TW201037006A - Thermosetting resin composition for forming protective film, protective film and method for forming protective film - Google Patents

Abstract

An object of the present invention is to provide a thermosetting resin composition capable of forming a protective film for display element having high evenness, moreover, good adherence, transparency and surface hardness on a substrate. A solution of the present invention is a thermosetting resin composition for forming protective film comprising [A] a copolymer formed by copolymerizing a monomer containing (a1) an epoxy group-containing compound and (a2) a unsaturated compound with radical polymerization ability and [B] at least one compound selected from multifunctional (meth)acrylate compound group modified with ethyleneoxide or propyleneoxide. As (a2) component, it is preferably selected from unsaturated carboxylic acid and unsaturated multivalent carboxylic acid anhydride; more preferably, it contains a polymeric unsaturated compound having acetal ester structure of carboxylic acid or 1-alkylcycloalkyl ester structure of carboxylic acid in a molecule.

Description

[Technical Field] The present invention relates to a curable resin composition for forming a protective film, a protective film formed of the composition, and a method for forming the protective film. More specifically, the present invention relates to a composition, a protective film formed from the composition thereof, and a method of forming the protective film. This composition is suitable as a material for forming a protective film for color filters for liquid crystal display elements (LCDs), color filters for charge-bonding elements (CCD), and touch panel displays.先前 [Prior Art] In the manufacturing steps of an element such as an LCD or a CCD, immersion treatment with a solvent, an acid or an alkali solution or the like is performed. Further, when the elements are formed by sputtering to form a wiring electrode layer, the surface of the element is partially exposed to a high temperature. Therefore, in order to prevent the element from being deteriorated or damaged by the immersion treatment or the high-temperature treatment caused by such a solvent or the like, the protective film is provided on the surface of the element to handle such problems. The protective film is required to have the following properties: the substrate or the lower layer on which the protective film is to be formed, and the layer formed on the protective film is highly adhesive; the film itself is smooth and strong; has transparency; heat resistance High, it will not cause coloring, yellowing, whitening and other deterioration during the long period; and excellent alkali resistance. Moreover, when such a protective film is used as a protective film for a color filter of a color liquid crystal display device or a charge-bonding element, in general, it is required to cause a height difference between the color filters formed on the substrate of the substrate. Flattener. For the material for forming a protective film that satisfies the above-mentioned properties, for example, a resin composition containing a polymer having an epoxy group of 201037006 is known (refer to Japanese Laid-Open Patent Publication No. Hei 5-78453 and Japanese Patent Application No. Hei. Bulletin No. 732). Furthermore, in a color liquid crystal display device, for example, STN (Super Twisted Nematic) mode or TFT (Thin Film)

In the color liquid crystal display device of the method of the present invention, in order to uniformly maintain the lattice gap of the liquid crystal layer, the bead-shaped spacer is spread on the protective film, and then the panel is bonded. The liquid crystal cell can be sealed by heat-pressing the sealing material after bonding the panel. Due to the heat and pressure during the heat pressing and sealing, 〇 a phenomenon in which the protective film in the portion where the bead spacer exists is observed, and an irregular situation in which the lattice gap is disordered is observed. In particular, in recent years, in order to improve the brightness of the panel, the pixels of the color filter are provided with openings in addition to the respective portions of red (R), green (G), and blue (B), and the opening portion is borrowed. It is planarized by a protective film formed from a resin composition. Since the width of such an opening is wide, an extremely high level difference flattening performance is required for the protective film. 〇 When forming such a protective film, it is desirable to use a resin composition which can form a protective film having excellent hardness in a simple manner. However, in order to form a strong cross-linking, when a compound having a reactive crosslinkable group or a resin composition containing a reaction-promoting high catalyst is used, there is a storage life of the resin composition itself (solution before hardening) The viscosity change stability over time) is a very short adverse situation. When the storage life of the resin composition is short, not only the coating performance of the resin composition deteriorates with time, but also the coating machine must be frequently maintained, washed, and the like. In the Japanese Laid-Open Patent Publication No. 2007-9 1 64, a curable resin composition is disclosed which uses a polymerizable unsaturated bond having ethylene oxide modification and/or propylene oxide modification. The compound (polyfunctional (meth) acrylate compound, etc.) has high developability and solubility, and when the pattern is formed, a column spacer which can form a sharp pattern without developing residue does not occur. However, in the publication of Japanese Laid-Open Patent Publication No. 2007-9164, the main purpose thereof is to impart hydrophilicity by modifying a compound having a polymerizable unsaturated bond with ethylene oxide modification and/or epoxy propylene modification. Further, improvement in developability is not disclosed for the use as a protective film or the improvement in properties such as adhesion to the substrate or flatness required for the protective film. Further, the curable resin composition of JP-A-2007-9164 is a photosensitive resin composition, and is not a thermosetting resin composition. Therefore, 'we strongly hope that we can develop the performance required to meet the general requirements of the protective film of the display element such as adhesion, flatness, transparency, etc., and hope that the protective film that can satisfy the required performance can be easily formed and preserved. A resin composition excellent in stability. CITATION LIST Patent Literature PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT The present invention has been made in view of the above circumstances, and an object thereof is to provide a thermosetting resin composition, a protective film formed of the composition thereof, and a method for forming a protective film thereof, which is even a color filter. A substrate having irregularities formed by a light sheet or the like, and a protective film for a display element can be suitably formed on the substrate, and the storage film is excellent in storage stability, and the flatness of the protective film for the display element is high (flattening performance) Moreover, it is excellent in adhesion, transparency, and surface hardness, and is excellent in various resistances, such as heat resistance, heat-resistant discoloration, and alkali resistance. In order to solve the problem, the present invention relates to a thermosetting resin composition for forming a protective film for a display element, comprising [A] containing (al) an epoxy group-containing unsaturated compound, and (a2) having a copolymer obtained by copolymerizing a monomer of a radically polymerizable unsaturated compound, and [B] at least one selected from the group consisting of the following formulas (1), (2) and (3). 201037006 R - ^-fxlrY is called (1)

CHz-^-X^-Y Y—X ^~HiC-C-CHa-^* XCHz"fxirY (2)

CH2*{-X^Y

4xtY-C-HaC-Z-H*c-C-CHa+X (3) CHz

C«Y (4)

• O——C——HN O (5).

O 〇 [In the formulae (1) to (3), 'R represents a C 1 to 20 alkyl group; X represents an epoxy group or a propylene oxide group; and Y groups each independently represent a hydrogen atom, a propylene group Any one of methacrylic fluorenyl groups, and at least two of the molecules are acryloyl or methacryl fluorenyl; η is an integer of 1 to 4; and Z is a formula (4) or (5) In the formula, m in the formula (5) is an integer of 1 to 12]. The polymorphism of the singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the sulphide And tree·', physical and chemical polymerization|combination heat ^^ The structure is made. 201037006 Excellent adhesion, transparency and surface hardness, heat resistance, heat discoloration, alkali resistance, etc. Storage stability. The U2) component in the thermosetting resin composition is more preferably at least one selected from the group consisting of a free-selective unsaturated carboxylic acid and an unsaturated polyvalent carboxylic acid anhydride. By using these compounds, the copolymerization reactivity can be improved when the component [A] is formed, and the heat resistance and surface hardness of the protective film formed of the thermosetting resin composition can be improved. More preferably, the U2) component in the thermosetting resin composition contains a polymerizable unsaturated unsaturated compound having a structure selected from the group consisting of acetal esters of carboxylic acids and carboxylic acids. At least one structure of the group consisting of an alkanecycloalkyl ester structure and a ternary butyl ester structure of a carboxylic acid. By using such a compound, the copolymerization reactivity at the time of forming the component [A] is improved, and the storage stability of the thermosetting resin composition can be improved. The thermosetting resin composition may further contain a [C] hardener. As a result, by containing the curing agent, the heat resistance and surface hardness of the protective film formed of the composition composed of the thermosetting resin can be improved. The thermosetting resin composition may be a combination of (1) a first component containing the [A] copolymer and the [B] compound, and (2) a two-component curing type containing the second component of the [C] curing agent. In this manner, the second component containing the curing agent of the [C] component is separated from the first component containing the components [A] and [B] to form a two-liquid hardening type composition, and the composition can be formed. High surface hardness protective film. More preferably, the thermosetting resin composition contains [D] a polyfunctional epoxy compound (except for the above [A] component). By using a polyfunctional epoxy compound having such a sensible heat exchange 201037006, the crosslinking reactivity of the thermosetting resin group can be improved, and the surface hardness of the film formed by the thermosetting resin composition can be further improved and relative to Adhesion of the substrate. The thermosetting resin composition preferably further contains a polyfunctional (meth) acrylate compound having one or more carboxyl groups in E, and a polyfunctional (methic acid ester compound) having one or more carboxyl groups in the molecule. The adhesion of the 0 film formed by the thermosetting resin composition to the substrate can be further improved. The step of heat-treating the film by using the thermosetting resin composition can form a display element. In this way, the film can be easily applied to the substrate in the liquid crystal display device. Further, the protective film thus formed has high flatness, adhesion, and surface hardness, heat resistance, heat discoloration resistance, and resistance. In the above, the protective film-forming resin composition of the display element of the present invention can be formed on a substrate even if it is formed as a color filter or the like. The protective film for the display element has a storage stability, and the flatness of the protective film for the display element is high. In addition to adhesion, transparency, and surface hardness, there is resistance. It is excellent in various resistances such as heat, color, and alkali resistance. Moreover, by using a composition of a thermosetting resin, it is easy to form such a protective film excellent in various properties. The molecular weight of the product is obtained by s) Propylene step and film. In the heat-resistant resin composition for forming a protective film of the display device of the present invention, the heat-resistant resin composition for forming a display element of the present invention contains: A] copolymer, [B] polyfunctional (meth) acrylate compound, and other optional components ([C] hardener, [〇] polyfunctional epoxy compound, [E] polyfunctional group having more than one carboxyl group (Meth) acrylate compound, etc.). Here, each component is explained as follows. ^ [A] component: a copolymer of the copolymer [A] component is polymerized by a monomer containing (ai) an epoxy group-containing unsaturated compound and (a2) a radical polymerizable unsaturated compound. The copolymer produced in the step. The epoxy group-containing unsaturated compound of the (al) component constituting the copolymer of the component (A) is not particularly limited as long as it has an epoxy group and is a polymerizable unsaturated bond. The (a 1) component may, for example, be a glycidyl (meth)acrylate, a glycidyl ethacrylate, a cyclopropyloxypropyl α-n-propyl acrylate or a glycidyl α-n-butyl acrylate. , (meth)acrylic acid-3,4-epoxybutyl acrylate, α-ethyl acrylate-3, 4-epoxybutyl acrylate, (meth)acrylic acid-6,7-epoxyheptyl ester, α-ethyl -6,7-epoxyheptyl acrylate, p-vinylbenzyl epoxidized propyl ether, 3-methyl-3-(methyl) propylene oxiranoxymethyl oxetane, 3-ethyl-3-( Methyl) propylene oxime methyl oxetane and the like. Among the epoxy group-containing unsaturated compounds, the reactivity at the time of forming a copolymer is high, and the heat resistance and surface hardness of the protective film formed of the thermosetting resin composition are excellent. Use methacrylic acid ring-11- 201037006 oxypropyl acrylate, methacrylic acid-6,7-epoxyheptyl ester, p-vinylbenzyl epoxidized propyl ether, 3-methyl-3-(methyl) propylene decyloxy Methyl oxetane, ethyl 3-(methyl) propylene methoxymethyl oxetane, and the like. The compound of the component (a 1) may be used singly or in combination of two or more. In the copolymer of the [Α] component, the content of the constituent unit derived from the (al) component is preferably from 10 to 90% by mass, particularly preferably from 20 to 80% by mass. When the content of the constituent unit derived from the (al) component is from 10 to 90% by mass, the heat-resistant, surface hardness, and alkali resistance of the protective film formed of the thermosetting resin composition 0 are excellent. The unsaturated polymerizable unsaturated compound constituting the U2) component of the copolymer of the component [A] is not particularly limited as long as it is a compound having an unsaturated bond which causes chain-radical polymerization. The component of U2) may, for example, be an unsaturated carboxylic acid, an unsaturated polyvalent carboxylic anhydride, a linear alkyl (meth)acrylate, a branched alkyl chain (meth)acrylate or a (meth) acrylate ring. An alkyl ester, a (meth) acrylate having a hydroxyl group, an aryl (meth) acrylate, an unsaturated dicarboxylic acid diester, a bicyclic unsaturated compound, a maleimide compound, a vinyl aromatic compound, A conjugated diene; a polymerizable unsaturated compound having a acetal structure of a carboxylic acid, a 1-alkalkane structure of a carboxylic acid, or a tertiary butyl ester structure of a carboxylic acid. Specific examples of the unsaturated carboxylic acid include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, ethacrylic acid, n-propylacrylic acid, and ct-n-butylacrylic acid; maleic acid and fubutene; Diacid, citraconic acid, 2-propenyloxyethyl succinic acid, 2-methylpropenyloxyethyl succinic acid, 2-propenyl oxiranyl hexahydrophthalic acid, 2-methylpropenyl oxirane Hexahydrophthalic acid, etc. -12-201037006 Dicarboxylic acid, and the like. Specific examples of the unsaturated polyvalent carboxylic acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and cis-1,2,3,4tetrahydrophthalic anhydride. Specific examples of the linear alkyl (meth)acrylate may, for example, be methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate or n-butyl (meth)acrylate. An ester, n-lauryl (meth)acrylate, tridecyl (meth)acrylate, n-stearyl methacrylate or the like. Specific examples of the (meth)acrylic acid branched chain 0-alkyl ester include, for example, (meth)acrylic acid secondary butyl ester and (meth)acrylic acid isodecyl ester. Specific examples of the (meth) acrylate cycloalkyl ester include cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, and 2-methylcyclohexyl (meth)acrylate. Tricyclo[5·2·1·02·6]decane-8 ester of (meth)acrylic acid (hereinafter referred to as tricyclo[5.2.1.0''6]nonane-8-yl is "dicyclopentyl". ), 2-dicyclopentyloxyethyl (meth)acrylate, isomeric (meth)acrylate, and the like. The (meth) acrylate having a hydroxyl group may, for example, be 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth) acrylate or 3-hydroxypropyl (meth) acrylate. , (meth)acrylic acid-2,3-dihydroxypropyl ester, and the like. Specific examples of the (meth)acrylic acid aryl ester may, for example, be phenyl (meth)acrylate or benzyl (meth)acrylate. Specific examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, diethyl itaconate and the like. Specific examples of the bicyclic unsaturated compound may, for example, be bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1] Hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, -13- 201037006 5,6-monomethoxybicyclo[ 2.2.1] Geng·2-ene, 5,6-diethoxybicyclo[2.2.1]heptane-2-refining, 5-tri-n-butoxycarbonylbicyclo[22.^hept-epene, 5_cyclohexene Oxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-di(tri-butoxycarbon)bicyclo[2.2.1]g 2-ene, 5,6-di(cyclohexyloxycarbonyl)bicyclo[2.2.1] hept-2-y, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2_- via B Bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1] 0 heptene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2- Alkene, 5-hydroxymethyl-5-methylbicyclo[2·2·1]hept-2-ene, and the like. Specific examples of the maleimide compound include N-phenyl maleimide, N-benzyl maleimide, and N-cyclohexylbutylene. Amine, N-succinimide-3-oxenimide benzoate, N-succinimide-4-butylimide butyrate, and the like. Specific examples of the vinyl aromatic compound include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene. The conjugated diene may, for example, be 1,3-butadiene, isoprene or 2,3-dimethyl-1,3-butadiene. Specific examples of the polymerizable unsaturated compound having a acetal structure of a carboxylic acid may, for example, be 1-ethoxyethyl (meth)acrylate or tetrahydro-2-indole-pyran-2-(meth)acrylate. 1-(cyclohexyloxy)ethyl (meth)acrylate, 1-(2-methylpropoxy)ethyl (meth)acrylate, 1-(1,1-dimethyl)(meth)acrylate Ethoxy)ethyl ester, 1-(cyclohexyloxy)ethyl (meth)acrylate, and the like. -14-201037006 Specific examples of the polymerizable unsaturated compound having an alkylcycloalkyl ester structure of a carboxylic acid may, for example, be 1-methylcyclopropyl (meth)acrylate or 1-methylcyclo(meth)acrylate. Butyl ester, 1-methylcyclopentyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, 1-methylcycloheptyl (meth)acrylate, 1-B (meth)acrylate Cyclopropyl ester, 1-ethylcyclobutyl (meth)acrylate, 1-ethylcyclopentyl (meth)acrylate, 1-ethylcyclohexyl (meth)acrylate, (meth)acrylic acid 1 - Ethyl cyclooctyl ester and the like. Further, specific examples of the 0 polymerizable unsaturated compound having a tertiary butyl ester structure of a residual acid may, for example, be a tertiary butyl (meth)acrylate. Among these U2) components, especially acrylic acid, methacrylic acid, 2-propenyloxyethyl succinate, 2-methylpropenyl oxyethyl succinate, maleic anhydride, (meth)acrylic acid-2 - hydroxyethyl ester, 2-hydroxypropyl (meth)acrylate, methyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, N-phenyl maleimide, N-cyclohexylmethyleneimine, styrene, p-methoxystyrene, tricyclo[5.2.1.0''6]nonane-8 ester, 1-ethoxylated methacrylate Ethyl ester, butyl methacrylate, tetrahydro 2H-pyran-2- methacrylate, 1-(cyclohexyloxy)ethyl methacrylate, 1-(2-methylpropoxy methacrylate) Ethyl ester, 1-(1,1-dimethyl-ethoxy)ethyl methacrylate, 1-ethylcyclopentyl (meth)acrylate, 1-ethylcyclohexyl (meth)acrylate The ester is best. By using the U2) component of the compound, the copolymerization reactivity with respect to the ui) component can be improved, and the heat resistance and surface hardness of the protective film formed of the thermosetting resin composition can be improved. -15 - 201037006 The compound of the component (a2) may be used singly or in combination of two or more. In the copolymer of the component [A], the content ratio of the constituent unit derived from the component (a 2) is preferably from 5 to 90% by mass, particularly preferably from 10 to 80% by mass. When the content of the constituent unit derived from the component (U2) is 5 to 90% by mass, the copolymerization reactivity at the time of copolymer formation is improved, and the heat resistance of the protective film formed of the thermosetting resin composition can be improved. Surface hardness and storage stability. In particular, when the unsaturated carboxylic acid or the unsaturated carboxylic acid anhydride is used as the component of the component (U), the content of the constituent unit derived from the compound of the component [A] is preferably from 5 to 60% by mass. More preferably, it is 7 to 50% by mass, and particularly preferably 8 to 40% by mass. The heat resistance, surface hardness, and thermosetting of the protective film formed of the thermosetting resin composition can be made by setting the content of the constituent unit derived from the unsaturated carbonic acid or the unsaturated carboxylic acid to 5 to 60% by mass. The properties such as the storage stability of the resin composition are optimized at a higher level. Further, in the case of the U2) component, when a polymerizable unsaturated compound having a acetal structure of a carboxylic acid, a 1-alkylcycloalkanoate structure of carboxylic acid or a tertiary butyl ester structure of a carboxylic acid is used, the component [A] is used. In the copolymer, the content of the constituent units derived from the compounds is preferably from 5 to 60% by mass, more preferably from 7 to 50% by mass, particularly preferably from 8 to 40% by mass. By the content ratio of the constituent unit of the polymerizable unsaturated compound (5 to 60% by mass, the heat resistance and surface hardness of the protective film formed of the thermosetting resin composition can be maintained at a high level, The storage stability of the thermosetting resin composition is improved. -16- 201037006 Next, a polymerization method for producing a copolymer of the component [A] will be described. The copolymer of the component [A] can be used in a suitable solvent. In the presence of a radical polymerization initiator, a monomer containing the above U1) component and (a2) component is copolymerized and produced. The solvent used in the copolymerization reaction is preferably diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, acetate or the like. These solvents may be used singly or in combination of two or more. The radical polymerization initiator to be used in the copolymerization reaction is not particularly limited, and examples thereof include 2,2--azobisisobutyronitrile and 2,2^azobis-(2,4-dimethylvaleronitrile). , 2,2·-azobis-(4-methoxy-2,4-dimethylvaleronitrile), 4,4^azobis(4-cyanovaleric acid), dimethyl-2,2' An azo compound such as azobis(2-methylpropionate) or 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile). These radical polymerization initiators may be used singly or in combination of two or more. The copolymer of the component [A] has a weight average molecular weight (Mw) of polystyrene by gel permeation chromatography (GPC), preferably 2,000 to 100,000' or more preferably 5,000 to 50,000. By setting the weight average molecular weight of the copolymer to 2,000 to 1,000,000, the properties such as surface hardness and heat resistance of the protective film formed of the thermosetting resin composition can be maintained in a good state. [B] Component: The polyfunctional (meth) acrylate compound of the polyfunctional (meth) acrylate compound [B] is selected from the above formulas (1), (2), and (3) (and formula (4). And (5)) at least one of the groups of compounds shown. Since the thermosetting resin composition of the present invention contains the component [A] and the component [B] of -17-201037006, it is possible to form a protective film for a liquid crystal display device having high flatness and excellent adhesion. Specific examples of the compound represented by the formula (4) in the above formulas (1), (2) and (3) (and the formulas (4) and (5)) may, for example, be trimethylolpropane. Propylene oxide modified triacrylate (n=l), trimethylolpropane propylene oxide modified triacrylate (n = 2), trimethylolpropane ethylene oxide modified triacrylate (n = l) , trimethylolpropane ethylene oxide modified triacrylate (η = 2), trimethylolpropane neopentyl alcohol ethylene oxide modified tetraacrylate (η = 1), ethylene oxide modified four Pentaerythritol acrylate (η=1), ethylene oxide modified neopentyl glycol triacrylate (η = 3), ethylene oxide modified neopentyl glycol tetraacrylate (η = 9), Ethylene oxide modified dineopentaerythritol hexaacrylate (η = 12). As a commercial item of such a compound, Aronics Μ-310, Μ-320, Μ-321, M-350, M-3 60, and M-370 (manufactured by Toagosei Co., Ltd.) can be exemplified. ATM-4E, ATM-3 5E (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD DPEA-12, and RP-1040 (manufactured by Nippon Kayaku Co., Ltd.). In the above formulas (1), (2) and (3) (and formulas (4) and (5)), the compound wherein Z is a group represented by the formula (5) can have a linear alkyl group structure a compound having two isocyanate groups, having one or more hydroxyl groups, an epoxy group or a propylene oxide group in the molecule, and having three, four or five (meth) acryloxy groups. The compound is obtained by reaction. In the case of such a compound, a compound obtained by reacting a diisocyanate compound of diisocyanate such as 1,6-hexamethylene diisocyanate with a compound substituted with a hydroxyl group of Y of the above formula (2) may, for example, be mentioned. . More specifically, it is preferred to use hexadecylmethyl -18-201037006 1,6-diisocyanate, and one of Y in the above formula (2) is substituted with a hydroxyl group, and X is an oxiranyl group, η The compound obtained is the compound of 2. In the thermosetting resin composition, the polyfunctional (meth) acrylate compound of the [Β] component may be used singly or in combination of two or more. The use ratio of the [Β] component is preferably from 10 to 300 parts by mass, more preferably from 20 to 200 parts by mass, per 100 parts by mass of the copolymer of the [Α] component. In the thermosetting resin composition, a liquid crystal display element protective film which is excellent in both flatness and adhesion to a substrate can be obtained by using the [Β] component in such a ratio. [C] component: curing agent The curing agent which is the component [C] may be added to the thermosetting resin composition to improve the heat resistance and surface hardness of the formed protective film. Further, the curing agent of the component [C] is a second component (second liquid) different from the first component (first liquid) containing the above-mentioned [Α] and [Β] components and other optional components, and may be A thermosetting resin composition as a two-liquid curing type is used. In this way, the second component containing the curing agent is separated from the first component of the thermosetting resin composition to form a two-liquid curing type composition, and the surface can be obtained while improving the storage convenience of the composition. A harder protective film. When the curing agent of the component [C] is used as the second liquid, the curing agent can be stored in a general organic solvent and stored. Examples of the curing agent of the component (C) include a copolymer of a polymerizable unsaturated compound having an acid anhydride group and an olefinic unsaturated compound (except for a copolymer of a component), a polyvalent carboxylic acid anhydride, and the like. -19-201037006 The polymerizable unsaturated compound having an acid anhydride group may, for example, be anaconic anhydride, citraconic anhydride, maleic anhydride or cis-1,2,3,4-tetrahydrophthalic anhydride. Further, examples of the olefinic unsaturated compound include styrene, p-methylstyrene, p-methoxystyrene, methyl methacrylate, butyl methacrylate, and trimethyl methacrylate [5, 2.1.02] 6] decane-8 ester, 2-methylcyclohexyl acrylate, phenyl maleimide, cyclohexene, and the like. The copolymer of the polymerizable unsaturated compound having an acid anhydride group and the olefinic unsaturated compound is preferably a maleic anhydride copolymer/styrene copolymer, citraconic anhydride/methacrylic acid tricyclic ring. [5.2.1.02 '6] decane-8 ester copolymer and the like. In the copolymerization reaction of the polymerizable unsaturated compound having an acid anhydride group and the olefinic unsaturated compound, the use ratio (mass ratio) of the two is preferably from 1:99 to 80:20, more preferably from 10:90 to 60:40. . By using the copolymerizable unsaturated compound having an acid anhydride group and the olefinic unsaturated compound in a ratio (mass ratio) of from 1:99 to 80:20, the formed copolymer is used as a hardener, and planarization properties can be obtained. Excellent protective film. Further, the copolymer of the polymerizable unsaturated group having an acid anhydride group and the olefinic unsaturated compound has a weight average molecular weight of converted polystyrene of preferably 500 to 50,000, more preferably 500 to 1 Torr. By using a copolymer having a weight average molecular weight in such a range as a curing agent, a protective film having high flatness can be obtained. Examples of the polyvalent carboxylic acid anhydride used as the curing agent include itaconic anhydride, succinic anhydride, citraconic anhydride, dodecene succinic anhydride, tricarballylic acid anhydride, maleic anhydride, and hexahydroanthracene. Anhydride, adipic dicarboxylic anhydride such as 201037006-based tetrahydrophthalic anhydride or himic anhydride; 1,2,3,4-butanetetracarboxylic dianhydride, cyclopentane tetracarboxylic acid An alicyclic polyvalent carboxylic acid dianhydride such as dianhydride; an aromatic polyvalent carboxylic acid like phthalic anhydride, pyromellitic anhydride, 1,2,4-benzenetricarboxylic anhydride, benzophenone tetracarboxylic anhydride, and hexahydrophthalic anhydride An acid anhydride; an acid anhydride-containing acid anhydride such as ethylene glycol trimellitic anhydride or glycerol (trimellitic anhydride). Among these polyvalent carboxylic anhydrides, a protective film having high heat resistance can be obtained, particularly an aromatic polyvalent carboxylic acid anhydride, particularly 1,2,4------- -------------

Benzoic anhydride and hexahydrophthalic anhydride are preferred. ________________ ----- In the thermosetting resin composition, the curing agent of the component [C] may be used singly or in combination of two or more. The use ratio of the curing agent of the component (C) is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less based on 100 parts by mass of the copolymer of the component [A]. By using the component (C) in a ratio of 30 parts by mass or less, the storage stability of the thermosetting resin composition can be maintained at a good level, and a protective film excellent in heat resistance and solvent resistance can be formed. 〇 [D] component: a polyfunctional epoxy compound of the polyfunctional epoxy compound [D], which improves the surface reactivity and improves the surface hardness of the protective film formed of the thermosetting resin composition while improving the crosslinking reactivity. The adhesion of the substrate can be added to the thermosetting resin composition. In the case of the polyfunctional epoxy compound, a cationically polymerizable compound having two or more epoxy groups in one molecule can be used (except for the above [A] component). -21- 201037006 A compound having two or more epoxy groups in the molecule can be exemplified by bisphenol A diglycidyl ether, bisphenol F diglycidyl ether bisphenol S diglycidyl ether, hydrogenation Polyglycidyl ethers of bisphenols such as bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether; 1,4·butanediol diepoxypropyl Ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, etc. Polyglycidyl ethers of polyvalent alcohols; aliphatic polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to an aliphatic polyvalent alcohol such as ethylene glycol, propylene glycol or 0 glycerol a compound having two or more 3,4-epoxycyclohexyl groups in a molecule; a phenolic novolac type epoxy resin such as a bisphenol A novolak type epoxy resin; a cresol novolac type epoxy resin; a polyphenol type Epoxy resin: cyclic aliphatic epoxy resin; di-glycidyl ester of aliphatic long-chain dibasic acid; glycidyl ester of higher fatty acid; epoxidized soybean oil, epoxidized Kernel oil. Among the compounds having two or more epoxy groups in the molecule, 'preferably a phenol novolak type epoxy resin and a polyphenol type epoxy resin. Specific examples of the compound having two or more 3,4-epoxycyclohexyl groups in the molecule can be exemplified by carboxylic acid 3,4-epoxycyclohexylmethyl_3', 4-epoxycyclohexyl ester, 2- (3,4-epoxycyclohexyl 5,5-helical-3,4-epoxy)cyclohexane-methyl-dioxane, bis(3,4-epoxycyclohexylmethyl) adipate , bis(3,4_epoxy-6-methylcyclohexylmethyl) adipate, carboxylic acid 3,4-epoxy 6-methylcyclohexyl_3·,4,_epoxy-6, -Methylcyclohexyl ester, methylene bis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol bis(3,4-epoxycyclohexylmethyl)ether , ethylene double-22- 201037006 (3,4-epoxycyclohexane carboxylate)' lactone modified carboxylic acid 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexyl ester Wait. In the case of a commercially available product having a compound having two or more epoxy groups in the molecule, the bisphenol A type epoxy resin can be exemplified by Epikote 1001, the same 1002, the same 1003, the same 1 004, the same 1007, the same 009, and the same. 1010, 828 (made by Nippon Epoxy Resin Co., Ltd.); bisphenol F type epoxy resin' can be exemplified by Epikote 807 (made by Nippon Epoxy Resin Co., Ltd.); phenolic novolac type 0 epoxy resin ( In terms of bisphenol A novolac type epoxy resin, etc., Epikote 152, 154, 157S65 (made by Nippon Epoxy Resin Co., Ltd.), EPPN201, and 202 (made by Nippon Kayaku Co., Ltd.); The phenolic novolac type epoxy resin can be exemplified by EOCN102, the same 103S, the same 104S, 1020, 1025, 1027 (manufactured by Nippon Kayaku Co., Ltd.), Epikote 180S75 (made by Nippon Epoxy Resin Co., Ltd.); Examples of the phenolic epoxy resin include Epikote 1032H60 and the same XY-4000 (manufactured by Nippon Epoxy Resin Co., Ltd.); and the cyclic aliphatic epoxy resin can be exemplified by CY-175, the same 177, and the same 179. , araldite CY-182, with 192, 184 (Ci Ba Special Chemicals Co., Ltd.), ERL-4234, 4299, 422 1, 4206 (U. C. C company), Showdyne 509 (made by Showa Denko Co., Ltd.), Epiclon 200, same 400 (made by Dainippon Ink Co., Ltd.), Epikote 871, 872 (made by Nippon Epoxy Resin Co., Ltd.), ED-5661 In the same manner as the 5662 (manufactured by Celanese Coating Co., Ltd.) and the aliphatic polyglycidyl ether, Epolight 100MF (manufactured by Kyoeisha Chemical Co., Ltd.) and EpiolTMP (manufactured by Nippon Oil & Fat Co., Ltd.) can be exemplified. -23- 201037006 The polyfunctional epoxide of the component [D] may be used singly or in combination of two or more kinds. The use ratio of the polyfunctional epoxy compound of the component [D] is preferably from 2 to 40 parts by mass, more preferably from 5 to 30 parts by mass, per 100 parts by mass of the copolymer of the component [A]. When the use ratio of the component [D] is 2 to 40 parts by mass, the surface hardness of the formed protective film and the adhesion to the substrate can be maintained while improving the crosslinking reactivity of the thermosetting resin composition. On the level of height. 0 [E] component: a polyfunctional methacrylate compound having one or more carboxyl groups in the molecule. In order to further improve the adhesion of the protective film formed of the thermosetting resin composition to the substrate, a molecule of the [E] component may be added. A polyfunctional (meth) acrylate compound having one or more carboxyl groups. The polyfunctional (meth) acrylate compound is not particularly limited as long as it is a compound having one or more carboxy groups in the molecule and having two or more (meth) acryl fluorenyl groups.多 A polyfunctional (meth) acrylate compound having one or more carboxyl groups in the molecule may have at least one compound having one or more acid anhydride groups in the molecule, and a hydroxyl group in the molecule and two or more (meth) groups. It is obtained by at least one reaction of a hydroxy group-containing hydroxyl group-containing (meth) acrylate. Specific examples of the compound having one or more acid anhydride groups in the molecule include succinic anhydride, 1-dodecene succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydroanthracene. Anhydride, methyl hexahydrophthalic anhydride, butyl maleic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, bridged ya-24- 201037006 methyl tetrahydrophthalic anhydride, methyl bridged methylene four a compound having one acid anhydride group such as hydroquinone anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, hydrazine or 2,4-benzenetricarboxylic anhydride: pyromellitic dianhydride, 3,3\4,4, benzophenone Tetracarboxylic dianhydride, 4,4·-biphthalic anhydride, 4,4′-side oxydiphthalic anhydride, 4,4′-(hexafluoroisopropylidene)diphthalic anhydride, 1,2,3,4 - cyclopentane tetracarboxylic dianhydride, 5-(2,5-di-oxo-tetrahydrofuranyl)-3-methyl-3.cyclohexyl-1,2-diresin anhydride, 4-(2,5- Bis-oxotetrahydrofuran-3-yl)-tetrahydronaphthalene·1,2-dicarboxylic anhydride, 3,4,9,10-nonanedicarboxylic acid bis-anhydride, bicyclo[2. 2. 2] A compound having two acid anhydride groups such as oct-7-ene-2,3,5,6-tetracarboxylic dianhydride. Among these, succinic anhydride is particularly preferred. Further, specific examples of the hydroxyl group-containing polyfunctional (meth) acrylate having a hydroxyl group and two or more (meth) acryloyl groups in the molecule include trimethylol acrylate and trishydroxy methacrylate. Methyl propyl ester, neopentyl glycol diacrylate, di neopentaerythritol triacrylate, di pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and the like. The polyfunctional (meth) 1 oxime acrylate compound having one or more carboxyl groups in the molecule of the [Ε] component may, for example, be a succinic acid mono-[3-(3-propene oxime) having a carboxyl group-containing 5-functional acrylate. Base-2,2-bis-propylene醯oxymethyl-propoxy)-2,2-bis-acrylomethoxymethyl-propyl]ester. In the thermosetting resin composition, the polyfunctional (meth) acrylate compound having one or more carboxyl groups in the molecule of the component (E) may be used singly or in combination of two or more. The use ratio of the component (E) is preferably from 30 to 200 parts by mass, more preferably from 50 to 150 parts by mass, per 100 parts by mass of the copolymer of the component [A]. By setting the use ratio of the component [E] to -25 to 201037006 30 to 200 parts by mass, storage stability, adhesion to the substrate to be formed of the protective film, and uniform thermal hardening at a height level can be obtained. Resin composition: [F] component: adhesion promoter In order to improve the adhesion between the formed protective film and the substrate, an adhesion aid of the component [F] may be added to the thermosetting resin composition. The adhesion aid is preferably a decane coupling agent having a reactive group such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group or an epoxy group. Specific examples of such a decane coupling agent include trimethoxy decyl benzoic acid, r-methyl propylene oxypropyl trimethoxy decane, ethylene triethoxy decane, ethylene trimethoxy decane, and r-isocyanate propyl. Triethoxyoxane, r-glycidoxypropyltrimethoxysilane, bis-(3,4-epoxycyclohexyl)ethyltrimethoxy-decane, and the like. In the thermosetting resin composition, the adhesion aid of the component [F] may be used singly or in combination of two or more. The amount of the adhesion aid of the component [F] in the thermosetting resin composition relative to 100 parts by mass of the copolymer of the component 1β [A] is preferably 0. 1 to 30 parts by mass, more preferably 1 to 25 parts by mass. The mixing amount of the adhesion aid of the component [F] is 0. When the amount is from 1 to 30 parts by mass, the heat resistance of the protective film formed of the thermosetting resin composition can be maintained at an extremely high level. Other optional components The thermosetting resin composition may be mixed with any of the components other than the above components, such as -26-201037006 surfactant, hardening accelerator, etc., as long as the effects of the present invention are not impaired. A surfactant may be added to improve the coating property of the thermosetting resin composition on the substrate. Further, a hardening accelerator may be used to further promote hardening of the thermosetting resin composition. A preferred example of such a surfactant is a fluorine-based surfactant, a polyoxyn surfactant, and the like. Examples of commercially available fluorine-based surfactants include BM-1000 and BM-1100 (manufactured by BMCH1M1D); Megafac F142D, Megafac F172, Megafac F173, Megafac F183, and Megafac R08-MH (Daily Ink Chemical Industry) Co., Ltd.); Fluorad FC-135 'Fluorad FC-170C 'Fluorad FC-430' Fluorad FC-431 (manufactured by Sumitomo 3M Co., Ltd.); Ftergent 250, 251, 222F, FTX-218 (Neos shares limited) Company system), Polyflow KL600, and KL800 (manufactured by Kyoeisha Chemical Co., Ltd.). Further, examples of commercially available polyfluorene-based surfactants include SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, and DC-190 (Toray· Dow Corning Co., Ltd.); KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); f-topDF301, f-top DF3 03, f-top DF3 5 2 (manufactured by New Akita Chemical Co., Ltd.). Further, as a commercial product of other surfactants, Polyflow No. of a (meth)acrylic copolymer may be mentioned. 57, Polyflow No. 90 (manufactured by Kyoeisha Chemical Co., Ltd.). The amount of the surfactant in the thermosetting resin composition is preferably 〇 with respect to 1 part by mass of the copolymer of the component [A]. 〇 1 to 5 parts by mass, more -27- 201037006 is 0. 05 to 3 parts by mass. The amount of surfactant mixed is 0. When it is 01 to 5 parts by mass, it is possible to suppress the occurrence of cracking of the surface film of the protective film formed of the thermosetting resin composition. The example of the curing accelerator is exemplified by 2_benzimidazole, 2'benzene-4-methylimidazole, 1-benzyl-2·benzimidazole, 2,4·diamino-6-[ 2′-methylimidazolium-(indenyl)]-ethyl-S-trimole, 2,4·diamino-6 -[ 2·-undecyl imidazolyl-(factory)]·ethyl-S-tripper, 2,4-diamino-6-[2,ethyl-4'-methylimidazolyl-11 Imidazolyl-(indenyl)]-ethyl-S-tripper, 2-phenyl-4,5-dihydroxymethylimidazole, and the like. The amount of the hardening accelerator in the thermosetting resin composition is usually 0% by mass based on 1 part by mass of the copolymer of the component [A]. 0001 to 10 parts by mass, more preferably 0. 001 to 1 part by mass. By setting the mixing amount of the hardening accelerator to 0. In the case of 0001 to 10 parts by mass, the thermosetting resin composition is cured, and the storage stability of the thermosetting resin composition and the heat resistance of the formed protective film are optimized. Solvent The thermosetting resin composition of the present invention is preferably prepared by dissolving or dispersing the above components in an appropriate solvent. The solvent used is preferably 'having a substance which is soluble or dispersible in the composition and which is not reactive with each component. The solvent is not particularly limited, and examples thereof include diethylene glycol dialkyl ether, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and propylene glycol monoalkyl ether acetate. Propylene glycol monoalkyl ether propionate, ketone, and the like. -28- 201037006 Specific examples of such solvents, in the case of diethylene glycol dialkyl ether, may be exemplified by diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, and the like; The ethylene glycol monoether ether acetate may, for example, be ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate; diethylene glycol monoalkyl ether The aspect of the acetate may, for example, be diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, or propylene glycol monoalkyl ether acetate. Examples of propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, etc.; propylene glycol monoalkyl ether propionate, propylene glycol monomethyl ether Propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate, etc.; and ketones, for example, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl- 2-pentanone, methyl isoamyl ketone, methyl-3-methoxypropionate, and the like. Among these solvents, diethylene glycol dialkyl ether, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and propylene glycol monoalkyl acetate are preferred. Further, in these examples, particularly preferred are diethylene glycol ethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate. , diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, methyl 3-methoxy propionate, and the like. In the thermosetting resin composition, the amount of the total solid matter in the composition (the amount of the solvent removed from the total amount of the solvent-containing composition) is preferably from 1 to 50% by mass, more preferably 5%. Up to 40% by mass. By setting the amount of the total solid matter at 1 to 50% by mass, the coating film property at the time of forming a coating film can be maintained in a good state. -29- 201037006 The above solvents and high boiling solvents can be used. The high-boiling solvent which can be used herein may, for example, be N-methylformamide, N,N-dimethylformamide, N-methyl-N-methylanilide or N-methylacetamidine. Amine, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl azine, benzyl ether, dihexanoic acid, acetone acetone, isophorone, hexanoic acid, octanoic acid, 7- Butyrolactone and the like. The amount of use in the case of using a high boiling point solvent is preferably from 1 to 40% by mass, more preferably from 3 to 30% by mass, based on the total amount of the solvent. By setting the use amount of the high-boiling solvent to the total solvent amount to 1 to 40% by mass, the coating film property at the time of forming a coating film can be further improved. The thermosetting resin composition prepared by adding a solvent may also preferably have a pore diameter of 0. 2 to 3. 0/zm or so, more preferably aperture 0. 2 to 0. A micropore filter of about 5 cm is filtered out and used. Formation of Protective Film Next, a method of forming a protective film on a substrate (a typical color filter substrate) using the thermosetting resin composition of the present invention will be described. The method for forming the protective film includes: (1) a step of applying a solution of a thermosetting resin composition on a surface of the substrate, (2) a step of removing the solvent by prebaking to form a coating film, and (3) having a heat treatment In the step of coating the film, a desired protective film can be formed on the substrate by the steps. Examples of the substrate which can be used include glass, quartz, chopped, resin, and the like. Specific examples of the resin may, for example, be agglomerated ethylene glycol vinegar, polypair 201037006 benzoic acid butyl acrylate butyl acrylate, polycarbonate, poly phthalimide, ring-opening polymer, hydrogenated product thereof, etc. A method of applying a thermosetting resin composition to a substrate is carried out by a spraying method, a roll coating method, a spin coating method, a bar coating method, or a spray method. For example, in the case of a coater, by using a spin coating spin coater or a slit die coater, it is possible to easily pre-bake the coating operation, and it is preferable to use 70 depending on the type or mixing of the components. The thickness of the left sheep coating film at 100 ° C for 1 to 15 minutes is preferably 0. 15 to 8. 5;tzm, better ί 6. 5/zm, especially good for 0. 15 to 4. 5/zm. Further, the thickness here is the thickness after removing the solvent. The heat treatment after the formation of the coating film can be carried out by a hot plate or a clean baking device. In terms of processing temperature, it is preferably 1503 right, and in terms of heating time, if a hot plate is used, it is 5 to 30, and when a clean oven is used, it is about 30 to 90 minutes. 1 θ In addition to the above-described prebaking and heat treatment after forming a coating film, the step is subjected to secondary heat treatment. The secondary heating temperature is compared. Up to 25 (about TC, the heating device can be used in the same way as above, and a suitable device such as a net oven is used. Moreover, the heating time at this time is also 5. . About 30 minutes, if you use a clean oven, it will take about 90 minutes. Protective film The surface of the cyclic olefin can be applied to the machine such as the ink method. The ratio is equal to the condition of ί. Special 0. 15 to the furnace of the coating film, etc. Appropriate € 2 50 °C Zuo Buzhong, you can also enter one: good for 150 ° hot plate, dry if used heat, also 3 0 -31- 201037006 so formed protection The film preferably has a film thickness of from 〇1 to more preferably 0. 1 to 6#m, more preferably 0. 1 to the other 'when the protective film is formed on the substrate having the height difference of the color filter', the film thickness is the thickness of the uppermost portion of the color filter. The protective film formed of the thermosetting resin composition of the present invention is also apparent from the following examples, and has excellent properties such as adhesion to the substrate, surface hardness, transparency, heat resistance, light resistance, and solvent resistance. In order to be excellent at the same time, even if there is no depression due to the load in the heat state, the performance of flattening the height difference of the color filter formed on the substrate of the substrate is excellent. Therefore, this protective film is extremely suitable as a protective film for display elements. EXAMPLES The present invention will be specifically described by way of exemplary synthesis examples and examples, but the present invention is not limited to the following examples. The weight average molecular weight (Mw) and the number average molecular weight (??) of the copolymer obtained in each of the following Synthesis Examples were measured by gel permeation chromatography (GPC) by the following method. Device: GPC-101 (made by Showa Denko Co., Ltd.) Column: A combination of GPC-KF-801, GPC-KF-802, GPC-KF-803, and GPC-KF-804 (made by Showa Denko Co., Ltd.) . Mobile phase: containing phosphoric acid 0. Synthesis Example of 5% by mass of tetrahydrofuran [A] copolymer 201037006 In a flask equipped with a cooling tube and a stirrer, 5 parts by mass of 2,21-azobisisobutyronitrile and 200 mg of diethylene glycol methyl ethyl ether were placed. Share. Next, 50 parts by mass of glycidyl methacrylate and 50 parts by mass of styrene were placed, and after nitrogen substitution, rapid stirring was started. After heating to a solution temperature of 70 ° C, the polymer solution containing the copolymer (A-1) was obtained by maintaining the temperature for 5 hours. The solid solution concentration of the obtained polymer solution was 33. 1% by mass (herein, "solid content concentration j means the ratio of the mass of the polymer in the polymer solution to the total mass of the solution (the same applies hereinafter)). The number average molecular weight (?n) of the obtained polymer is 5,000, The molecular weight distribution (Mw/Mn) was 2. [Synthesis Example 2] 5 parts by mass of 2,2·-azobisisobutyronitrile and diethylene glycol methyl ethyl ether 200 were placed in a flask equipped with a cooling tube and a stirrer. Then, 70 parts by mass of 3-ethyl-3-methylpropenyloxymethyloxetane and 30 parts by mass of styrene were placed, and after nitrogen substitution, rapid stirring was started. Heating to the solution temperature At 70 ° C, the polymer solution containing the copolymer (α·2) / was obtained by maintaining the temperature for 5 hours. The solid solution concentration of the obtained polymer solution was 3 2. 8% by mass. The obtained polymer had a number average molecular weight (??) of 6,000 and a molecular weight distribution (Mw/Mn) of 2. [Synthesis Example 3] 5 parts by mass of 2,2·-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol methyl ethyl ether were placed in a flask equipped with a cooling tube and a stirrer. * Next, 30 parts by mass of glycidyl methacrylate, 1 part by mass of styrene, 30 parts by mass of methacrylic acid, and 3 parts by mass of N-cyclohexylmethyleneimine, -33 - 201037006 parts, Rapid stirring was started after substitution with nitrogen. After heating to a solution temperature of 70 ° C, the polymer solution containing the copolymer (A-3) was obtained by maintaining the temperature for 5 hours. The solid solution concentration of the obtained polymer solution was 33 · 2 mass%. The obtained polymer had a number average molecular weight (??) of 7,300 and a molecular weight distribution (Mw/Mn) of 2. [Synthesis Example 4] 5 parts by mass of 2,2--azobis(2,4-G-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol methyl ethyl ether were placed in a flask equipped with a cooling tube and a stirrer. . Next, 30 parts by mass of glycidyl methacrylate, 1 part by mass of styrene, 30 parts by mass of tetrahydro-2H-piperidin-2-yl methacrylate, and a tricyclic ring were placed. 2. 1. 30 parts by mass of decane-8-yl methacrylate was rapidly stirred after being substituted by nitrogen. After heating to a solution temperature of 70 ° C, the polymer solution containing the copolymer (A-4) was obtained by maintaining the temperature for 5 hours. The solid solution concentration of the obtained polymer solution was 33. 2% by mass. The obtained polymer had a number average molecular weight (??) of 6,800 and a molecular weight distribution (Mw/Mn) of 2.合成 [Synthesis Example 5] 5 parts by mass of 2,21· azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol methyl ethyl ether were placed in a flask equipped with a cooling tube and a stirrer . Next, 30 parts by mass of glycidyl methacrylate, 1 part by mass of styrene, 30 parts by mass of ethyl ethyl pentyl methacrylate, and tricyclomethyline [5. 2. 1. 02'6] 30 parts by mass of decane-8-ester, which was rapidly stirred after being substituted by nitrogen. After heating to a solution temperature of 70 ° C, the polymer solution containing the copolymer (A-5) was obtained by maintaining the temperature for 5 hours. The solid solution of the obtained polymer solution -34- 201037006 has a concentration of 33. 0% by mass. The obtained polymer had a number average molecular weight (Mn) of 7,200 and a molecular weight distribution (Mw/Mn) of 2. [Synthesis Example 6] 5 parts by mass of 2,2,-azobis(2,4-dimethylacetonitrile) and 2 parts by mass of diethylene glycol methyl ethyl ether were placed in a flask equipped with a cooling tube and a stirrer. . Next, 30 parts by mass of methyl acrylate acid propylene glycol vinegar, 10 parts by mass of methacrylic acid, 10 parts by mass of styrene, 1 乙基 ethyl cyclopentyl methacrylate 2 〇 mass fraction and N - 30 parts by mass of cyclohexyl cis-butane diimide was rapidly stirred after being replaced by nitrogen. The polymer solution containing the copolymer (A-6) was obtained by heating to a solution temperature of 70 X: by maintaining the temperature for 5 hours. The solid solution concentration of the obtained polymer solution was 33. 4% by mass. The obtained polymer had a number average molecular weight (??) of 7,800 and a molecular weight distribution (Mw/Mn) of 2. [Synthesis Example 7] In a flask equipped with a cooling tube and a stirrer, 5 parts by mass of 2,2·-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol methyl ethyl ether were placed. Next, > 30 parts by mass of glycidyl methacrylate, 1 part by mass of methyl propyl succinic acid, 10 parts by mass of styrene, 20 parts by mass of butyl methacrylate, and N-cyclohexyl cis-butyl 30 parts by mass of eneimine was rapidly stirred after being substituted by nitrogen. After heating to a solution temperature of 70 ° C, the polymer solution containing the copolymer (A-7) was obtained by maintaining the temperature for 5 hours. The solid solution concentration of the obtained polymer solution was 33. 4% by mass. The obtained polymer had a number average molecular weight (??) of 7,500 and a molecular weight distribution (Mw/Mn) of 2. Preparation of thermosetting resin composition and formation of protective film - 35 - 201037006 '[Example 1] A solution containing copolymer (A-1) obtained in Synthesis Example 1 (corresponding to copolymer (Al) 100 mass (B-1) a trimethylolpropane propylene oxide-modified triacrylate (n=l) of a (B-1) polyfunctional (meth) acrylate compound (manufactured by Toagosei Co., Ltd.) "Aronics M-310") 40 parts by mass, (C-1) hardener benzoic anhydride 10 parts by mass, (D-1) polyfunctional epoxy compound novolac type epoxy resin (Japanese epoxy resin limited stock) 0"Epikote 152" manufactured by the company) 20 parts by mass, (F) 5 parts by mass of γ-glycidoxypropyltrimethoxide in the adhesion aid, and propylene glycol monomethyl ether acetate is added to make the solid concentration After becoming 20% by mass, the aperture is 〇. The microporous filter of 5 μm was filtered to prepare a thermosetting resin composition. This thermosetting resin composition was applied onto a Si〇2-impregnated glass substrate using a spinner, and then prebaked on a hot plate at 80 ° C for 3 minutes to form a coating film. Next, the substrate on which the coating film was formed was heat-treated at 230 ° C for 30 minutes in a clean oven to form a film thickness of 2. A protective film of 0/zm (a Cr substrate was used in one of the adhesion tests described later, and a Si〇2 impregnated glass substrate on which a color filter was formed in the test for flattening energy). [Examples 2 to 20 and Comparative Examples 1 to 4] A thermosetting resin composition was prepared in the same manner as in Example 1 except that the types, amounts, and solid contents of the respective components were as described in Table 1. Next, a protective film was formed in the same manner as in Example 1 using the prepared thermosetting resin composition as described above. Physical Property Evaluation - 36 - 201037006 The physical properties of the protective films formed in Examples 1 to 20 and Comparative Examples 1 to 4 and the evaluation methods for the storage stability of the thermosetting resin composition are described below. (1) Evaluation of the transparency of the protective film Using a spectrophotometer (Doublebeam No. 50-20 manufactured by Hitachi, Ltd.), the substrate having the protective film as described above was measured for wavelength 400 in each of Examples and Comparative Examples. Light transmittance (%) to 800 nm. The transparent zero evaluation is shown in Table 1 as the minimum 透光 of the light transmittance (%) at a wavelength of 400 to 800 nm. When the enthalpy is 95% or more, the transparency of the protective film is good. (2) Evaluation of heat resistance of protective film (stability of film thickness during heating) For each of Examples and Comparative Examples, the substrate on which the protective film was formed was heated at 250 ° C for one hour in a clean oven, and before and after heating was measured. The film thickness of the protective film. The film thickness stability (%) calculated according to the following formula was evaluated as heat resistance, and is shown in Table 1. When the enthalpy is 95% or more, the heat resistance of the protective film is good.膜 Film thickness stability when heated = (film thickness after heating) / (film thickness before heating) X 100 (%) (3) Evaluation of heat discoloration resistance of protective film With respect to each of Examples and Comparative Examples, the method was formed as described above. The substrate having the protective film was heated at 250 ° C for one hour in a clean oven, and the light transmittance before and after heating was measured by the method described in (1) "Evaluation of transparency of protective film". The heat discoloration resistance (%) was calculated according to the following formula and is shown in Table 1. When the enthalpy is 5% or less, the heat-resistant discoloration property of the protective film is good. Heat-resistant discoloration = light transmittance before heating - light transmittance after heating (%) -37 - 201037006 (4) Measurement of pencil hardness (surface hardness) of protective film With respect to each of Examples and Comparative Examples, protection was formed as described above. The substrate of the film, by J1S K-5400-1990 8. 4. 1 Pencil scratch test The pencil hardness (surface hardness) of the protective film was measured, and the results are shown in Table 1. When the crucible is 3H or more than 3H, the surface hardness of the protective film is good. (5) Evaluation of the adhesion of the protective film With respect to each of the examples and the comparative examples, a pressure cooker test (120T: humidity: 100%, 4 hours) was carried out by forming a base plate having a protective film as described above. Carry out 〗 〖1S K-5400- 1 990. 5. 3 The crosscut taping method was used to obtain the number of chess discs remaining in one of the checkerboard eyes, and the evaluation of the adhesion of the protective film (adhesion to SiCh) is shown in Table 1. Further, the Cr substrate was used instead of the Si〇2 immersed glass substrate, and the above-mentioned checkerboard tape method was used to evaluate the adhesion to Cr. The results are shown in Table 1. (6) Evaluation of the flattening energy (flatness) of the protective film on the Si〇2-impregnated glass substrate using "JCR RED 689", "JCR GREEN 706" and "CR 8200B" manufactured by the pigment-based color resist USR Co., Ltd. 'As shown below, a strip-shaped color filter of three colors of red, green, and blue is formed. Namely, a color of the above-mentioned color resist was applied onto a Si〇2-impregnated glass substrate using a spinner, and prebaked on a hot plate at 90 ° C for 150 seconds to form a coating film. Thereafter, using the exposure machine Canon PLA501F (manufactured by Canon Co., Ltd.), the ghi line (intensity ratio of the wavelengths of 4 6 nm, 40511 111, and 35511111 = 2) was passed through a preset pattern mask. 7:2. 5:4. 8) Convert the 丨 line, illuminate at 2,000:[/1112 -38- 201037006, then use 0. The 05 mass% potassium hydroxide aqueous solution was developed and rinsed with ultrapure water for 60 seconds. Next, a monochromatic strip-shaped color filter was formed by further heat-treating at 230 ° C for 30 minutes in an oven. This operation is repeated by three colors each time to form strip-shaped color filters of three colors of red, green, and blue (bar width 200 " m). The measurement is 2,000 μm long, the measurement range is 2,000 μm, the measurement direction is the short-axis direction of the stripe line in the red, green, and blue directions, and the long-axis of the stripe line of the same color of red, red, green, green, and 0 blue and blue. In the two directions of the direction, the number of measurement points n = 5 (the total number of η is 10) is measured in each direction, and the color film measuring device ("α-step" manufactured by KLA-Tencor Co., Ltd.) is used to measure the color furnace film. When the surface of the substrate is uneven, it is Ι. Ομιη. After coating various thermosetting resin compositions on the substrate on which the color filter is formed by a spinner, prebaking on a hot plate at 90 ° C for 5 minutes to form a coating film, and further in a clean oven In the middle, the post-baking is performed at 230 ° C for 60 minutes, and the film thickness formed from the color filter is about 2. 0#m protective film.基板 The surface of the protective film formed on the color filter thus formed was measured for the surface unevenness of the protective film by a contact-type film thickness measuring device ("α-step" manufactured by KLA-Tencor Co., Ltd.). This measurement is to measure the 2,000 μm length, the measurement range of 2,000 μm, the direction of the short-axis direction of the stripe line in the red, green, and blue directions, and the stripe line of the same color of red, red, green, blue, and blue. In the two directions in the long axis direction, the direction is measured by the number of measurement points n = 5 (the total number of η is 10), and the average of 10 times the height difference (nm) between the highest part and the bottom part of each measurement is obtained. The flattening performance (flatness) of the protective film is evaluated in -1 - 201037006 and the price is shown in Table 1. When the ruthenium is 200 nm or less, the planarization performance of the protective film is good. (8) Evaluation of alkali resistance of the protective film (film thickness stability during alkali immersion) For each of the examples and the comparative examples, the substrate having the protective film formed as described above was immersed in 30 ° C, 5% NaOH for 30 minutes. The film thickness after removing the water by the hot plate was measured. The film thickness stability (%) at the time of alkali immersion was calculated according to the following formula, and the alkali resistance evaluation is shown in Table 1. When the enthalpy is 95% or more, the alkali resistance is good. Alkali resistance = (film thickness after moisture removal) / (film thickness before immersion) x 100 (%) (7) Evaluation of storage stability of thermosetting resin composition using a viscometer ("Tokyo Keiki Co., Ltd." The ELD type viscometer ") measures the viscosity of the thermosetting resin composition in 25t. Thereafter, the composition was allowed to stand at 25 ° C while measuring the viscosity at 25 ° C every 24 hours. Based on the viscosity of the thermosetting resin composition immediately after preparation, the number of days required for 5% tackification was determined, and the number of turns was used as the storage stability 〇 evaluation, and is shown in Table 1. When the number of days is 15 days or more, the storage stability of the thermosetting resin composition is good. Further, in Table 1, (B) a polyfunctional (meth) acrylate compound, (C) a curing agent, (D) a polyfunctional epoxy compound, and (E) a polyfunctional group having one or more carboxyl groups in the molecule (A) (Acrylate) compound, (F) adhesion aid, (G) unmodified (meth) acrylate compound (modified without ethylene oxide or propylene oxide) and (meth)acrylic acid having no carboxyl group The abbreviations of the ester compounds are each as follows. -4U- 201037006 Bl : Trimethylolpropane propylene oxide modified triacrylate (n = l) ("Aronics M-310" manufactured by Toagosei Co., Ltd.) Β·2: Trimethylolpropane propylene oxide modified three Acrylate (n = 2) ("Aronics M-320" manufactured by Toagosei Co., Ltd.) Β·3: Trimethylolpropane oxirane modified triacrylate (η=ι) (manufactured by Toagosei Co., Ltd.) "Aronics M-350") B-4: Ethylene oxide modified neopentyl glycol tetraacrylate (n=l) ("ATM-4E" manufactured by Shin-Nakamura Chemical Co., Ltd.) B-5: Ring Ethylene oxide modified neopentyl glycol tetraacrylate (n = 9) (ATM-35E) manufactured by Shin-Nakamura Chemical Co., Ltd.) B-6: Ethylene oxide modified dineopentaerythritol hexaacrylate (n=12) (KAYARAD DPEA-12j, manufactured by Sakamoto Chemical Co., Ltd.) B-7: 1,1-hexamethylene diisocyanate and one of Y in the above formula (2) A compound obtained by reacting a compound having a hydroxyl group, X is an oxirane group, and η is 2 ί C-1 : 1,2,4,-benzenetricarboxylic anhydride D-1 : a phenol novolak type epoxy resin (Japanese ring) Oxygen Resin Co., Ltd. "Epikote 152") D-2: bisphenol A novolac type epoxy resin ("Epikote 157S65" manufactured by Nippon Epoxy Co., Ltd.) E-1: succinic acid mono-[3-( 3·Acetyloxy-2,2-bis-acrylomethoxymethyl·propoxy)-2,2-bis-propylene醯oxymethyl-propyl]ester-41 - 201037006 Fi: r-epoxy Propoxypropyltrimethoxydecane G-1: Trimethylolpropane Triacrylate (Aronics M-309, manufactured by Toagosei Co., Ltd.) G-2: Dipentaerythritol hexaacrylate (Nippon Chemical Co., Ltd.) Company KAYARAD DPHA")"

-42- ❹ ο )06 < 1 8 1 , t 1 1 1 1 1 I 1 < «ο 1 1 S: & m w-> s R 15^ 1 1 Comparative example cn > 1 8 1 1 ' i 1 1 1 t 1 1 1 1 1 « w-ί 1 1 冢ON 〇\ 忒cn S 8 8 cs 15^ CNJ t 1 8 1 H 1 1 1 1 1 • 1 1 幽1 f 1 1 1 \rt 1 8 On Os OO 〇\ s: m u-\ O ο § 15^ 8 1 1 1 1 1 1 1 1 1 - 1 • 1 1 r 1 1 Another 1 冢s CO K ms ο § 15^ Kun Mm S 1 1 1 t 1 8 1 1 1 1 1 1 1 1 1 S s lH \η 1 1 Os 〇On <7>s; CO K 8 8 § 30^ | On 1 • 1 1 8 1 1 1 s 1 1 1 1 1 S 1 ... 1 1 ON ON VO ON cn 8 S 30 ^ OO 1 1 1 1 1 8 1 1 1 1 1 t 1 1 1 S g wi 1 t OO Os sa cn wn 8 8 ο 30 S • 1 1 1 1 8 ^ 1 1 I 1 1 1 1 1 S sm 1 1 S OO Os VD 〇\ * {^> \n 8 s Product 30^ 1 1 1 1 1 8 tH 1 l 1 1 1 1 1 1 1 R s w-» • 1 〇\ Os & «ΓΛ K m 8 8 30 S 1 • 1 f 8 t 1 1 1 1 1 • 8 1 1 1 8 1 Vi 1 t OO ON CO 8 S ο <—Η 30 S 1 Responsibility 1 1 8 1 1 1 1 1 1 • 1 • S 1 1 Different ON ON CO ON s CO 8 8 1—^ § 30 S cn 1 1 1 t 8 1 1 ' • s 1 1 1 g U~V 1 1 ON as \〇ON cn ffi vr> 8 8 S 30芸1 1 1 8 1 VQ 1 1 ' 1 1 Another 1 ' vrj 1 Pan ON OS Os cn Write 8 No g, 30 helmet - 1 § 1 1 1 1 1 * 1 VQ « 1 VQ wi 1 〇\ as VO ON §: cn w> 8 8 s 15g o 1 • 8 1 1 1 1 1 8 1 1 1 1 Different W1 1 Pan ON ON VO ON 冢m CO 8 茬s rH i 15^ ON 1 1 8 1 1 • 1 tg 1 < 1 1 1 g yr\ 1 1 ON ON v-> ON g; CO ffi ir> 8 S g \15^ OO 1 1 8 1 1 1 1 This l < 1 1 S s 1 1 〇\ 〇\ 〇ON s CO K vn 8 ·—» 8 8 15^ Bu 1 I 8 t 1 1 1 1 沄1 1 • 1 1 1 1 〇\ ON ON ON s; CO S 8 8 纭15芸Ό 1 1 8 1 1 s 1 1 1 t 1 1 different m ( 1 ON ON Ό ON 冢CO ui 8 8 s T-H 15^ vr> 1 1 8 1 1 io 1 1 1 1 1 t 1 S 1 t vn 1 1 R 卺〇\ ON CO CO 8 § § 15 inches < 8 1—^ 1 t 1 1 s • 1 1 1 S 1 1 Wi 1 - OS OS ON ON ΓΛ X cn 8 »-H 8 ? 15^ 8 1 • 1 1 1 § 1 1 1 1 1 1 o SI 1 \r\ i S OS On vn ON 冢cn ffi vn s 冢o 15 ^ CS 8 1 1 i 1 1 1 1 t 1 1 t 11 v〇1 1 On ON Os 〇\ cn K 8 8 o 15^ A 8 1 « « 1 1 〇1 • t 1 1 1 o 1 W) 1 1 8 Ov Os o 〇\ cn K cn 8 8 g 5 A-2 cn < Wi <fc Ό <i < PQ <N CQ cn CQ t PQ CQ v〇ώ rp OQ 3 ά ΟΪ d ώ ώ 6 CS Solid concentration (%) Transparency (%) Heat resistance (%) Resistance to heat (%) Heat discoloration (% ) Hardness Si〇2 Flattening energy (nm) 1 Storage stability (day) (A) Component (B) Component 1 (c) Component I (D) Component (E) Component (F) Component (G) Component Sex

CO 201037006 It is understood from the results shown in Table 1 that the thermosetting resin compositions of Examples 1 to 20 of the present invention have not only flattening properties (flatness), adhesion, and composition compared with the compositions of Comparative Examples 1 to 4. The transparency and the surface hardness are excellent and excellent in balance, and a protective film having high heat resistance, heat discoloration resistance, and alkali resistance can be formed. In addition, it is known that a polymerizable unsaturated compound having a acetal structure of a carboxylic acid, a 1-alkane cycloester structure of a carboxylic acid, or a tertiary butyl ester structure of a carboxylic acid is used as a copolymer component. The thermosetting resin compositions of Examples 12 to 20 were particularly excellent in storage stability. Industrial Applicability The thermosetting resin composition of the present invention has high flatness, good adhesion, transparency, and surface hardness, and is excellent in various resistances such as heat resistance, heat discoloration resistance, and alkali resistance. The protective film is extremely suitable for use as a color filter for liquid crystal display elements (LCD), a color filter for charge-bonding elements (CCD), and a protective film for a touch panel display.

C Ming] said. The number of the object is a simple one. yuan. Fat type has no tree picture main 0 [ ί -44 -

Claims (1)

201037006 VII. Patent application scope: 1. A thermosetting resin composition for forming a protective film, comprising [A] containing (al) an epoxy group-containing unsaturated compound, and (a2) having radical polymerization property. a copolymer obtained by copolymerizing monomers of an unsaturated compound, and [B] at least one selected from the group consisting of compounds represented by the following formulas (1), (2) and (3): 〇 (5) :__c—c^-fx^v (1) —1—CH*+xtY (2) Wide fxirY Υ-^Χ^-ΗΛ — C—HtC—Z~HjC- CH*-fXtY " HxirY (3) CKHxirY [In the formulae (1) to (3), 'R represents a carbon number of 1 to 2 alkyl group; X represents an epoxy group or a propylene-based group: the Y system each independently represents a hydrogen atom, Any one of acrylonitrile or methacryl fluorenyl, and at least two of 丨 molecules -45 - 201037006 are acryl fluorenyl or methacryl fluorenyl; η is an integer from 1 to 4; Z is a formula (4) Or (5), m in the formula (5) is an integer of 1 to 12]. 2. The thermosetting resin composition for forming a protective film according to the first aspect of the invention, wherein the component (a2) contains at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated polyvalent carboxylic anhydrides. . 3. The thermosetting resin composition for forming a protective film according to the first aspect of the invention, wherein the component (a2) contains a 1-alkalane having a carboxylic acid acetal ester structure and a carboxylic acid. A polymerizable unsaturated compound having at least one structure of the group consisting of an ester structure and a ternary butyl ester of a carboxylic acid. 4. The thermosetting resin composition for forming a protective film according to the first aspect of the invention, further comprising a [C] curing agent. 5. The thermosetting resin composition for forming a protective film according to the first aspect of the invention, wherein the combination (1) contains the first component of the [A] copolymer and the [B] compound, and (2) contains [C] 〕 The second component of the hardener is a two-liquid hardening type. Q. The thermosetting resin group for forming a protective film according to the first aspect of the invention, which further comprises [D] a polyfunctional epoxy compound (except for the component [A] above). 7. The thermosetting resin composition for forming a protective film according to the first aspect of the invention, further comprising a polyfunctional (meth) acrylate compound having one or more carboxyl groups in the molecule [E]. A protective film of a display element, which is formed by the thermosetting resin composition according to any one of claims 1 to 7. A method of forming a protective film for a display element, comprising the step of forming a film by using a thermosetting resin composition according to any one of claims 1 to 7 of claim 46-201037006, and heat-treating the film A step of. Ο 201037006 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: and. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: