KR102005472B1 - Thermosetting resin composition - Google Patents

Abstract

The present invention includes a compound having a glycolluryl group together with a carboxyl group or a carboxylic acid anhydride group and a copolymer containing an epoxy group as a crosslinking agent to satisfy the properties required conventionally as a protective film and effectively improve the crosslinking density To a thermosetting resin composition which is excellent in mechanical properties and heat resistance and can provide a cured film free from yellowing at a high temperature.

Description

TECHNICAL FIELD The present invention relates to a thermosetting resin composition,

The present invention relates to a thermosetting resin composition, and relates to a thermosetting resin composition useful as a material for forming a protective film for an optical device.

When an optical device such as a liquid crystal display device is immersed in an organic solvent, an acid, an alkali solution or the like during the manufacturing process, or when a wiring electrode layer is formed, the surface is subjected to severe treatment such as local heating at a high temperature by sputtering. Therefore, in these devices, a protective film (Overcoat) may be provided on the surface thereof in order to prevent deterioration at the time of manufacturing.

The protective film is excellent in heat resistance and light fastness so that it can withstand the above-described treatments and is excellent in adhesion with the substrate or the under layer, has a high smoothness and surface hardness, is excellent in transparency and does not deteriorate over a long period of time such as coloration, yellowing, whitening, , Acid resistance, alkali resistance, and other chemical resistance and water resistance. Further, when such a protective film is applied to a color filter of a color liquid crystal display device, it is preferable that a step of an ordinary color filter can be flattened as a base substrate.

The protective film is a cured film of a curable resin composition, wherein the curable resin composition can be largely divided into a thermosetting property and a light curable property (photosensitive property). When a protective film pattern is required, a photosensitive resin composition is required. Otherwise, a thermosetting resin composition is used. This is because the thermosetting resin composition is convenient in the process in comparison with the photosensitive resin composition, can increase the crosslinking density, and is excellent in mechanical properties and heat resistance.

Examples of technologies relating to a protective film made of such a thermosetting resin composition include the techniques described in Japanese Patent Application Laid-Open Nos. 2000-103937, 2000-119472, and 2000-143772.

As an example of the thermosetting resin composition used for forming the protective film, a composition comprising an acrylic resin containing a carboxyl group or an epoxy group, a polyfunctional monomer containing an ethylenic unsaturated group serving as a crosslinking agent, and a thermal polymerization initiator is mainly used.

However, conventional thermosetting resin compositions having such a composition are not excellent in mechanical properties, and in many cases, exhibit yellowing due to poor heat resistance at high temperatures. In order to prevent such a phenomenon, a polyfunctional monomer containing an ethylenic unsaturated group may be used in excess, but such an excessive use has a problem of exacerbating yellowing at a high temperature.

The present invention relates to a thermosetting resin composition which satisfies the properties required conventionally as a protective film and which is excellent in mechanical properties and heat resistance by effectively improving the crosslinking density and is highly suitable as a material for forming a protective film for optical devices, .

(A2) an unsaturated compound containing an epoxy group; (a3) an olefinically unsaturated compound other than the above (a1) and (a2); and A copolymer of a compound; [B] A compound having a glycoluril group And a thermosetting resin composition.

In one embodiment of the present invention, the compound having the glycoluril group is any one or more selected from among compounds represented by the following formulas (1) to (6).

Formula 1

(2)

(3)

Formula 4

Formula 5

6

In another embodiment of the present invention, the compound having the glycoluril group is contained in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the copolymer [A].

In another embodiment of the present invention, the thermosetting resin composition may further comprise [C] a polymerizable compound having an ethylenically unsaturated bond and [D] a thermal radical polymerization initiator, wherein the [C] The polymerizable compound is contained in an amount of 0.1 to 150 parts by weight based on 100 parts by weight of the copolymer [A], and the thermal radical polymerization initiator [D] is contained in an amount of 0.1 to 20 parts by weight with respect to 100 parts by weight of the copolymer [A] do.

Another constitution of the present invention provides a cured film made of the above-mentioned thermosetting resin composition.

The thermosetting resin composition according to the present invention comprises a compound having a carboxyl group or a carboxylic acid anhydride group and a copolymer containing an epoxy group and having a glycoluril group serving as a crosslinking agent so that the cured film is a protective film which satisfies the properties At the same time, the cross-linking density is effectively improved to provide excellent mechanical properties and heat resistance, and there is no yellowing at high temperatures.

Hereinafter, the present invention will be described in more detail.

(A2) an epoxy group-containing unsaturated compound (hereinafter referred to as a compound (a2)), (a3) an epoxy group-containing unsaturated compound (hereinafter referred to as (a3) an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride a copolymer of an olefinically unsaturated compound other than (a1) and (a2) (hereinafter referred to as compound (a3)); [B] A compound having a glycoluril group To a thermosetting resin composition.

First, the copolymer [A] is obtained by a known polymerization method, that is, the compound (a1), the compound (a2) and the compound (a3) can be synthesized by radical polymerization in a solvent in the presence of a polymerization initiator.

The copolymer [A] may contain 5 to 40% by weight, preferably 10 to 30% by weight, of the compound (a1). This is because the heat resistance, chemical resistance, surface hardness, It is preferable in view of storage stability.

Examples of the compound (a1) include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; Or anhydrides of these dicarboxylic acids. Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used because they are excellent in copolymerization reactivity, heat resistance and availability. These compounds may be used alone or in combination.

The copolymer [A] may contain 10 to 70% by weight, preferably 20 to 60% by weight, of the compound (a2), considering the heat resistance and surface hardness of the resulting cured film, Which may be desirable.

Examples of the compound (a2) include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α- Acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, Heptyl, o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and the like, can be preferably used because they increase the heat resistance and hardness of the obtained protective film and the resulting protective film. These compounds may be used alone or in combination.

 The copolymer [A] may contain 10 to 70% by weight, preferably 20 to 50% by weight, of the compound (a3), which is preferable in view of the storage stability of the copolymer and the heat resistance and surface hardness of the cured film can do.

Examples of the compound (a3) include methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate and t-butyl methacrylate; Alkyl acrylate esters such as methyl acrylate and isopropyl acrylate; Methacrylic acid cycloalkyl esters such as cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate and isobornyl methacrylate; Acrylic acid cycloalkyl esters such as cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, and isobornyl acrylate; Methacrylic acid aryl esters such as methyl methacrylate, butyl methacrylate and benzyl methacrylate; Acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate; Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate; Hydroxyalkyl esters such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; And styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, Vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like. Of these, styrene, t-butyl methacrylate, dicyclopentenyl methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate and 1,3-butadiene may be preferable from the viewpoint of copolymerization reactivity and heat resistance . These compounds may be used alone or in combination.

Such a copolymer [A] has a carboxyl group or a carboxylic acid anhydride group and an epoxy group, and can be easily cured by heating even when a special curing agent is not used in combination.

Examples of the solvent usable for the synthesis of the copolymer [A] include alcohols such as methanol and ethanol; Ethers such as tetrahydrofuran, diethylene glycol dimethyl ether and diethylene glycol diethyl ether; And propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and propylene glycol butyl ether acetate.

As the polymerization initiator that can be used in the synthesis of the copolymer [A], those generally known as radical polymerization initiators can be used. Azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy- 4-dimethylvaleronitrile); Organic peroxides such as benzoyl peroxide, t-butyl peroxypivalate, and 1,1'-bis- (t-butylperoxy) cyclohexane; And hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, the peroxide may be used as a redox initiator together with a reducing agent.

The thermosetting resin composition of the present invention contains the compound [B] having a glycoluril group together with the copolymer [A], and the compound [B] having a glycoluril group can act as a curing agent for the copolymer [A] .

The compound having the glycoluril group is excellent in reactivity, and the cured film obtained therefrom can secure a higher curing density, and as a result, it is possible to prevent deterioration of heat resistance, UV resistance, and chemical resistance of the cured film.

The compound having such a glycoluril group is any one or more selected from compounds represented by the following general formulas (1) to (6).

Formula 1

(2)

(3)

Formula 4

Formula 5

6

The content of the compound [B] having the glycoluril group is 0.1 to 50 parts by weight, preferably 0.1 to 40 parts by weight, relative to 100 parts by weight of the copolymer [A], to form a cured film having a high crosslinking density, And a compound [B] having a glyuroryl group in the inside of the cured film can be prevented from remaining, thereby preventing the problem of unstable property of the cured film or deteriorating adhesiveness.

In another embodiment of the present invention, a polymerizable compound having an ethylenically unsaturated bond [hereinafter referred to as a polymerizable compound (C)] may be used in addition to the compound [A] and the compound having a glycoluril group [B] , And [D] a thermal radical polymerization initiator (hereinafter referred to as a thermal radical polymerization initiator [D]).

As the polymerizable compound [C], a monofunctional, bifunctional, or trifunctional or more functional (meth) acrylate may be preferable from the viewpoints of good polymerizability and improved heat resistance and surface hardness of the resulting cured film.

Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobonyl (meth) acrylate, 3-methoxybutyl (Meth) acryloyloxyethyl 2-hydroxypropyl phthalate, and the like.

Examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexanediol (meth) acrylate, 1,9-nonanediol (meth) (Meth) acrylate, tetraethylene glycol (meth) acrylate, and bisphenoxy ethyl alcohol fluorene diacrylate.

Examples of the (meth) acrylate having three or more functional groups include trishydroxy ethylisocyanurate tri (meth) acrylate, trimethyl propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol Tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

These monofunctional, bifunctional or trifunctional (meth) acrylates may be used alone or in combination.

When the polymerizable compound [C] is contained in the thermosetting resin composition, the content thereof is not more than 150 parts by weight, preferably not more than 120 parts by weight, more preferably 0.1 to 100 parts by weight based on 100 parts by weight of the copolymer [A] It may be advantageous from the viewpoint of the adhesion of the cured film.

Examples of the thermal radical polymerization initiator [D] include 2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis - (4-methoxy-2,4-dimethylvaleronitrile), and 1,1'-azobis-1-cyclohexylnitrile; Organic peroxides such as benzoyl peroxide, t-butyl peroxide, and 1,1'-bis- (t-butylperoxy) cyclohexane.

The content of the thermal radical polymerization initiator [D] is 20 parts by weight or less, preferably 15 parts by weight or less, more preferably 0.1 to 12 parts by weight based on 100 parts by weight of the copolymer [A] It can be advantageous from the side.

The thermosetting resin composition of the present invention is prepared by homogeneously mixing the respective components of the copolymer [A] and the compound [B] having a glycoluril group, and if necessary, the polymerizable compound [C] and the thermal radical polymerization initiator [D] can do. Usually, the thermosetting resin composition of the present invention is dissolved in a suitable solvent and used in a solution state. That is, the thermosetting resin composition is prepared by mixing the copolymer [A], the compound [B] having a glycoluril group, the polymerizable compound [C], the thermal radical polymerization initiator [D] It is prepared. The composition of the present invention must contain the copolymer [A] and the compound [B] having a glycoluril group.

As the solvent used for preparing the thermosetting resin composition of the present invention, the respective components of the copolymer [A], the compound having a glycoluril group [B], the polymerizable compound [C] and the thermal radical polymerization initiator [D] It is acceptable that it does not react with any one component. Specifically, for example, alcohols such as methanol and ethanol; Ethers such as tetrahydrofuran, diethylene glycol dimethyl ether and diethylene glycol diethyl ether; And propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and propylene glycol butyl ether acetate. Of these solvents, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and propylene glycol methyl ether acetate may be preferable in terms of solubility, reactivity with each component, and convenience of forming a coating film.

It is also possible to use a high boiling point solvent together with the above-mentioned solvent. Examples of the high boiling point solvent which can be used in combination include N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide , Benzyl ethyl ether and the like.

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.

The other component may be a surfactant for improving the coatability. Examples of the surfactant include fluorine and silicon surfactants such as FC-129, FC-170C and FC-430 of 3M, KP322, KP323, KP340 and KP341 of Shinetsu Silicones. Such a surfactant is preferably used in an amount of 5 parts by weight or less, preferably 2 parts by weight or less, more preferably 0.1 to 1.5 parts by weight based on 100 parts by weight of the copolymer [A]. This is because when the thermosetting resin composition is applied, It may be advantageous in terms of prevention.

The composition solution prepared as described above can be used after filtration using a filter having a pore size of about 0.1 to 5 mu m.

The desired protective film can be obtained by applying the thermosetting resin composition of the present invention to a base substrate and treating the film in an oven at 150 to 300 DEG C for 10 to 100 minutes.

Hereinafter, the present invention will be described in detail with reference to Examples, but it should be understood that the present invention is not limited to these Examples.

<Production Example>

In a reaction vessel equipped with a cooling tube and a stirrer, a monomer (20% by weight of styrene, 30% by weight of methacrylic acid, 40% by weight of glycidyl methacrylate, and dicyclopentenyloxyethyl methacrylate 10 weight%) 5 parts by weight of 2,2'-azobisisobutyronitrile as a polymerization initiator was dissolved in 200 parts by weight of diethylene glycol dimethyl ether as a solvent, based on 100 parts by weight of the total amount. Subsequent to nitrogen substitution, gentle stirring was begun.

The temperature of the solution was raised to 80 캜 and maintained at this temperature for 4 hours to obtain a polymer solution containing the copolymer [A-1]. The solid concentration of the obtained polymer solution was 33% by weight.

&Lt; Example 1 >

1] as a compound [B] having a glycoluril group based on 100 parts by weight (based on solid content) of the copolymer [A-1] obtained in the above Preparation Example and 100 parts by weight of the copolymer [A- 20 parts by weight of the compound and 0.1 part by weight of 3M Company FC-430 (fluorine surfactant) as a surfactant were dissolved in a mixed solvent of diethylene glycol dimethyl ether and N-methylpyrrolidone (weight ratio 80:20) 25% by weight. Thereafter, the solution was filtered through a filter having a pore diameter of 0.45 mu m to prepare a thermosetting resin composition solution (S-1).

&Lt; Example 2 >

(2) as a compound [B] having a glycoluril group based on 100 parts by weight (based on solid content) of the copolymer [A-1] obtained in the above Production Example and 100 parts by weight of the copolymer [A- 20 parts by weight of a compound and 0.1 part by weight of a surfactant, Shin-Etsu Silicone KP341 (silicone surfactant) were mixed and dissolved in a mixed solvent of diethylene glycol dimethyl ether and N-methylpyrrolidone (weight ratio 80:20) 25% by weight. Thereafter, the solution was filtered through a filter having a pore diameter of 0.45 mu m to prepare a thermosetting resin composition solution (S-2).

&Lt; Example 3 >

(3) as a compound [B] having a glycoluril group based on 100 parts by weight (based on solid content) of the copolymer [A-1] obtained in the above Production Example and 100 parts by weight of the copolymer [A- , 100 parts by weight of trimethylpropane trimethacrylate as the polymerizable compound [C], 5 parts by weight of benzoyl peroxide as a thermal radical polymerization initiator [D], and 3 parts by weight of 3M Company FC-430 (fluorinated surfactant 0.1 Was dissolved in a mixed solvent of diethylene glycol dimethyl ether and N-methylpyrrolidone (weight ratio 80:20), and the solid content concentration was adjusted to 25 wt%. Then, the solution was filtered with a filter having a pore diameter of 0.45 μm A thermosetting resin composition solution (S-3) was prepared.

<Example 4>

(B) having a glycoluril group based on 100 parts by weight (based on solid content) of the copolymer [A-1] obtained in the above Production Example and 100 parts by weight of the copolymer [A- 20 parts by weight of the compound, 100 parts by weight of pentaerythritol tetramethacrylate as the polymerizable compound [C], 5 parts by weight of 1,1'-azobis-1-cyclohexyl nitrile as a thermal radical polymerization initiator [D] And 0.1 part by weight of Shin-Etsu Silicone Co., Ltd. KP341 (silicone surfactant) were mixed and dissolved in a mixed solvent of diethylene glycol dimethyl ether and N-methylpyrrolidone (weight ratio 80:20) to give a solid content concentration of 25% by weight. Thereafter, the solution was filtered with a filter having a pore diameter of 0.45 mu m to prepare a thermosetting resin composition solution (S-4).

&Lt; Example 5 >

(B) having a glycoluril group based on 100 parts by weight (based on solid content) of the copolymer [A-1] obtained in the above Production Example and 100 parts by weight of the copolymer [A- 20 parts by weight of the compound, 100 parts by weight of dipentaerythritol penta methacrylate as the polymerizable compound [C], 5 parts by weight of 1,1'-azobis-1-cyclohexyl nitrile as the thermal radical polymerization initiator [D] , 0.1 part by weight of Shin-Etsu Silicone Co., Ltd. KP341 (silicone surfactant) were mixed and dissolved in a mixed solvent of diethylene glycol dimethyl ether and N-methylpyrrolidone (weight ratio 80:20) to give a solid content concentration of 25% by weight. Thereafter, the solution was filtered through a filter having a pore diameter of 0.45 mu m to prepare a thermosetting resin composition solution (S-5).

&Lt; Comparative Example 1 &

A thermosetting resin composition solution was prepared in the same manner as in Example 1 except that the compound [B] having a glycoluril group was not added.

&Lt; Comparative Example 2 &

A thermosetting resin composition solution was prepared in the same manner as in Example 3, except that the compound [B] having a glycoluril group was not added.

&Lt; Comparative Example 3 &

A thermosetting resin composition solution was prepared in the same manner as in Comparative Example 2 except that the content of the polymerizable compound [C] was 200 parts by weight.

&Lt; Formation of cured film &

The above-mentioned thermosetting resin composition was coated on a glass substrate so as to have a film thickness of 2 탆 by using a spin coater and then fired in a clean oven at 220 캜 for 30 minutes to form a cured film on the glass substrate.

The evaluation methods for the above-mentioned Examples and Comparative Examples are as follows.

(1) Adhesiveness

According to the checkerboard tape method, 11 lines of cuts having a spacing of 1 mm were cut out to a depth of the upper surface of the glass substrate using a cutter knife using a cutter knife, and 11 lines of cuts having a length of 1 mm After forming 100 checkerboard patterns, an adhesion test was performed in which an adhesive tape (Elcometer, Part Number K0001539M001) was placed on the checkerboard pattern and peeled off. The number of peeled checkerboard patterns was measured and the adhesion of the cured film was evaluated Respectively.

○: Number of peeled checkered patterns No more than 5

B: Number of peeled checkered patterns 6 to 49

X: Number of peeled checkered patterns 50 or more

(2) Surface hardness

The cured film was subjected to the pencil hardness test according to the pencil hardness method (test standard: ASTM D3363) to evaluate the surface hardness.

(3) Transparency

The transmittance of the cured film in a wavelength range of 400 to 700 nm was measured using a spectrophotometer (UV-3101PC, manufactured by Shimadzu Corporation) and the transparency of the cured film was evaluated according to the following criteria.

○: Minimum transmittance of 95% or more

?: Minimum transmittance of 90% or more and less than 95%

×: Minimum transmittance less than 90%

(4) Flatness

The surface irregularities of the cured film were irradiated using an? Step (manufacturer: KLA Tencor, equipment name: AS-500) and the step height of the substrate was measured.

(5) UV resistance

The transmittance of the protective film was measured at 400 to 700 nm using a spectrophotometer (UV-3101PC, manufactured by Shimadzu Corporation). Separately, the cured film was irradiated with UV (wavelength: 254 nm, irradiation amount: 200 mJ / cm 2) and the transmittance was measured by the same method. From each transmittance, the UV resistance of the protective film was evaluated according to the following criteria.

?: Transmission spectrum change within 1%

X: Change in transmission spectrum exceeds 1%

(6) Heat resistance (yellowing degree)

The transmittance of the protective film was measured at 400 to 700 nm using a spectrophotometer (UV-3101PC, manufactured by Shimadzu Corporation). Separately, the cured film was heated in a clean oven at 240 캜 for 60 minutes and the transmittance was measured in the same manner. The heat resistance of the protective film was evaluated from each transmittance by the following criteria.

?: Transmission spectrum change within 1%

X: Change in transmission spectrum exceeds 1%

(7) Acid resistance

The glass substrate on which the cured film was formed was immersed in a 25 wt% hydrochloric acid aqueous solution at 30 DEG C for 20 minutes, and then the appearance change of the cured film was observed to evaluate the acid resistance.

(8) Alkalinity

The glass substrate on which the cured film was formed was immersed in a 10 wt% aqueous solution of sodium hydroxide at 30 DEG C for 60 minutes, and then the appearance change of the cured film was observed to evaluate the alkali resistance.

The evaluation results are shown in Table 1 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Adhesiveness ○ ○ ○ ○ ○ ○ ○ ○ Surface hardness 5H 5H 5H 5H 5H 3H 3H 5H Transparency ○ ○ ○ ○ ○ ○ ○ ○ Planarization property 0.1 탆
Below 0.1 탆
Below 0.1 탆
Below 0.1 탆
Below 0.1 탆
Below 0.3 탆
Below 0.3 탆
Below 0.1 탆
Below UV resistance ○ ○ ○ ○ ○ × × × Heat resistance
(Yellowing degree) ○ ○ ○ ○ ○ × × × Acid resistance No change No change No change No change No change No change No change No change Alkali resistance No change No change No change No change No change No change No change No change

From the results shown in Table 1, it can be seen that when a compound having a glycorrile group is contained as a curable compound, the surface hardness is improved and the planarization property is improved as the crosslinking density is effectively increased, and the UV resistance and heat resistance are improved .

When a compound having a polyfunctional ethylenically unsaturated group as in Comparative Example 3 was used in excess, the formation of a hard cured film having a surface hardness of about 5H could be made equal, but the heat resistance was poor and the yellowing phenomenon was intensified.

Claims (7)

[A] a copolymer of an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride, (a2) an epoxy group-containing unsaturated compound, (a3) an olefinically unsaturated compound other than the above (a1) and (a2);
[B] A compound having a glycoluril group As the thermosetting resin composition,
Wherein the compound having the glycoluril group is any one or more selected from compounds represented by the following Chemical Formulas (3) to (6).
(3)

Formula 4

Formula 5

6

delete The thermosetting resin composition according to claim 1, wherein the compound having the glycoluril group is contained in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the copolymer [A]. The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition further comprises [C] a polymerizable compound having an ethylenic unsaturated bond and [D] a thermal radical polymerization initiator. 5. The thermosetting resin composition according to claim 4, wherein the polymerizable compound having an ethylenically unsaturated bond is 0.1 to 150 parts by weight based on 100 parts by weight of the copolymer [A], the thermal radical polymerization initiator [D] 0.1 to 20 parts by weight based on 100 parts by weight of the thermosetting resin composition. A cured film produced from the thermosetting resin composition according to any one of claims 1 to 5. The curing film according to claim 6, wherein the cured film is a color filter protective film of an optical device.