene glycol dimethyl ether (52) 1286563 (52)

CV1撇Comparative example 1 100 1 1 1 IT) 1 1 1 ώ Colorless transparent 00 σ> CO Ο) CM 00 CM Ο τ — I loo ... I o T — I 210 I C0 100 1 1 1 1 o 1 1 1 CO ώ 1 colorless and transparent | 7 G) C0 〇CM size 7 CVJ CsJ C\l 100 o 210 C0 T— 100 1 Ink S 1 LO 1 1 (N ώ colorless transparent Ο) Ο) Ο) 〇> CM work IT) CM CM 100 100 200 (MT—100 1 1 S 1 LO 1 1 CM ώ colorless transparent 7 σ> Ο) Ο) CM work CD Another LO <M 100 100 200 T— 1 100 1 1 1 LO CM 1 CO ώ colorless transparent 〇 7 CM work CD CvJ CO 100 100 200 U 〇 1 100 1 1 s 1 LO 1 1 ώ colorless transparent Ο) Ο) Ο) CM work CD ω CVJ LO CM 100 100 205 σ> 1 S 1 1 1 1 CO ώ colorless transparent σ> Ο) Ο) Ο) CM work LO Ύ — CO CD CM 100 100 220 00 100 1 1 1 o 1 1 1 CO ώ colorless transparent Ο) Ο) Ο) CM CD Gi CM 100 100 210 ώ CM LLJ ώ C\J ώ cp CD iL CM iL ώ G-2 Solvent solid content (%) Appearance transparency of the composition prepared (%) Heat resistance dimensional stability (%) Heat resistance Discoloration (%) Pencil hardness 1 23〇C 140°C Si〇2 o Tannin energy (nm) copolymer [Ε] [Quenching component [F] component [G] component dynamic microhardness adhesion - 56-1286563 (53) As described above, if the present invention is used, it can be obtained In addition to being able to satisfy various characteristics that are required as a protective film, specifically, adhesion, surface hardness, transparency, heat-resistant dimensional stability, thermal discoloration resistance, and anti-plating property are applied In the hot state, it is not recessed by the load, and is applicable to a composition of a protective film forming material for an optical device which is excellent in flattening the level difference of the color filter formed on the substrate, and thus A protective film is formed.

-57-

Claims (1)

1286563 (1) Picking up, applying for patent coverage No. 92 1 1 2983 Patent application Chinese patent application scope amendments October 4, 1995 Revision 1. A resin composition characterized by: [A] (al) a copolymer containing an epoxy group-containing unsaturated compound, and an alkene unsaturated compound having a (a2) and (al) component, [B] (bl) a hydroxyl group-containing epoxy resin and (b2) alkoxydecane The reactants, and the cationically polymerizable compound in which [C] is different from the [A] component and the [B] component. 2. The resin composition as recited in claim 1, wherein the [D] curing agent is further contained. 3. A resin composition characterized by containing [E] (el) unsaturated carboxylic acid and/or unsaturated carboxylic anhydride, (e2) an epoxy group-containing unsaturated compound, and (e3) and (el) a copolymer of an olefinic unsaturated compound having a different composition and (e2) component, [B] (bl) a reactant of a hydroxyl group-containing epoxy resin and (b 2) alkoxydecane, and [F] and [ The resin composition according to the third aspect of the invention, which further contains [G] a compound which generates an acid due to heat and/or radiation. 5. A method for forming a protective film, which is characterized in that: [A] component, [B] component, [c] component, and [D] curing agent described in the first item of Patent No. 1286563 (2) Mix and apply the mixture to the substrate, followed by heat and/or radiation. 6. A method for forming a protective film, characterized in that: [E] component, [B] component, [F] component, and [G] according to item 3 of the patent application scope are generated by heat and/or radiation. The acid compounds are mixed and the mixture is applied to a substrate and then treated by heat and/or radiation. 7. A protective film formed by the resin composition described in any one of claims 2 to 4.