KR20190067411A - Thermosetting resin composition - Google Patents

Abstract

The present invention relates to a thermosetting resin composition which comprises a copolymer comprising a carboxyl group or an epoxy group together with an oxazoline group-containing resin as a crosslinking agent to satisfy properties required conventionally as a protective film, and at the same time, to effectively improve a crosslink density, thereby having excellent mechanical properties and heat resistance, and being able to provide a yellowing-free cured film 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, specifically a thermosetting resin composition which is used as a material for forming a protective film for an optical device and which has excellent mechanical properties and heat resistance, and a cured film made of the composition.

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 composed of 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 related 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 ethylenically unsaturated group serving as a crosslinking agent, and a thermal polymerization initiator is mainly used. Include the techniques described in Korean Patent Laid-Open Publication No. 10-2001-0085203 and Korean Patent Registration No. 10-1062250.

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.

DISCLOSURE OF THE INVENTION An object of the present invention is to solve the problems of the prior art as described above and to provide a resin composition which satisfies the characteristics required in the prior art and effectively improves the crosslinking density and is excellent in mechanical properties and heat resistance, , And to provide a thermosetting resin composition free from yellowing at a high temperature.

(A2) an epoxy group-containing unsaturated compound, (a3) an olefin other than the above-mentioned (a1) or (a2), an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride, Copolymer [A] of the unsaturated compound; And an oxazoline group-containing resin [B].

Such an oxazoline group-containing resin is a compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1, n is an integer of 1 to 100, m is an integer of 0 to 100, 1 is an integer of 0 to 100, X is a linear or cyclic alkyl group having 1 to 6 carbon atoms, an alkyl group having 2 to 6 carbon atoms A linear or cyclic alkylene group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylene group having 7 to 20 carbon atoms.

According to another embodiment of the present invention, the thermosetting resin composition may include up to 150 parts by weight of a polymerizable compound having an ethylenic unsaturated bond per 100 parts by weight of the copolymer [A].

According to another embodiment of the present invention, the thermosetting resin composition may contain 20 parts by weight or less of a thermal radical polymerization initiator per 100 parts by weight of the copolymer [A].

In addition, the present invention may include a cured film made of the thermosetting resin composition.

According to another embodiment of the present invention, the cured film may be a color filter protective film of an optical device.

The thermosetting resin composition according to the present invention contains a carboxyl group or a copolymer containing an epoxy group together with an oxazoline group-containing resin serving as a crosslinking agent, so that the cured film produced by using the thermosetting resin composition has characteristics And at the same time, it is possible to effectively improve the crosslinking density and to provide a cured film for an optical device which is excellent in mechanical properties and heat resistance and has no yellowing at high temperature.

Hereinafter, the thermosetting resin composition according to the present invention and the cured film for an optical device using the same will be described in detail. It will be apparent to those skilled in the art from this disclosure that the following description is only illustrative of the present invention and is not intended to limit the scope of the present invention. It will be understood that various modifications and equivalent embodiments are possible. Accordingly, the true scope of the present invention should be determined by the technical idea of the appended claims.

(A2) an epoxy group-containing unsaturated compound (hereinafter referred to as a compound (a2)), (a3) an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride ) A copolymer of an olefinically unsaturated compound other than the above (a1) or (a2) (hereinafter referred to as a compound (a3)); [B] The oxazoline group-containing resin And a thermosetting resin composition containing the 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, Can be determined in consideration of 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, and 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 or the storage stability of the copolymer . ≪ / RTI >

Examples of the compound (a2) include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-propyl acrylate, glycidyl α-n-butyl acrylate, Epoxy heptyl methacrylate, 6,7 epoxy heptyl methacrylate, 6,7 epoxy heptyl ethyl acrylate, o vinyl benzyl glycidyl ether, m vinyl benzyl glycidyl ether, p-vinylbenzyl glycidyl ether and the like can be preferably used in view of improving the copolymerization reactivity and the heat resistance and hardness of 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), because the storage stability of the copolymer and the cured film can be determined in consideration of heat resistance and surface hardness have.

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; 2 hydroxyalkyl esters such as 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, , 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, a carboxylic acid anhydride group or an epoxy group, and can be easily cured by heating even if 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) and 2,2 'azobis (4 methoxy 2,4 dimethylvaleronitrile) Azo compounds; Organic peroxides such as benzoyl peroxide, t-butyl peroxypivalate, 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 an oxazoline group-containing resin [B] together with the copolymer [A], and the oxazoline group-containing resin [B] can act as a curing agent for the copolymer [A].

The oxazoline group-containing resin is excellent in reactivity, and the cured film obtained from the oxazoline group-containing resin can secure a higher curing density, and as a result, deterioration of the heat resistance, UV resistance, and chemical resistance of the cured film can be prevented.

Such an oxazoline group-containing resin is a compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1, n is an integer of 1 to 100, m is an integer of 0 to 100, 1 is an integer of 0 to 100, X is a linear or cyclic alkyl group having 1 to 6 carbon atoms, an alkyl group having 2 to 6 carbon atoms A linear or cyclic alkylene group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylene group having 7 to 20 carbon atoms.

The content of the oxazoline group-containing resin [B] 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, Of the oxazoline group-containing resin [B] is prevented from remaining in the cured film and the oxazoline group-containing resin [B] is prevented from remaining in the cured film, thereby preventing the problem of unstable property of the cured film or deterioration of adhesion.

Examples of the oxazoline group-containing resin include, but are not limited to, EPOCROS K-2010E, K-2020E, K-2030E and RPS-1005.

In another embodiment of the present invention, in addition to the copolymer [A] and the oxazoline group-containing resin [B], a polymerizable compound having an ethylenically unsaturated bond [hereinafter referred to as "polymerizable compound [C] [D] thermal radical polymerization initiator (hereinafter referred to as 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 , 2 (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, and the like.

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

Examples of the trifunctional or more (meth) acrylate include (meth) acrylic acid esters such as ethylene glycol (meth) acrylate, trishydroxy ethylisocyanurate tri (meth) acrylate, trimethylpropane tri 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 cyclohexyl nitrile; 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 components [A] and oxazoline group-containing resin [B], and if necessary, the respective components of the polymerizable compound [C] and the thermal radical polymerization initiator [D] . 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 in a solution state by mixing the copolymer [A], the oxazoline group-containing resin [B], the polymerizable compound [C], the thermal radical polymerization initiator [D] . The composition of the present invention must contain the copolymer [A] and the oxazoline group-containing resin [B].

As the solvent used for preparing the thermosetting resin composition of the present invention, the respective components of the copolymer [A], the oxazoline group-containing resin [B], the polymerizable compound [C] and the thermal radical polymerization initiator [D] And it is acceptable if 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, N dimethylformamide, Nmethylacetamide, N, N dimethylacetamide, Nmethylpyrrolidone, dimethylsulfoxide, benzylethylether .

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 FC129, FC170C and FC430 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 탆.

The target 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 more detail with reference to Examples, but the scope of the present invention is not limited to these Examples.

<Production Example>

The reaction vessel equipped with a cooling tube and a stirrer was charged with 100 parts by weight of monomers (compound (al), compound (a2), and compound (a3)) used in the synthesis of the copolymer, And 5 parts by weight of bisisobutyronitrile as a solvent were dissolved in 200 parts by weight of diethylene glycol dimethyl ether.

Subsequently, 20 wt% of styrene, 30 wt% of methacrylic acid, 40 wt% of glycidyl methacrylate, and 10 wt% of dicyclopentenyloxyethyl methacrylate were charged, and after purging with nitrogen, And a stirring speed of 80 rpm was maintained.

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 [A1]. To measure the solid content of the solution, 1 g of the solution was weighed and placed in an oven at 220 ° C. for 60 minutes. After removing all of the solvent, the weight of the solid was weighed, and the solid weight was divided by the weight of the solution to calculate the percentage by weight Respectively. The solid concentration of the obtained polymer solution was 33% by weight.

&Lt; Example 1 >

100 parts by weight (based on the solid content) of the copolymer [A] obtained in the above Production Example and 100 parts by weight of the copolymer [A] were used as a base to prepare the oxazoline group- 20 parts by weight of EPOCROS K-2010E and 0.1 part by weight of 3M Company FC430 (fluorine surfactant) as a surfactant were dissolved in a mixed solvent of diethylene glycol dimethyl ether and N-methylpyrrolidone (weight ratio 80:20) Was 25 wt%.

Thereafter, the solution was filtered with a filter having a pore diameter of 0.45 mu m to prepare a thermosetting resin composition solution (S1).

&Lt; Example 2 >

100 parts by weight (based on the solid content) of the copolymer [A] obtained in the above Production Example and 100 parts by weight of the copolymer [A] were used as a base to prepare the oxazoline group- , 20 parts by weight of EPOCROS K-2020E and 0.1 part by weight of a surfactant, Shin-Etsu Silicones KP341 (silicone surfactant) were mixed and dissolved in a mixed solvent of diethylene glycol dimethyl ether and N-methylpyrrolidone (weight ratio 80:20) So that the solid concentration was 25 wt%.

Thereafter, the solution was filtered with a filter having a pore diameter of 0.45 mu m to prepare a thermosetting resin composition solution (S2).

&Lt; Example 3 >

100 parts by weight (based on the solid content) of the copolymer [A] obtained in the above Production Example and 100 parts by weight of the copolymer [A] were used as a base to prepare the oxazoline group- , 20 parts by weight of EPOCROS K-2030E, 100 parts by weight of trimethylpropane trimethacrylate as polymerizable compound [C], 5 parts by weight of benzoyl peroxide as thermal radical polymerization initiator [D], and 3 parts by weight of 3M Company FC430 (fluorochemical surfactant Were dissolved in a mixed solvent of diethylene glycol dimethyl ether and N-methylpyrrolidone (weight ratio 80:20), and then the solid concentration was adjusted to 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 (S3).

<Example 4>

100 parts by weight (based on the solid content) of the copolymer [A] obtained in the above Production Example and 100 parts by weight of the copolymer [A] were used as a base to prepare the oxazoline group- 50 parts by weight of EPOCROS K-2020E, 150 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 a surfactant Were dissolved in a mixed solvent of diethylene glycol dimethyl ether and N-methylpyrrolidone (weight ratio 80:20), and then the solid concentration was adjusted to 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 (S4).

&Lt; Example 5 >

100 parts by weight (based on the solid content) of the copolymer [A] obtained in the above Production Example and 100 parts by weight of the copolymer [A] were used as a base to prepare the oxazoline group- 10 parts by weight of EPOCROS RPS-1005, 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) so that the solid concentration was 25 wt%.

Thereafter, the solution was filtered through a filter having a pore diameter of 0.45 mu m to prepare a thermosetting resin composition solution S5.

&Lt; Example 6 >

100 parts by weight (based on the solid content) of the copolymer [A] obtained in the above Production Example and 100 parts by weight of the copolymer [A] were used as a base to prepare the oxazoline group- 20 parts by weight of EPOCROS RPS-1005, 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 a 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 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 (S6).

&Lt; Example 7 >

100 parts by weight (based on the solid content) of the copolymer [A] obtained in the above Production Example and 100 parts by weight of the copolymer [A] were used as a base to prepare the oxazoline group- , 0.1 part by weight of EPOCROS K-2020E, 150 parts by weight of trimethylpropane trimethacrylate as polymerizable compound [C], 5 parts by weight of benzoyl peroxide as thermal radical polymerization initiator [D], and 3 parts by weight of 3M Company FC430 Were dissolved in a mixed solvent of diethylene glycol dimethyl ether and N-methylpyrrolidone (weight ratio 80:20), and then the solid concentration was adjusted to 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 (S7).

&Lt; Comparative Example 1 &

A thermosetting resin composition solution was prepared in the same manner as in Example 1 except that the oxazoline group-containing resin [B] 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 oxazoline group-containing resin [B] was not added.

&Lt; Comparative Example 3 &

A thermosetting resin composition solution was prepared in the same manner as in Example 3 except that the oxazoline group-containing resin [B] was changed to 55 parts by weight.

&Lt; Comparative Example 4 &

A thermosetting resin composition solution was prepared in the same manner as in Example 3 except that the content of the polymerizable compound [C] was 160 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.

Evaluation methods for the above Examples and Comparative Examples are as follows.

(1) Adhesiveness

According to a 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, After forming a checkerboard pattern, an adhesive tape (Elcometer Co., Part Number K0001539M001) was placed on a checkerboard pattern and peeled off. The number of peeled checkerboard patterns was measured, and the adhesion of the cured film was evaluated according to the following criteria.

○: 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.

division Example
One Example
2 Example
3 Example 4 Example
5 Example
6 Example
7 Comparative Example
One Comparative Example
2 Comparative Example
3 Comparative Example
4 Adhesiveness ○ ○ ○ ○ ○ ○ ○ ○ ○ × ○ Surface hardness 5H 5H 5H 5H 5H 5H 5H 3H 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 0.1 탆
Below 0.1 탆
Below 0.3 탆
Below 0.3 탆
Below 0.3 탆
Below 0.1 탆
Below UV resistance ○ ○ ○ ○ ○ ○ ○ × × ○ ○ Heat resistance
(Yellowing degree) ○ ○ ○ ○ ○ ○ ○ × × ○ × Acid resistance change
none change
none change
none change
none change
none change
none change
none change
none change
none change
none change
none Alkali resistance change
none change
none change
none change
none change
none change
none change
none change
none change
none change
none change
none

From the results shown in Table 1, when the oxazoline group-containing resin is contained in an amount of 50 parts by weight or less based on 100 parts by weight of the copolymer [A], 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.

However, when the oxazoline group-containing resin is contained in an amount of more than 50 parts by weight based on 100 parts by weight of the copolymer [A] as in Comparative Example 3, the surface hardness, adhesiveness and planarizing property are lowered.

On the other hand, when a compound having a polyfunctional ethylenic unsaturated group is used in an excess amount exceeding 150 parts by weight based on 100 parts by weight of the copolymer [A] as in Comparative Example 4, a hardened film having a surface hardness of about 5H is formed Can be equalized, but the heat resistance is lowered and yellowing phenomenon is intensified.

Claims (7)

(a1) 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) or (a2); And
And an oxazoline group-containing resin [B]. The method according to claim 1,
Wherein the oxazoline group-containing resin [B] comprises a compound represented by the following formula (1).
[Chemical Formula 1]

In Formula 1, n is an integer of 1 to 100, m is an integer of 0 to 100, 1 is an integer of 0 to 100, X is a linear or cyclic alkyl group having 1 to 6 carbon atoms, an alkyl group having 2 to 6 carbon atoms A linear or cyclic alkylene group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an arylene group having 7 to 20 carbon atoms. The method according to claim 1,
Wherein the oxazoline group-containing resin [B] is contained in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the copolymer [A]. The method according to claim 1,
Wherein the thermosetting resin composition further comprises 150 parts by weight or less of a polymerizable compound having an ethylenic unsaturated bond per 100 parts by weight of the copolymer [A]. The method according to claim 1,
Wherein the thermosetting resin composition further comprises 20 parts by weight or less of a thermal radical polymerization initiator per 100 parts by weight of the copolymer [A]. A cured film made 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.