TW201237098A - Thermal curing resin, cured film, color filter, liquid crystal display device, solid photographic device and LED luminous body - Google Patents

Abstract

A cured film especially excellent in light resistance, evenness and also excellent in heat resistance, chemical resistance such as solvent resistance, acid resistance, base resistance, etc., water resistance, adhesive property for substrate such as glass, etc., penetrability, damage resistance and coating ability is provided, and also a resin composition for the cured film is provided. A thermal curing resin composition includes: a polyester amide acid, an epoxy resin and an epoxy curing agent, characterized in that the polyester amide acid is obtained by performing a reaction using a tetracarboxylic dianhydride, a diamine and polyprotic hydroxy compound as necessary materials, and the epoxy resin is obtained by performing a reaction using a glycidyl (meth)acrylate and 2 functional (meth)acrylate as necessary materials.

Description

201237098 41171pif VI. Description of the invention: [Technical field to which the invention pertains] It is a cured film obtained by heating and hardening a thermosetting tree. Hunting is carried out by various chemical treatments such as the steps of manufacturing liquid crystal display elements, such as liquid crystal display elements, acid, alkali solution, etc., when the organic Luo wire electrode is introduced, the surface is locally twisted to form a film. To prevent deterioration of the surface of various components, damage to the manufacturing process, solvent resistance, solvent resistance, acid resistance, and resistance to chemical heat: adhesion, transparency, and scratch resistance of a base substrate such as glass; Betty, lightfast, etc. In addition, when the development of the solar cell display element, the south-speed response, and the high-definition, and the development of the towel protective film, it is desirable to flatten it to mention that 3 is related to light resistance. Ultraviolet ozone treatment was carried out in order to protect the film surface & month wash. However, especially the cross-field electric field mode and color filter 'light film protection wealth, for the coating property of the 'pieces', higher energy UV ozone treatment = inter = symmetry (polym (10) stained alignment, p / light The ultraviolet light exposure step such as the polymerization step or the photo-alignment step of the alignment film is added, and the light resistance becomes a very important characteristic. 3 As a protective ruthenium material having such excellent characteristics, there is a composition containing Shi Xi 201237098 41171 pif acid (refer to the patent) Documents υ, poly (refer to the special offer 2, 3). Containing inhibition of training Lin = flat (four) words for non-f «reading materials, but there are _ sexual shirts in the shortcomings of the test of production. Special offer 2 (4) The composition of the stern ship is not enough to be quite entangled. The special composition is a material with excellent flatness, heat resistance and Wei Xue character. However, the tree is not sufficient, and it is treated with UV ozone or There is a disadvantage that the ultraviolet light is exposed in the ultraviolet exposure step. Therefore, any material is not used as a protective film material to sufficiently satisfy light resistance, flatness, heat resistance, chemical resistance, and other characteristics. [Prior Art Document] [Patent Literature] patent In the above-mentioned situation, the demand is disclosed in Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. For example, a resin composition excellent in chemical resistance such as heat resistance, solvent resistance, acid resistance, and alkali resistance, water resistance, adhesion to a base substrate such as glass, transparency, scratch resistance, and coating property. In particular, the present inventors have conducted various studies in order to solve the above problems, and have found that polyester is contained in the cured resin film, which is excellent in light resistance and light resistance. a proline (the polyester proline is obtained by a compound comprising a tetracarboxylic dianhydride, a diamine and a polyvalent hydroxy compound, and a polyester phthalic acid obtained from 201237098 41171pif), an epoxy resin The epoxy resin is an epoxy resin obtained by reacting glycidyl (meth)acrylate with a bifunctional (fluorenyl) acrylate as an essential raw material component, and a resin composition of an epoxy curing agent, and The cured film obtained by curing the resin composition can be far from the above object, and the present invention has been completed. The present invention has the following constitution. [1] A thermosetting resin composition comprising a polyester proline, an epoxy A resin composition of a resin and an epoxy hardener, wherein the polyester phthalic acid is obtained by reacting a tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound as essential raw materials. A polyester decylamine obtained by reacting X-molar tetraphthalic acid dianhydride, Y-mole diamine, and z-mole polyhydroxy compound at a ratio in which the relationship of the following formula (1) and formula (2) is established. Acid, 0.2SZ/YS8.0 ...... (1) 0.2^ (Y + Z) /X^1.5 ...... (2) Each oxy resin is obtained by glycidyl acrylate and difunctional (fluorenyl) acrylate An epoxy resin having a weight average molecular weight of 1,000 to 50,000 obtained by reacting an ester as an essential raw material component, and an epoxy resin is 20 parts by weight to 400 parts by weight based on 100 parts by weight of the polyester phthalic acid. Compared with 1 part by weight of the epoxy resin, the epoxy hardener is ~ 60 parts by weight parts by weight. [2] The thermosetting resin composition according to [1], wherein the polyester phthalic acid is an essential raw material by using a tetracarboxylic dianhydride, a diamine, a polyvalent hydroxy compound, and a decyl alcohol. A reaction product obtained by reacting a component. 6 201237098 41171pif 丨 心 哎 哎 哎 树脂 是 是 是 是 是 是 是 是 是 是 是 是 是 是 是 是 是 是 是 是 是 是 是 是 是 是 是 是 是 是 是 是 是 是 是 是 是 是 是 是[4] The thermosetting resin composition according to any one of [1] to [3] wherein the polyester phthalic acid is further reacted by adding a stupid ethylene maleic anhydride copolymer as a raw material component. The polyester proline obtained. [5] The thermosetting resin composition according to any one of [1] to [4] wherein the polyester phthalic acid has the following formula (3) and formula (4) Structural unit; 〇II cv 〇

HOOC COOH NH-

-N- H (3) Ο (4) ——cx β—O—R3 〇 〇 R1

HOO (/, COOH where R1 is a tetrahydro acid diterpene residue 'R2 is an amine residue' R3 is a residue of a polyvalent hydroxy compound. [6] As described in any one of [1] to [5] The thermosetting resin according to any one of [1] to [6], wherein the poly-amino acid has a weight average molecular weight of from 1 000 to 200,000 〇 [7]. Composition 201237098 41171pif, wherein the tetracarboxylic dianhydride is selected from 3,3',4,4'-diphenylsulfone tetraphthalic acid dianhydride, 3,3',4,4'-diphenyl One or more of ether tetradecanoic acid dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, and ethylene glycol bis(hydrogen trimellitate). [8] The thermosetting resin composition according to any one of [1], wherein the diamine is selected from the group consisting of 3,3'-diaminodiphenylsulfone and bis[4-(3) The thermosetting resin composition according to any one of [1] to [8] wherein the polybasic compound is One selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol Above. [10] The thermosetting resin composition according to any one of [1] to [9] wherein the bifunctional (fluorenyl) acrylate is selected from the group consisting of ethylene glycol di(decyl) acrylate, diethyl Diol bis(indenyl) acrylate, 1,4-butanediol bis(indenyl) acrylate, 1,3-butanediol bis(indenyl) acrylate, neopentyl glycol di(indenyl) propyl The thermosetting resin composition of any one of [1] to [1], wherein the thermosetting resin composition of any one of the above-mentioned [1] to [1] The above-mentioned epoxy hardener is one or more selected from the group consisting of a sulphuric acid anhydride and a hexahydro sulphuric acid.酉夂一轩 is 3,3,4,4-a-based tetracarboxylic acid di-hepatic, the diamine is 3,3'-diaminodiphenyl fluorene. The polyhydroxy compound is 1,4-butyl The diol 'the epoxy resin is glycidyl methacrylate and hydrazine, 4 - butanediol 201237098 4ll71pif dimethacrylate or 1,3-butanediol dimercapto acrylate has a weight average molecular weight of 1, 〇〇〇~50,000 copolymer, The epoxy hardening = benzotrilin, which is a thermosetting resin composition according to the above [2], wherein the tetracarboxylic dianhydride is 3 , 3', 4, 4 ·-diphenyl ether tetraphthalic acid dianhydride, the diamine is 3,3'-diaminodiphenyl sulfone, and the polyvalent hydroxy compound is 4-butanediol. The monohydric alcohol is phenyl decyl alcohol, and the epoxy resin is the weight of methacrylic acid glycerin and 1,4-butanediol dimercapto acrylate or butane diol dimethacrylate. The average molecular weight is! , 〇〇〇~5〇, 〇〇〇-*: ^Polymer The epoxy hardener is trimellitic anhydride, and further contains decyl propionate as a solvent. [14] A cured film obtained by the thermosetting resin composition according to any one of (1) to [13]. A color calender sheet using the cured film as described in [14] as a protective film. [16] A liquid crystal display element, a light sheet. It uses a color filter [17] as described in [15] as a solid-state photographic element light sheet. It uses the color filter [=- liquid crystal display element according to [15], which uses a transparent display formed between the bright electrodes of the film, and uses the hard device as described in [14] above. 3 A transparent insulating film formed between the films. A net-growing illuminant using the hardened 201237098 41171 pif film as described in (10) above as a protective film. [Effects of the Invention] The thermosetting resin composition of the preferred embodiment of the present invention is a material which is used for a flat color and a light resistance (4) slit material, and is used as a color filter sheet as a color liquid crystal display element. Can improve display quality and reliability. Further, the cured film obtained by heating the thermosetting resin composition of the present invention is also a practical one in that it is balanced in transparency, chemical resistance, adhesion, and sputter resistance. In particular, it can be used as a protective film for a color filter produced by a dyeing method or a pigment dispersion method. Moreover, it can also be used as a protective film and a transparent insulating film for various optical materials. [Embodiment] 1. Thermosetting resin composition - The thermosetting resin composition of the present invention is a resin composition comprising polyester glutamic acid, ring = tree, and J hen oxygen curing agent, said polyester Proline is a polyester lysine obtained by reacting four thief dianhydrides, diamines, and polybasic compounds, which is obtained by a knife reaction. The epoxy resin is a sulphuric acid. Glycerol_ an epoxy obtained by reacting a bifunctional (meth)acrylic acid as a raw material component, which is characterized in that it is characterized by a percentage by weight of the polyamic acid (10) by weight The resin is 20 parts by weight to 4 parts by weight, and the epoxy curing agent is 0 parts by weight to 60 parts by weight based on the parts by weight of the epoxy resin. 1-1. Polyester phthalic acid The polyglycolic acid is obtained by reacting a compound of a tetrabasic acid, a diamine, and a polybasic 201237098 41171pif compound as essential raw materials. More specifically, the reaction is carried out by the ratio of the relationship of the following formula (1) and formula (2) by using X mole 4 tetrahydro acid dianhydride, Y mole diamine and Z mole polyhydroxy compound. And get. (1) (2) 0.2^Z/Y^8.0 0.2^ (Y + Z) /X^1.5 At least the solvent must be used in the synthesis of polyacetic acid, so that the solvent can remain in the residue and be considered for operation. The composition of the liquid or gel-like thermosetting resin such as a liquid or the like may be removed by the solvent to obtain a solid shape composition in consideration of handling properties and the like. Further, in the synthesis of the polyester phthalic acid, one or more kinds of raw materials selected from the group consisting of a hydrazine alcohol and a stupid ethylene-maleic anhydride copolymer are preferably used as a raw material, and among them, a monohydric alcohol is preferable. . Moreover, the synthetic smear of the ugly smear can also be used as a supplement to the object of the present invention without damaging the purpose of the present invention. As such an example of the raw material, a monoamine containing hydrazine can be mentioned. Specific examples of the four-n-two-nixuan used in the tetracarboxylic dianhydride 2 can be exemplified by the following fragrant four-week, such as 3,3,,4,4,-diphenylfluorene-tetracarboxylic acid; 2 drunk 2,3,3'_diphenyl hydrazine with tetradecanoic acid di-hepatic, 2,3,3,,4,-diphenyl fluorenone oxime & _ 3,3,4,4·· Styrenone sulfone tetra-f acid dianhydride, 2,2',3,3,-diphenyl sulfone anhydride 2,3,3,4'-diphenyl stone wind tetracarboxylic dianhydride, 3 3 ', 4, 4' - diphenyl t ^ formic acid: anhydride, 2, 2', 3, 3, · diphenyl _ formic acid read, ' 2,3,3,,4 ·- two = (10) tetradecanoic dianhydride, 2, 2_[ Bis(3,4-di-phenylphenyl)]hexafluoropropanone- and ethylene glycol bis (dehydrated trimellitic acid trade name 201237098 41171pif TMEG-100, New Japan Physical and Chemical Co., Ltd.); alicyclic four Acidic dianhydrides such as cyclobutane tetraphthalic acid dianhydride, fluorenylcyclobutane tetradecanoic acid two needles, cyclopentane tetracarboxylic acid dianhydride, and cyclohexene tetracarboxylic acid two needles; aliphatic tetrazoic acid A dianhydride such as acetylated tetracarboxylic dianhydride and dibutyl succinic acid bismuth. Preferred among these compounds are 3,3',4,4'-diphenylphosphonium tetraphthalic acid dianhydride and 3,3',4,4'-diphenyl bond which can impart a resin having good transparency. Tetracarboxylic acid dianhydride, 2,2-[bis(3,4-di-t-phenylene)]hexafluoropropane dianhydride, ethylene glycol bis(hydrogen trimellitate) (trade name TMEG-100, New Japan Physical and Chemical Co., Ltd.) 'Specially good is 3,3',4,4'-diphenyl shunt tetradecanoic dianhydride, 3,3,,4,4,- a basal tetradecanoic acid wild·. M-2. Diamine Specific examples of the diamine used in the present invention include 4,4,-diaminodiphenyl, 3,3'-diaminodiphenylsulfone, and 3,4f-di Aminodiphenyl, bis[4-(4-aminophenyloxy)phenyl]sulfone, bis[4-(3-aminophenyloxy)phenyl]sulfone, bis[3-(4-amine) Phenyloxy)phenyl]hard, [4-(4.aminophenoxy)phenyl][3_(4-aminophenoxy)phenyl]sulfone, [4-(3-aminophenoxy) Phenyl][3_(4-aminophenoxy)phenyl]sulfone, and 2,2-bis[4-(4-aminophenyloxy)phenyl]hexafluoropropane. Preferred among these compounds are 3,3-aminodiphenylsulfone and bis[4-(3-aminophenyloxy)phenyl]sulfone which can impart a resin having good transparency. It is 3,3'-diaminodiphenyl sulfone. 1-1-3. Polybasic compound Specific examples of the polybasic compound used in the present invention include: ethyl alcohol, monoethyl alcohol, diethylene glycol, tetraethylene glycol, and a weight average molecular weight of 1,000. The following polyethylene glycol, propylene glycol, bis = 12 201237098 41171pif alcohol C & heavy 罝 average molecular weight of 1,2-butanediol, 13_丁-domain 7 ^ Bu of polypropylene glycol, 予,J 丁一知, 1,4-butanediol, pentane-ruthenium, 2,4-decanediol, u,5-pentanetriol, pentyl Tt: this alcohol, U, 6 · hexamethyl heptanediol , heart 4 hexanediol, heptanediol, 1,2-octanediol, heptyl-alcohol, 1,2,7·^^ 肀-alcohol, 3,6-octanediol, 0 0 containing monool, 1,2-decanediol, acetamethylene glycol, sulphate, 9- decyl alcohol, bis: diterpenediol 'U, 1G• decyl alcohol, 12 dioxin, monool, Glycerol, trimethylol-6:- double-age μ product name), double-named product name), bisdiethanolamine, and triethanolamine. Also divided into business. . Preferred), = = some of the compounds are preferably soluble in the solvent of ethylene di-butanediol, ruthenium phthalate ' 1,6-hexanediol, 17 G-I, and 1,8-octanediol, particularly good brewing and 1,6-hexanediol.羿i, 5-pentalol, 1-1-4. 1 alcohol ^ used in the invention! Specific alcohols of the alcohol, 1-propanol, isopropyl g|, _ _ ping 1 ^ ethyl ethyl ester, propyl - chlorin two methanol, methacrylic acid hydroxy field ·, propylene glycol monocarboxylic acid, dipropylene glycol single B Test, two = floor, ethylene glycol single sulphur, ethylene glycol monomethyl hydrazine, diethyl _ Ϊ alcohol single ethyl _, benzene, borneol, maltol, aromatic i burning. Preferred among A farinol, monomethyl octyl methanol, and 3-ethylhexylmethyl propylene oxide compound are isopropyl alcohol, propyl scale, phenyl propylene acetonate, propylene glycol monoethyl hydrazine, 3_ethyl merylmethyl ring 13 201237098 41171pif oxypropane. Consider the compatibility in the case where the polyester phthalic acid obtained by using these compounds is mixed with an oxygen generating resin and an epoxy curing agent, or the thermosetting resin composition as a final product on a color filter. More preferably, the benzyl alcohol is benzyl alcohol. The monohydric alcohol is preferably contained in an amount of 2 parts by weight to 3 parts by weight based on 100 parts by weight of the total of four tetrahydrous dianhydrides, diamines, and polybasic compounds. More preferably, it is 5 parts by weight to 2 parts by weight. 1-1-5. Styrene-maleic anhydride copolymer Further, the polyester phthalic acid used in the present invention may be subjected to a synthesis reaction by adding a compound having three or more acid anhydride groups. Specific examples of the compound having three or more acid anhydride groups include a styrene-maleic anhydride copolymer. With respect to the ratio of the components constituting the stupid ethylene-maleic anhydride copolymer, the molar ratio of styrene/maleic anhydride is from 0.5 to 4, preferably from 1 to 3, and more preferably from about 1, to about 1, 2 or about 3, still more preferably about 1 or about 2, and particularly preferably about 1.

Specific examples of the styrene-maleic anhydride copolymer include commercially available products such as SMA3000P, SMA2000P, and SMA1000P of Chuan Petrochemical Co., Ltd. Among these, the SMA1000P is excellent in heat resistance and alkali resistance. The styrene-maleic anhydride copolymer preferably contains 〇 parts by weight to 500 parts by weight based on 100 parts by weight of the total of the tetrabasic acid dianhydride, the diamine, and the polyvalent hydroxy compound. More preferably, it is 10 parts by weight to 300 parts by weight. 1-1-6. The synthesis of the monoamine containing Shixi in the synthesis of the polyester phthalic acid may also be carried out as a raw material as needed in the range of 201237098 41171pif, which does not impair the object of the present invention. Examples of such other raw materials include a monoamine containing Shi Xi. Specific examples of the monoamine containing ruthenium used in the present invention include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, and 3-aminopropylmethyl-methoxyl. Base, 3-aminopropylmethyldiethoxy oxacyclohexane, 4-aminobutyltrimethoxydecane, 4-aminobutyltriethoxydecane, 4-aminobutylphosphonium Diethoxy decane, p-aminophenyl trimethoxy decane, p-aminophenyl triethoxy decane, p-aminophenyl methyl dimethoxy decane, p-aminophenyl fluorenyl di Oxydecane, m-aminophenyltrimethoxy-zetan-sinter, and m-aminophenylmethyldiethoxylate. Preferred among these compounds are 3 - aminopropyl diethoxy calcination of a coating film which is excellent in acid resistance, and an aminophenyl bisphosphonate calcination, from the viewpoints of acid resistance and compatibility. Particularly preferred is 3-aminopropyltriethoxydecane. The monoamine containing hydrazine is preferably contained in an amount of from 300 parts by weight to 100 parts by weight based on 100 parts by weight of the total of the tetracarboxylic dianhydride, the diamine, and the polyvalent hydroxy compound. More preferably, it is 5 parts by weight to 200 parts by weight. 1-1-7. A solvent used in the synthesis reaction of the polyester phthalic acid to obtain a solvent used in the synthesis reaction of the polyester phthalic acid: diethylene glycol dioxime, two Ethylene glycol methyl ethyl ether, diethyldiethanol diethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxypropionic acid Ester, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, N-methyl-2-pyrrolidone, and hydrazine, hydrazine-dimercaptoacetamide. Preferred among the solvents are propylene glycol monoacetate acetate, 3-methoxy 15 201237098 41171pif decyl propionate, and diethylene glycol decyl ethyl ether. These solvents may be used singly or in combination of two or more kinds. Further, in the case of a ratio of 30 Wt ° /o or less, it is also possible to use a solvent other than the above solvent. 1-1-8. Method for synthesizing polyester proline acid The method for synthesizing polyester proline in the present invention can be used to make tetracarboxylic dianhydride X-mole, diamine Y-mole, and polyvalent hydroxy compound z. The moles are reacted in the above solvent. In this case, X, Y and Z are preferably determined such that the relationship between the following formulas (1) and (2) is established. When the content is in this range, the solubility of the polyester valine acid in the solvent is high, so that the coating property of the composition is improved, and as a result, a cured film excellent in flatness can be obtained. 0.2^Z/Y^8.0 ...... (1) 0.2^ (Υ+Ζ) /Χ^1.5 ...... (2) The relationship of (1) is preferably 0.7SZ/YS7.0, more preferably 1.3. SZ/YS7.0. Further, the relationship of the formula (2) is preferably 0.5S ( γ + Z) / Χ $ 〇 · 9, and more preferably 〇.7$ ( Υ + Ζ ) / Χ $ 〇 · 8. When the polyester glutamic acid used in the present invention has an acid anhydride group at the molecular terminal, the above-mentioned monohydric alcohol may be added as needed to carry out the reaction. The polyester phthalic acid obtained by the reaction of adding a monohydric alcohol can improve the compatibility with the epoxy resin and the epoxy hardener, and can improve the coating of the thermosetting resin composition of the invention containing the compounds. Cloth. Further, in the case where the above-mentioned monoamine containing Shixi and the polylysine having an acid group at the molecular end are reacted, the acid resistance of the obtained coating film is improved. Alternatively, the monohydric alcohol and the monoamine containing (iv) may be simultaneously reacted with poly_201237098 41171pif aminic acid. When the reaction solvent is used in an amount of 100 parts by weight or more based on 100 parts by weight of the total of the tetracarboxylic dianhydride, the diamine and the polyhydric hydroxy compound, the reaction proceeds smoothly. The reaction is preferably from 40 ° C to 200 ° C. (The reaction is carried out for 0.2 hours to 20 hours. When the reaction of the monoamine containing ruthenium is carried out, after the reaction of the tetracarboxylic dianhydride with the diamine and the polyvalent hydroxy compound is completed, the reaction solution is cooled to 40 ° C or lower. The reaction may be carried out at a temperature of 0.1 Torr to 40 ° C for 0.1 hour to 6 hours, and the monohydric alcohol may be added at any time point of the reaction. The order of addition in the system is not particularly limited. That is, 'the tetracarboxylic dianhydride and the diamine and the polyvalent hydroxy compound may be simultaneously added to the reaction solvent; after the diamine and the polyvalent hydroxy compound are dissolved in the reaction solvent' a tetracarboxylic dianhydride is added; after the tetracarboxylic dianhydride and the polyvalent hydroxy compound are reacted in advance, a diamine is added to the reaction product; or the tetracarboxylic dianhydride and the diamine are reacted in advance, and the reaction product is formed. Any method such as a polyvalent hydroxy compound is added. Preferably, the polyacetic acid which is synthesized in this manner comprises a structural unit composed of the general formula (3) and the general formula (4) whose end is derived from a raw material. Tetracarboxylic acid An acid anhydride group, an amine group or a hydroxyl group of a diamine or a polyvalent hydroxy compound or an additive other than the compound constitutes a terminal. In the formula (3) and the formula (4), R1 is a tetracarboxylic dianhydride. The residue is preferably an organic group having a carbon number of 2 to 30. R2 is a diamine residue, preferably an organic group having a carbon of 2 to 30. R3 is a residue of a polybasic compound, preferably It is an organic group having a carbon number of 2 to 20. 17 201237098 41171pif The weight average molecular weight of the obtained polyester glutamic acid is preferably 1, 〇〇〇 200,000, more preferably 3,000 50,000 to 50,000. In the present specification, the flatness and heat resistance are improved. The weight average molecular weight in the present specification is by gel permeation chromatography (GPC) method (column temperature is 35 ° C, flow rate is 1 ml/min) And the value of the polystyrene conversion is obtained. The standard polystyrene uses a polystyrene with a molecular weight of 645 to 132,900 (for example, VARIAN polystyrene calibration kit pL2〇1〇_〇1〇2), the column Using PLgel MIXED-D (VARIAN), the mobile phase was measured using tetrahydrofuran (THF). In addition, the weight average molecular weight of the commercially available product in the present specification is a catalogue value. 1-2. Epoxy Resin The epoxy resin used in the present invention can be obtained by shrinking with (mercapto) propylene glycolate The bifunctional (fluorenyl) acrylate is obtained by reacting the essential raw material components. Wei Guruo is not limited to the other components of the thermosetting resin composition of the invention.丙 缩 缩 甘 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ It is preferable that the epoxy resin of the silk and the lining has a high transparency of the film which is hardened by the hardening of the composition, and can suppress the decrease in the permeability in the step of the ultraviolet ozone treatment step m. In view of the flat dilute acidity, it is preferred that (mercapto) propyl hydrazine is contained in all monomers constituting the epoxy resin. 5〇201237098 4:ll71pif wt〇/〇 ~99 Wt%. = other free-filament-forming monomer, if a monofunctional (meth)acrylic acid vinegar is used, the heat-resistant and chemical-resistance of the cured film obtained from the thermosetting resin composition is insufficient, and if more than three functional groups are used, The functional thiol group is a bifunctional (meth) acrylate, since the flatness is insufficient and the compatibility with the polyester tyrosine is deteriorated. 2 preferred examples of the lyophilized (f-based) acrylate include: ethylene glycol diyl) acetoacetate, diethylene glycol bis(indenyl) propylene _, M_butanediol dipropylene @夂酉Day, 1,3 - butanediol di(indenyl) acrylate vinegar, neodecyl diol, dioxane dimethanol di(meth) acrylate. It is preferred that the poly(tetra)amine-phase of the transformer obtained by the reaction with the (meth)acrylic acid glycidol vinegar is good. From the viewpoints of flatness, heat resistance, and chemical resistance, it is preferably bifunctional; 2 acid is contained in all the monomers constituting the epoxy resin, and tw group is contained in the monomer. From the viewpoint of the characteristics of the radically polymerizable monomer as a raw material to form a monomer, it is preferred that such a == a monomer contains 0 wt. %~2G wt%. The mosquito free radical polymerization is obtained by reacting with (mercapto) acrylic acid glycidol vinegar = two, and the ring is obtained. The car is preferably 1,000 to 5 〇, 〇〇〇, more preferably 曰 20 , _. If the molecular weight is within these ranges, a charge of 'flat two 201237098 41171pif is obtained, and ten heat and chemical resistance are obtained. I'2'1. Solvent used in the synthesis of epoxy resin At least a solvent must be used in the synthesis of the epoxy resin. Specific examples of the solvent used in the polymerization reaction for obtaining an epoxy resin include: diethyl methylene glycol decyl ethyl ether, di-ethyl-ethyl ketone, and ethylene glycol mono-glycolic acid Ethylene glycol monoacetate acetate: propylene glycol monomethyl ether acetate, decyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, N-fluorenyl 2-pyrrolidone, and N,N-dimercaptoacetamide. Preferred among the solvents are propylene glycol monocarboxylic acid acetate, 3-methoxypropionic acid methylation, and diethylene glycol methyl ethyl sulphate. » Some solvents may be used alone or in combination of two or more. Further, in the case of a ratio of 3 Å by weight or less, other solvents than the above solvents may be used in combination. 1-2-2. Method for synthesizing epoxy resin The method for synthesizing the epoxy resin used in the present invention is not particularly limited, and is preferably a radical polymerization in a solution using a solvent. If the reaction solvent is used in an amount of 100 parts or more based on 1 part by weight of the total of (glycosyl) acrylate, difunctional (fluorenyl) acrylate, and other radical polymerizable monomers, the reaction is smooth. It is better to carry out the ground. The polymerization temperature is not particularly limited as long as it is a radical which sufficiently generates a radical by the polymerization initiator, and is usually not particularly limited, and is usually in the range of from 1 hour to 24 hours. Further, the polymerization can be carried out under any pressure of pressure, reduced pressure or atmospheric pressure. 201237098 41.171pif The synthesis of the coating 9 can be carried out using a known polymerization initiator. The poly: starting, a compound which generates a radical due to heat, an azo initiator such as azobisisodin, and a peroxide such as benzophenone benzoate are described as radical polymerization. In order to adjust the amount of the copolymer to be produced, a chain transfer agent such as thioglycolic acid may be suitably added. The epoxy resin used in the reduction of the money can be used to make the solvent (4) remaining in the shot, and the epoxy resin solution in consideration of operability and the like can be prepared. Solid shape epoxy resin. 1-3. Epoxy curing agent In the thermosetting resin composition of the present invention, an epoxy curing agent may be added in order to improve the quality of the material. Epoxy hardeners are used in the form of phthalic anhydride graders, _hard layers, chemicals, etc., from the aspects of coloring and stagnation resistance. In the case of "born considerations", preferred examples of the acid anhydride-based hard acid anhydride = a chemical agent include the following: aliphatic hexachlorophthalic anhydride, hexa LL acid: a neighboring ship needle, for example, a stupid Dicarboxylic anhydride, trimellitic anhydride, styrene, 2, anhydride copolymer. From the heat resistance and the solubility in the solvent, it is particularly preferable that the compound is a benzotriene and in the thermosetting resin composition of the present invention, the ratio of the polyglycine (10) by weight is relative. It is more preferable that the epoxy resin has a balance of 50 parts by weight of the epoxy resin and a good balance of the adhesion to the range of 300 parts by weight. For the purpose of improving the chemical properties and chemical resistance, epoxy hard m 2 + 5 times is added, and the method is added. This day, the temple, the sour needle soil "into the calculation. It is more preferable if the phthalic anhydride group or the wire is added in such a manner that it is in the form of Qi 5 equivalents to 〇·8 times equivalent. Other constituent materials of the thermosetting resin composition As the solvent used in the resin composition of the present invention, the compound used in the polymerization reaction in the case of synthesizing polylysine and epoxy resin can be used as it is. The solid content of the thermosetting resin composition can be selected according to the film thickness of the coating film, and is usually in the range of 5 parts by weight to 50 parts by weight based on 1 part by weight of the resin composition. Further, the amount of the solvent can be appropriately determined in association with problems such as the operation of the resin composition. Further, for example, a resin composition which is in a solid state by removing a solvent from the resin composition. The thermosetting resin composition of the present invention may contain other components than those described above as needed within the range not impairing the object of the present invention. Examples of such other components include a coupling agent, a surfactant, an antioxidant, a curing accelerator, a heat-sensitive acid generator, and the like. Moreover, in the case where the polyester proline does not contain styrene - 22 201237098 4ll71pif = = = = ?, a stupid ethylene male coupler may be added to improve the adhesion to the substrate, relative to the above heat. The solid content of the curable resin composition (removing the remaining component of the solvent from the fat) is added in an amount of 1 (). As the coupling agent, a compound of a decane type, an aluminum type, and a titanate type can be used. Specifically, Lu can be cited as: vinyl triclosan eve 6, ethylene trimethoxy smoldering, vinyl triethoxy wei, 2 - (3, 4-epoxycyclohexyl) ethyl trimethoxy Wei, 3. Glycidoxypropyl dimethyl ethoxy group, 3 _ glycidoxy propyl group? Di-diethoxy Wei, 3 • glycidoxypropyl triethoxy decane, 3 — glycidoxypropyl trimethoxy decane, aminopropyl trimethoxy decane, 3-aminopropyl a decane-based, ethoxylated alkoxy group such as a triethoxy decane, a 3-methyl propyl methoxy propyl tri methoxy wei, and a 3 fluorenyl (tetra) decyloxy bis-triethoxy decane An aluminum system such as aluminum diisopropoxide or a barium titanate such as tetraisopropyl bis(monooctyl linoleic acid) titanate. Among these coupling agents, 3-glycidoxypropyltrimethoxydecane is preferred because it has a large effect of improving the adhesion. The surfactant is used to increase the wettability, the homogenization property, or the applicability to the base substrate, and is added in an amount of 0.01 part by weight based on 100 parts by weight of the thermosetting resin composition. Such a surfactant may be exemplified by p〇lyfl〇W No. 45, Polyflow KL_245, Polyflow Νο·75, Polyflow Νο·90, Polyfl〇w N〇.95 (all of which are trade names, Gongrongshe Chemical Co., Ltd.) Company), Disperbyk 23 201237098 41171pif 161, Disperbyk 162, Disperbyk 163, Disperbyk 164, Disperbyk 166, Disperbyk 170, Disperbyk 180, Disperbyk 181, Disperbyk 182, BYK-300, BYK-306, BYK-310, BYK-320, BYK -330, BYK-344, BYK-346, BYK-UV3500, BYK-UV3570 (all of which are trade names, BYK-CHEMIE JAPAN KK·), KP-341, KP-358, KP-368, KF-96-50CS , KF-50-100CS (all of which are trade names, Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflon KH-40 (all of which are trade names, AGC Qingmei Chemical Co., Ltd.), Ftergent 222F, Ftergent 251 , FTX-218 (all of which are trade names, Neos Co., Ltd.), EFTOP EF-351 ' EFTOP EF-352 ' EFTOP EF-601 ' EFTOP EF-801, EFTOPEF-802 (all of which are trade names, Mitsubishi Materials) Co., Ltd.), Megafac F-410, Megafac F-430, Megafac F-444, Megafac F-472SF, Megafac F-475, Megafac F-477, Megafac F-552, Megafac F-553, Megafac F-554, Megafac F-555 > Megafac F-556 ' Megafac F-558 &gt Megafac R-94 ' Megafac RS-75, Megafac RS-72-K (all of which are trade names, DIC Corporation), TEGO Rad 2200N, TEGO Rad 2250N (all of which are trade names, Evonik Degussa Japan Co·, Ltd.) The surfactant used in the present invention may be one type of compound or a mixture of two or more types of compounds. The antioxidant is used to improve the transparency and prevent yellowing of the cured film when exposed to a high temperature, and 100 parts by weight of the solid matter of the thermosetting resin composition (after removing the solvent from the resin composition) Residue 24 201237098 retained knife) and g, added 〇. 1 part by weight to 5 parts by weight and used. As the antioxidant, a hindered amine system, a hindered phenol system or the like can be used. Specific examples include IRGAFOS XP40, IRGAFOS XP60, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, 1RGANOX 1520L (trade name; BASF Japan Co., Ltd.) and the like. The hardening accelerator is used to promote the reaction between the epoxy resin and the epoxy curing agent, and to improve the heat resistance and chemical resistance of the cured film, and the solid content of the thermosetting resin composition is 1 part by weight. The residual component after removing the solvent in the resin composition is added in an amount of 1 part by weight to 5 parts by weight. Any curing agent which has a function of promoting the reaction between the epoxy resin and the epoxy curing agent can be used as the curing accelerator, and examples thereof include an imidazole curing accelerator, a phosphine curing accelerator, and an ammonium hardening accelerator. A reagent, a Lewis acid hardening accelerator, and the like are exemplified. The heat-sensitive acid generator is capable of imparting sufficient hardness and chemical resistance to the cured film even if the heat-hardened knot-tree composition of the present invention is used under low-temperature hardening conditions of less than 2〇〇t>c. The composition of the thermosetting resin composition was used in an amount of 100 parts by weight (remaining component from the solvent in the surface of the surface), and GGG1 parts by weight to 3 parts by weight was added and used. Examples of the heat-sensitive acid generator include a salt of a town, a benzopyrene salt, a scale salt, and the like. Solitary 2. Hardened film obtained from thermosetting resin composition 2012 20129898 41171pif Weiyue's hot resin composition can be prepared by mixing poly-amine acid and oxynium tree sulphate, adding solvent and epoxy hardening according to the target characteristics. The agent, the coupling agent, and the surfactant == the agent, and the compounds are uniformly mixed and dissolved to obtain /L, and the thermosetting resin group prepared as described above is added to the solvent, and then dissolved in a solvent, such as When the solvent is removed by heating or the like, coating can be formed. The coating of the hot-wet tree test on the surface of the substrate can be formed by a conventional method such as a coating method, a dip plating method, and a slit method. Next, the coating film is heated by a hot plate or an oven or the like (pre-baked). The wire feeder varies depending on the surface and the proportion of each component, and is usually 7 〇C to 15 (at TC, if it is an oven, it is 5 minutes to 15 minutes, and if it is a heating plate, i minutes to 5 minutes). Thereafter, In order to harden the coating film, it is (10) C~25 (TC, preferably 2〇〇t~2 thief, if it is a flood box, it will be heated for 30 minutes~9〇 minutes, if it is a heating plate, then The heat treatment is performed for 5 minutes to 30 minutes, whereby a cured film can be obtained. ^When the cured film obtained is heated, 1) the polyamic acid of the polyester proline is partially dehydrated and cyclized to form a quinone bond. 2) Polyester phthalic acid carboxylic acid, ring, resin reaction and high molecular weight, and 3) epoxy resin hardening and high molecular weight, so it is very strong, and transparency, heat resistance, chemical resistance Excellent in flatness, adhesion, light resistance, and sputter. Therefore, the cured film of the present invention can be effectively used as a protective film for a color filter, and a color filter can be used to manufacture a liquid crystal display element or a solid-state imaging element. Moreover, the cured film of the present invention may be used as a transparent film for the color filter, and may be used as a transparent film formed by the TF T and the transparent electrode. The electric film is also effectively used as a protective film for an LED illuminator. In addition, the hardening of the present invention [example] is described in the following, and the present invention is not limited to the present invention. What is the age limit? /, First, synthesize the domain containing the four-in-one, two-in-one, and the compound in the way shown below.

]. Synthesis Example 2, Table 1). Wind 1 J

[Synthesis Example 1] Synthesis of polyester glutamic acid solution (Al) was placed in a four-necked flask of a .000 ml having a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet, and was charged with dehydrated purified 3-methoxypropane. Methyl ester (hereinafter referred to as "MMP") 446.96 g, l,4-butanediol 31.93 g, benzene f-alcohol 25.54 g, 3,3',4,4'-diphenyltetracarboxylic dianhydride (below Referred to as "ODPA") 183.20 g ', stirred under a dry nitrogen stream at 13 ° C for 3 hours. Then, 'cool the reaction solution to 25 ° C', put 3,3,-diaminodiphenyl hydrazine (hereinafter abbreviated as "DDS") 29.33 g, MMP 183.04 g, K2 (TC ~ 3 ° ° C stirring After 2 hours, the mixture was stirred at 115 ° C for 1 hour and cooled to 30 ° C or lower, thereby obtaining a 30 wt% solution (A1) of pale yellow transparent polyester lysine. The rotational viscosity of the solution was 28.5 mPa. · s. Moreover, the weight average molecular weight measured by GPC is 4,200 (in terms of polystyrene). Here, the rotational viscosity in this specification is an E-type viscosity meter (trade name: VISCONIC END, Tokyo Keiki Co., Ltd.) And the viscosity measured at 25 201237098 41171pif at 25 ° C. [Synthesis Example 2] Synthesis of polyester proline solution (A2) in a four-necked flask of 1000 ml with a thermometer, a stirrer, a raw material inlet and a nitrogen inlet. Dehydrated and purified propylene glycol monoterpene ether acetate (hereinafter referred to as "PGMEA") 504.00 g, ODPA 47.68 g, SMA1000P (trade name; styrene-maleic anhydride copolymer, Chuan crude oil chemical co., Ltd.) ) 144.97 g, phenyl decyl alcohol 55.40 g, 1,4-butanediol 9.23 g, dehydrated and purified diethylene glycol decyl ethyl ether (hereinafter referred to as "EDM") 96.32 g, and stirred under a dry nitrogen stream at 130 ° C for 3 hours. Thereafter, the reaction solution was cooled to 25 ° C. DDS 12.72 g and EDM 29.68 g were charged, and the mixture was stirred at 20 ° C to 30 ° C for 2 hours, and then stirred at 115 t for 1 hour, and cooled to 30 ° C or lower, thereby obtaining a pale yellow transparent polyester proline. 30 wt% solution (A2) The rotational viscosity of the solution was 36.2 mPa·s, and the weight average molecular weight measured by GPC was 21,000 (in terms of polystyrene) [Table 1] A1 (g) A2 (g Ingredient Material Tetracarboxylic Acid dianhydride ODPA 183.2 47.68 Diamine DDS 29.33 12.72 Polybasic compound 1,4-butanediol 31.93 9.23 1 hydroxyl octanol 25.54 55.40 Styrene-maleic anhydride copolymer SMA1000P 0 144.97 Solvent MMP 630.00 0 PGMEA 0 504.00 EDM 0 126.00 MMP : methyl 3-methoxypropionate ODPA : 3,3\4,4 匕diphenyl ether tetraphthalic acid dianhydride DDS : 3,3'-diaminodiphenyl基飒28 201237098 41171pif PGMEA : Propylene glycol monomethyl ether acetate SMA1000P: styrene_maleic anhydride copolymer Company) EDM: diethylene glycol decyl ethyl ether. Next, an epoxy resin solution containing a reaction product of glycidyl (meth)acrylate and a bifunctional (meth) acrylate is synthesized in the following manner. (Synthesis Example 3, Synthesis Example 4, Synthesis Example 5, Synthesis Example 6, Synthesis Example 7, Table 2). [Synthesis Example 3] Synthesis of epoxy resin solution (B1) In a four-necked flask of 000 ml having a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet, a dehydrated and purified MMP 300.00 g, glycidyl methacrylate was charged. (hereinafter referred to as "GMA") 18〇〇〇丨, 4_ Γdiol dimercapto acrylate 20.00 g, 2,2, _ dioxin (2,4-dimercaptocarbonitrile) as polymerization initiator 20.00 g, polymerization was carried out by heating at a polymerization temperature of 90 ° C for 2 hours. The 4 〇 w t% solution of the epoxy resin (B work) was obtained by cooling the reaction liquid to F. The weight average molecular weight of the solution as measured by Gp c was 12, 〇〇〇 (in terms of polystyrene). [Synthesis Example 4] Synthesis of epoxy resin solution (B2) in a four-necked flask having a thermometer, a stirrer, a raw material inlet, and a nitrogen introduction port, and a dehydration-purified MMP 300.00 g, 〇MA 180.00 g , 1>3 • Butanediol dimercapto acrylate 2, g, as a combination, 2, 2, azobis(2,4-dimercapto valeronitrile) 20.00 g, polymerization at 90 C, Heating was carried out for 2 hours at a temperature to carry out & The 4 〇 wt% solution (B2) of the epoxy resin was obtained by cooling the 29 201237098 41171 pif reaction solution to below 30 °C. The weight average molecular weight of the solution as measured by Gpc was 12.000 (in terms of polystyrene). [Synthesis Example 5] Synthesis of epoxy resin solution (B3) was placed in a 1000 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet, and was subjected to dehydration purification of mmp 300.00 g, GMA 180.00 g, and neopentane. 2 〇〇〇g of diol dimercapto acrylate, 2,2,-azobis(2,4-dimercapto valeronitrile) 20.00 § as a polymerization initiator, carried out at a polymerization temperature of 90 2 2 The polymerization was carried out by heating for an hour. The 4 〇 wt% solution (B3) of the epoxy resin was obtained by cooling the reaction liquid to below 30 °C. The weight average molecular weight measured by GPC of 5 hai bath was 11,000 (in terms of polystyrene). [Synthesis Example 6] Synthesis of epoxy resin solution (B4) In a 1000 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet, a dehydrated and purified MMP 300.00 g, GMA16d〇〇g, κ 4〇〇〇g of butanediol dimethacrylate, 30.00 g of 2,2,-azobis(2,4-dimercaptophthalonitrile) as a polymerization initiator, at a polymerization temperature of 90 C The polymerization was carried out by heating for 2 hours. A 4 wt% solution of the epoxy resin (B4) was obtained by cooling the reaction solution to 30 ° CW. The weight average molecular weight of the solution as determined by GPC was 18.000 (in terms of polystyrene). [Synthesis Example 7] Synthesis of epoxy resin solution (B5) MMP 300.00 g, 201237098 41171 pif GMA 180, 00, which was dehydrated and purified in a 1000 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet. g, 2, 2, aging initiator 2, 2, _ even! ^ = ? 基_赖2_g, dimethyl valeronitrile) 2〇.〇〇g at the polymerization temperature of the polymerization, and polymerization was carried out by heating the thief .A. A 40 wt% solution of epoxy resin (Β5) was obtained by reacting the reaction below. The weight average molecular weight measured by GPC was U, _ (polystyrene conversion).

GMA: glycidyl methacrylate MMP : 3 · methyl methoxypropionate [Table 2] B3 (g) Β 4 (g) B5 (g) 180 160 180 0 40 0 0 0 0 20 0 0 ίγ\π 20 20 jUU 30 20 11,000 18,000 11,000 Next, an epoxy resin solution containing a reaction product of glycidyl (meth) acrylate and monofunctional (fluorenyl) acrylate was synthesized by the following method (Comparative Synthesis Example) 1, Table 3). [Comparative Synthesis Example 1] Synthesis of epoxy resin solution (C1) in a four-necked flask of 000 ml having a thermometer, a stirrer, a raw material inlet, and a nitrogen introduction port + a dehydrated purified MMP 300.00 g, GMA 180.00 g, 20.00 g of decyl methacrylate, 8.00 g of 2,2,-azobis(2,4-dioxyl valeronitrile) as a polymerization initiator, heated at a polymerization temperature of 90 ° C for 2 hours. Perform polymerization. A 40 wt% solution (Cl) of an epoxy resin was obtained by cooling the reaction liquid to 31 201237098 41171 pif 30 ° C or less. The solution had a weight average molecular weight of 15,000 (polystyrene conversion) as determined by GPC. Next, an epoxy resin solution containing a reaction product of glycidyl (meth)acrylate and a bifunctional (meth) acrylate (weight average molecular weight: 20,000 or more) was synthesized by the following method (comparative synthesis example) 2, Table 3). [Comparative Synthesis Example 2] The synthesis of the epoxy resin solution (C2) was carried out in a four-point boiling of 1000 ml with a thermometer, a mixer, a raw material inlet, and a nitrogen inlet, and was loaded into a dehydrated and purified jyjMp 〇〇g, GMA. 180.00 g, 1,4-butanediol dimercapto acrylate, 2 〇〇〇g, 2,2,-azobis(2,4-dioxyl valeronitrile) 13 作为 as a polymerization initiator 〇g, polymerization was carried out by heating for 2 hours at 3 ° C. The epoxy solution (9) secret solution (ci) was obtained by cooling the liquid below the machine. The solution was determined by GPC to be 58,000 (聚聚乙驰算). Xia Shi knives ten miles is [Table 3]

MMP · 3-methoxypropionic acid methyl ketone 32 201237098 41171pif Next, using the polyester amide (S1, A2) obtained in Synthesis Example 1, Synthesis Example 2, Synthesis Example 3, Synthesis Example 4, Synthesis Example 5, Synthesis Example / Epoxy resin obtained in Synthesis Example 7 (Bl, B2, B3, B4, By, epoxy resin obtained in Synthesis Example 1 and Comparative Synthesis Example 2 (C1, ^ and commercially available polyfunctional and weight average) The cycloaliphatic resin having a molecular weight of less than 3 调制 is prepared as follows, and a thermosetting resin composition is prepared, and a cured film is obtained from the curable resin composition, and the cured film is evaluated. Example 6, Comparative Example 1, Comparative Example 2, Comparative Example 3, Table 4, and Table 7). ~ Table 6 [Example 1] A 500 ml separable flask equipped with a stirring blade was purged with nitrogen. The flask was charged with 1 〇〇g of the polyester phthalic acid solution (A1) obtained in Synthesis Example 1, and the epoxy resin solution (Βι) obtained in Synthesis Example 3, g, trimellitic anhydride 6 g, 3-shrinkage Glyceroxypropyltrimethoxysulfonium 4 8 g, IRGANOX 1010 (trade name; BASF Japan Co., Ltd.) 0.5〇g, dehydrated and purified MMP 160. 8 g, 5 hours at room temperature, 'mixed it' to dissolve evenly. Secondly, put BYK-344 (trade name, BYK-CHEMIE JAPAN KK) 0.42 g, stir at room temperature for f hours, borrow The coating liquid was prepared by filtration through a membrane filter having a pore size of 0.2 μm. 〜° Next, the coating liquid was spin-coated on a glass substrate and a shirt filter substrate at 800 rpm for 1 sec. On the hot plate, 8 Torr. The pre-baking was carried out for 3 minutes under the arm to form a coating film. Thereafter, heating was carried out in an oven at 23 (TC, 33, 2012, 098, 00, 41, 171, pif, for 3 minutes, thereby hardening the coating film. The film thickness is a cured film of 1 5%. 卜~ The cured film obtained in this way is evaluated for its transparency, light resistance, flatness, heat resistance, and chemical resistance. In Table 7. I. [Evaluation method of transparency] The obtained glass substrate A with a cured film was obtained by an ultraviolet visible near-infrared spectrophotometer (trade name: V. (4), Japan Optical Co., Ltd.) Determination of only the cured film at a wavelength of light of 4 〇〇 nm The transmittance is 97% or more. The less than 97% is X. [Evaluation method of light resistance] By ultraviolet ozone cleaning device (trade name: pL2003N_ i 2, the light source is a low-pressure mercury lamp) , SEN LIGHTS CG., Ltd., for the [Evaluation Method of Transparency], after the ultraviolet ray treatment of the glass substrate of the wei film with 3 I/em2 (2) 4 nm conversion, after UV penetration, it is visible by ultraviolet light. The near-infrared spectrophotometer (trade name: v_67〇, 曰本分光股份有限公司) was used to measure the transmittance of only the cured film at a wavelength of light of 4 (8) nm. A case where the transmittance is 96% or more is taken as X in the case where 〇 = 96% is less than. [Evaluation method of flatness] The obtained color film substrate with a cured film was measured using a step, a surface roughness, and a fine shape measuring device (trade name: P-15, KLA TENCOR Co., Ltd.). The step of the surface of the cured film. The maximum value of the step difference between the R, G, and B elements of the black matrix of the packaged person 34 201237098 41l71pif (hereinafter referred to as the maximum step difference) is less than 〇·2 μιη, and the case of 〇2 μηη or more is taken as X. . Further, the color filter substrate used is a pigment dispersion color filter (hereinafter abbreviated as CF) using a resin black matrix having a maximum step difference of about 1.1 μm. ^ [Evaluation method of heat resistance] The obtained glass substrate with a cured film was placed at 25 Å. (: Next: After reheating for an hour, the film thickness before heating and the film thickness after heating were measured, and the residual film ratio was calculated by the following calculation formula. The case where the residual film ratio after heating was 95% or more was taken as 〇, the case where the residual film rate after heating is less than 95% is taken as x. Residual film rate = (film thickness after heating/film thickness before heating) xl 〇〇 [evaluation method of chemical resistance] a glass substrate having a cured film, which is subjected to an impregnation treatment at 60 ° C for 10 minutes in a 5 wt% sodium hydroxide aqueous solution (hereinafter referred to as

NaOH treatment) 'In a mixture containing 36% hydrochloric acid / 60% nitric acid / water = 40 / 20 / 40 (weight ratio), 50 ° C for 3 minutes of impregnation treatment (called acid treatment in the daytime) , in N-mercapto-2-° ratio D each. The crucible treatment (hereinafter referred to as NMP treatment;) was carried out at 50 ° C for 3 minutes, and then reheated at 2 3 〇 T for 1 hour. The residual film ratio after reheating and the transmittance after reheating were measured. The residual film ratio after reheating was 95% or more, and the transmittance at 400 nm after reheating was 95% or more. The case where the residual film ratio after reheating is less than 95% or the transmittance after reheating is less than 95% is taken as X. Remaining film rate after reheating == (film thickness after reheating / film 35 before reheating 2012 20129898 41171pif thick) ΧίΟΟ [Example 2] 500 ml of separable flask with stirring wings was purged with nitrogen, The flask was charged with 100 g of the polyester phthalic acid solution (A2) obtained in Synthesis Example 2, 150 g of the epoxy resin solution (B1) obtained in Synthesis Example 3, 6 g of trimellitic anhydride, and 3-glycidoxypropyl c. 4.8 g of methoxymethoxy decane, IRGANOX 1010 (trade name; BASF Japan Co., Ltd.) 50·50 g, dehydrated and purified MMP 160.8 g, and stirred at room temperature for 5 hours to uniformly dissolve. Next, 0.42 g of BYK-344 (trade name, BYK-CHEMIE JAPAN K.K,) was placed, and the mixture was allowed to stand at room temperature for an hour, and the coating liquid was prepared by transitioning through a film filter having a pore size of 0.2 Å. The same as Example 1 is the same as Saki, Nana: Chemical resistance _ price. (Example 3) In the same manner as in Example 1, except that the epoxy resin solution (Bj) was used, the transparency and chemical resistance were evaluated in the properties of ping. [Example 4] Changed to an epoxy resin solution (Β: method to prepare a coating liquid. Properties, light resistance, flatness ± ^. This is the result of the heat, and the result of the sweat price is shown in In addition to the epoxy resin solution (Β1), the coating liquid was prepared by the same method as the example! The coating liquid was prepared by the coating of the resin solution (Β3). 36 201237098 41171pif Xingbei 1st, J丄HT water bar everywhere-k The properties of %, flatness, orbitality, and chemical resistance were evaluated. The evaluation results of Λ4 are shown in Table 7 [Example 5] The epoxy resin solution (B1) was changed to a ring ^ In the same manner as in Example 1, except for the method liquid (B4)', the transparency, the light resistance, the coating liquid, and the chemical property were evaluated in the same manner as in Example 1. The flatness and the finernity were evaluated. The results of the evaluation of Λ4 are shown in Table 7. [Example 6] The epoxy resin solution (Β1) was changed to the same method (8) as in Example ,, and the transparency m was applied in the same manner as in Example 1. Cloth liquid. And characterization of chemical properties. _ L flat domain, heat resistance, medium. The results of the 3rd parity of a are shown in Table 7 [Comparative Example 1] The epoxy resin solution (8) was changed to the same. The same as Example 1 except for the cold liquid (C1), the transparency was the same as in Example 1. , resistance to coating liquid. And financial chemical riding evaluation. Will rail, heat resistance, medium. The results are shown in Table 7. [Comparative Example 2] The epoxy resin solution (Bi) was changed to rabbits. (4) Adding and sucking ((7), 37 7 201237098 41171pif » Similarly, transparency, light resistance, flatness, The enthusiasm of the scorpion. Aitit line characteristic evaluation. The evaluation results of these are shown in the table. [Comparative Example 3] For the 500 ml separable flask with Heiyi, nitrogen was placed in the bottle cap For example, the polymyginic acid solution (Al) obtained by the towel is 100g, polyfunctional and the weight average molecular weight is less than 3. The resin TECHM〇RE VG31G1L (trade name; 卩 leg, post) 6〇g, trimellitic acid gf 6g '3·glycidoxypropyltrimethoxy 4.8 g, IRGANOX 1〇1〇 (trade name; BASF Kun (10) share limited = division) 0.50 g, dehydrated purified MMP 25〇8 g, at room temperature 5 = Stirring at the time to make it dissolve evenly. Next, 0.42 g of byK_344 (trade name, BYK-CHEMIE JAPAN K.K.) was placed, stirred at room temperature for ^ hours, and filtered to obtain a coating liquid by a membrane filter having a pore size of 0.2 μm. -D〇 ^ In the same manner as in Example 1, the properties of transparency, light resistance, flatness, heat resistance and chemical resistance were evaluated. The evaluation results of these are shown in the table. , 7

38 201237098 41171pif [Table 5] Ingredient Material Example 4 (g) Example 5 (g) Example 6 (g) Polyester phthalic acid A1 100 100 100 Epoxy resin B3 150 B4 150 B5 150 Epoxy hardener 6 6 6 Coupler 3-GPMS 4.8 4.8 4.8 Antioxidant IRGANOX1010 0.50 0.50 0.50 Solvent MMP 160.8 160.8 160.8 Surfactant BYK-344 0.42 0.42 0.42 [Table 6] Component Materials Comparative Example 1 (g) Comparative Example 2 (g) Comparison Example 3 (g) Polyester phthalic acid A1 100 100 100 Epoxy resin C1 150 C2 150 TECHMORE VG3101L 60 Epoxy hardener trimellitic anhydride 6 6 6 Coupler 3-GPMS 4.8 4.8 4.8 Antioxidant IRGANOX1010 0.50 0.50 0.50 Solvent MMP 160.8 160.8 160.8 Surfactant BYK-344 0.42 0.42 0.42 TECHMORE VG3101L : PRINTEC, INC. 3-GPMS : 3-glycidoxypropyl trimethoxy decane IRGANOX1010 : BASF Japan MMP : 3-methoxypropionic acid Oxime ester BYK-344 : BYK-CHEMIE JAPAN KK 39 201237098 41171pif [Table 7] Evaluation item 1 2 Example comparison example, transparency 〇0 ό 〇4 〇5 〇6 0 1 〇2 3 Pair of light flat Frank heat resistance 〇0 〇〇〇〇〇〇X 〇〇〇0 〇0 〇X 0 〇〇〇〇〇X 〇0 Chemical resistance 1—1~~~ 0 L" A 0 〇〇〇X 〇 〇1 ""I - According to the results shown in Table 7, the cured films of Examples 1 to ό are excellent in light resistance and flatness, and further in all aspects of transparency, heat resistance, and chemical resistance. Get balanced. On the other hand, in the comparative example 1, the cured film of the epoxy resin obtained by reacting glycidyl methacrylate with a monofunctional thiol acrylate has excellent light resistance and flatness, but heat resistance and chemical resistance. Poor sex. In Comparative Example 2, the cured film of the epoxy resin having an amount of 5 Å or more of 〇〇〇 (the epoxy resin obtained by reacting glycidyl methacrylate with a bifunctional methacrylate) was poor in flatness. . Further, in Comparative Example 3, the polyfunctional weight was used and the weight average molecular weight was less than 3, and the cured film of the epoxy resin of the ruthenium was inferior in light resistance. As described above, all of the cases are satisfied when the epoxy resin (weight average molecular weight is 1,000 to 50, 〇〇〇) obtained by reacting glycidyl methacrylate with a bifunctional methacrylate is used. characteristic. [Industrial Applicability] The cured film obtained by the thermosetting resin composition of the present invention is excellent in transparency, light resistance, sputtering resistance, and the like as an optical material, and is considered to be excellent in this respect. It is used as a protective film for various optical materials such as color filters, LED light-emitting elements, and light-receiving elements, and a transparent insulating film formed between a TFT and a transparent electrode and between a transparent electrode and an alignment film. 201237098 41171pif 】 No. [Main component symbol description] 〇 〇»>

Claims (1)

201237098 41171pif VII. Patent Application Range: 1. A thermosetting resin composition which is a resin composition comprising a polyester phthalic acid, an epoxy resin, and an epoxy hardener, characterized in that a polyester lysine It is obtained by reacting a tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound as essential raw material components, and by making X Moer's four diacids, dioxane, gamma molar diamine, and z mo Polyester phthalic acid obtained by reacting a polyvalent hydroxy compound of the ear with a ratio of the following formula (1) and formula (2), 0.2SZ/YS8.0 (1) 0.2^ (Y + Z) /X^1.5 (2) The epoxy resin is obtained by reacting glycidyl (meth) acrylate with a bifunctional (meth) acrylate as a necessary raw material component to obtain a weight average molecular weight of 1 , 〇〇〇~5〇, 环氧树脂 epoxy resin, relative to 100 parts by weight of polyester lysine, epoxy resin is 20 parts by weight to 400 parts by weight 'relative to epoxy resin 1 〇〇 weight The epoxy hardener is -60 parts by weight in parts by weight. 2. The thermosetting resin composition according to claim 1, wherein the polyester phthalic acid is required by using a tetracarboxylic dianhydride, a diamine, a polyvalent hydroxy compound, and a monohydric alcohol. The reaction product obtained by the reaction of the broad component is carried out. The thermosetting resin composition according to claim 2, wherein the monohydric alcohol is selected from the group consisting of isopropyl hydrazine, acryl alcohol, benzoquinone, and mercapto acrylate. One or more kinds of propylene glycol monoethyl amide and 3-ethyl·3_ mercaptomethyl epoxide. The thermosetting resin composition according to any one of claims 1 to 3, wherein the polyester phthalic acid is further added with a styrene-maleic anhydride copolymer. A polyglycolic acid obtained by a reaction as a raw material component. 5. The thermosetting resin composition according to any one of claims 1 to 3, wherein the polyester phthalic acid has the following general formula (3) and formula (4) The structural unit represented; 〇II -C 0 ϋ:—N: η—r (3) Η HOOC COOH Ο Ο (4) -0—II II , —c, ^C—Ο—R3- HOOC COOH Here, R1 is a tetracarboxylic dianhydride residue R2 is a diamine residue 'R3 is a residue of a polyvalent hydroxy compound. 6. The thermosetting resin composition according to any one of claims 1 to 3, wherein the polyester glutamic acid has a weight average molecular weight of 1,000 to 200,000. 7. The thermosetting resin composition according to any one of claims 1 to 3, wherein the four acid-lowering needles are selected from the group consisting of 3, 3', 4, 4, - Phenyl sulfone tetraphthalic acid dianhydride, 3,3,,4,4,-diphenyl ether tetraphthalic acid dianhydride, [bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride and ethylene One or more types of alcohol double (dehydration partiality 43 201237098 41171pif diester). Lin! ^Application for a patent, Item 1 to 3, and the composition of the hot benzene and 1 composition, wherein the diamine is selected from the group consisting of 3,3,-diaminodi-based wind and double One or more kinds of [4_(3·aminophenoxy)phenyl] are hard. 9. The scope of the patent application range i to 3 = the hard: r composition, wherein the multiple: = a drunk monol, 1,4-butanediol, 15 - Λ - Age 1 < 1 Hep or more of heptanediol and W octanediol. —b,···································酉 t t - alcohol mono (meth) acrylate, diethylene glycol bis (indenyl hydrazine, 1,4-butanediol di (meth) acid dilute vinegar, neopentyl glycol A, filament , Ding Yi drunk one (曱基), propyl (meth) propyl _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ In the above, the epoxy curing agent is one or more selected from the group consisting of heparan-acid liver and/or hydrogen-terminated tris. , the side of the item (4), the composition of the acid, the diamine is 3, the j, 3, 4, 4, _ diphenyl tetracarboxylic acid is 14_, ~ amine-based sulfone, The polyhydric hydroxyl group and the 14-V di-epoxy resin are the weight average of methyl methacrylate glycidyl acrylate = enoate or butanediol dimethyl endoic acid t00ZT00 1 as a solvent. -·Reading 'Step-in-containing 3-methoxypropionic acid formazan as 201237098 41171pif ^The thermosetting resin composition as described in claim 2 of the patent scope Ί 'The four lining gf is 3,3 , 4, 4, _ two stupid shouting tetracarboxylic acid liver: the diamine is 3,3,-diaminodiphenyl stone, the polybasic compound is 1,4-butanediol, The hydrazine alcohol is benzyl alcohol, and the ring: the weight average molecular weight of the f-based glycidic vinegar and the i, butanediol dimethacrylate or the 3-butanediol dimethacrylate is 丨, (9) 〇 A copolymer of two M),000, the epoxy hardener is trimellitic anhydride, and further contains decyl 3-methoxyoxypropionate as a solvent. A hardened film obtained by the thermosetting resin composition according to any one of the above claims. A color filter using the cured film as described in claim 14 of the patent application as a protective film. A liquid crystal display element using a color filter as described in the patent application. 17. A solid-state photographic element using a color filter as described in the scope of claim μ. 18. A liquid crystal display element using a cured film as described in the item [51] of the patent application as a transparent insulating film constituting a TFT between transparent electrodes. 19. A liquid crystal display element, which is used as in the patent application. The sclerosing film described in the item is used as a transparent insulating film for the reverse electrode. 20. An LED light-emitting body using the cured film as described in claim No. 1 as a protective film. 45 201237098 41171pif IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: None. 5. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: