KR101062250B1 - Thermosetting resin composition for optical device protective film formation - Google Patents

Abstract

The present invention relates to a thermosetting resin composition suitable as a protective film forming material for an optical device. According to the present invention, the optical device protective film not only satisfies the characteristics required in the related art, but also improves UV resistance and heat resistance as well as surface hardness. Also, it is possible to provide a thermosetting resin composition capable of forming a protective film excellent in mechanical properties and heat resistance and free from yellowing at high temperatures by improving flatness and effectively improving crosslinking density.

LCD, protective film, thermosetting resin, epoxy resin

Description

Thermosetting resin composition for overcoating material of photo-device

1 is a diagram illustrating a laminated structure of a TFT-LCD. An overcoat layer is an example of the protective film coated with the composition of the present invention.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin composition suitable as a material for forming an optical device protective film. More particularly, the present invention relates to a protective film formed to prevent deterioration of a substrate generated during a manufacturing process of an optical device such as a liquid crystal display device. It relates to a thermosetting resin composition.

An optical device such as a liquid crystal display device is subjected to harsh processing such as being immersed by an organic solvent, an acid, an alkali solution, or the like during the manufacturing process, or subjected to localized high temperature heating by sputtering when forming a wiring electrode layer. Therefore, in order to prevent the deterioration at the time of manufacture, these elements may provide a protective film in the surface.                         

This protective film withstands the above treatments and has excellent adhesion to the substrate or lower layer, has high smoothness, high surface hardness, excellent transparency, and excellent heat resistance and light resistance without deterioration such as coloring, yellowing and whitening over a long period of time. What is excellent in chemical-resistance, such as chemical resistance, acid resistance, and alkali resistance, water resistance, etc. is calculated | required. In addition, when applying such a protective film to the color filter of a color liquid crystal display element, it is preferable that the level | step difference of a general color filter can be planarized with a base substrate.

Such a material is manufactured in the form of curable resin composition, and is largely classified into thermosetting and photocurable (photosensitive). When the patterning of the protective film is required, a photosensitive resin composition is required, but otherwise, a thermosetting resin composition is used because it is convenient in the process and can increase the crosslinking density, thereby providing excellent mechanical properties and heat resistance.

Japanese Patent Laid-Open Nos. 2000-103937, 2000-119472, and 2000-143772 are patents related to a protective film made of such a thermosetting resin composition. In these inventions, a composition composed of 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 initiator is used as a material to be applied to the protective film.

However, in the case of such a conventional thermosetting resin composition, the mechanical properties are not excellent, and in particular, the yellowing phenomenon is often exhibited due to poor heat resistance at high temperatures. In order to prevent this phenomenon, the polyfunctional monomer containing an ethylenically unsaturated group is excessively used, and such excessive use has a disadvantage in that yellowing at a high temperature becomes severe.

The present invention, in order to solve the problems of the prior art as described above, by using the epoxy compound in the form of a resin as a crosslinking agent, while satisfying the characteristics conventionally required as a protective film, while effectively improving the crosslinking density to excellent mechanical properties and heat resistance It is an object of the present invention to provide a thermosetting resin composition which is free from yellowing at a high temperature and which is very suitable as a protective film forming material for an optical device.

The object of the present invention can be embodied from the following description.

The technical problem and object

(A) (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride (hereinafter referred to as compound (a1)), (a2) epoxy group-containing unsaturated compound (hereinafter referred to as compound (a2)), (a3) above (a1) and ( copolymers of olefinically unsaturated compounds other than a2) (hereinafter referred to as compound (a3)) (hereinafter referred to as copolymer [A]),

[B] A thermosetting resin composition comprising an epoxy compound (hereinafter referred to as curable compound [B]) in the form of one or two or more resins selected from formula (1).

<Formula 1>                     

(n=1-10의 정수)

(an integer from n = 1-10)

In the above formula, A is -H, -CH ₃ and B is selected from the following compounds.

The thermosetting resin composition of the present invention will be described below in detail.

1) Copolymer A                     

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

The copolymer [A] used in the present invention preferably contains 5 to 40% by weight, particularly preferably 10 to 30% by weight, of structural units derived from compound (a1). Copolymers having a structural unit of less than 5% by weight tend to lower heat resistance, chemical resistance and surface hardness, while copolymers of more than 40% by weight lower storage safety. As a compound (a1), dicarboxylic acids, such as monocarboxylic acid maleic acid, such as acrylic acid, methacrylic acid, and crotonic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and anhydrides of these dicarboxylic acids are mentioned, for example. Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used in view of copolymerization reactivity, heat resistance and easy availability. These compounds (a1) are used individually or in combination.

Copolymer [A] used in the present invention preferably contains 10 to 70% by weight, particularly preferably 20 to 60% by weight, of structural units derived from compound (a2). The copolymer of which the structural unit is less than 10% by weight tends to lower the heat resistance and the surface hardness of the protective film to be obtained, whereas when it exceeds 70% by weight, the storage safety of the copolymer tends to be lowered. Examples of the compound (a2) include glycidyl acrylate, glycidyl methacrylate, α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, and acrylic acid. -3,4-epoxy butyl, methacrylic acid-3,4-epoxy butyl, acrylic acid-6,7-epoxy heptyl, methacrylic acid-6,7-epoxy heptyl, α-ethyl acrylic acid-6,7-epoxy Heptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether and the like are preferably used in view of increasing the copolymerization reactivity and the heat resistance and hardness of the resulting protective film. These compounds (a2) are used individually or in combination.

Copolymer [A] used in the present invention preferably contains 10 to 70% by weight, particularly preferably 20 to 50% by weight, of structural units derived from compound (a3). When this structural unit is less than 10 weight%, the storage stability of copolymer [A] tends to fall, and when it exceeds 70 weight%, the heat resistance and surface hardness of copolymer [A] tend to fall. As the compound (a3), for example, methacrylic acid alkyl ester methyl acrylate such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, Acrylic acid alkyl ester cyclohexyl methacrylate, such as isopropyl acrylate, 2-methyl cyclohexyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, isoboroyl methacrylate, etc. Acrylic acid cycloalkyl esters such as methacrylic acid cycloalkyl ester cyclohexyl acrylate, 2-methyl cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, isoboroyl acrylate Methacrylic acid aryl ester phenyl arc such as methacrylate and benzyl methacrylate Hydroxy, such as dicarboxylic acid diester 2-hydroxy ethyl methacrylate and 2-hydroxy propyl methacrylate, such as acrylate ester diethyl maleate, diethyl fumarate, and diethyl itaconic acid, such as the acrylate and benzyl acrylate Alkyl esters and styrenes, o-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p-methoxy styrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacryl Amide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like. Among them, styrene, t-butyl methacrylate, dicyclopentenyl methacrylate, p-methoxy styrene, 2-methyl cyclohexyl acrylate, 1,3-butadiene, and the like are preferred from the viewpoint of copolymerization reactivity and heat resistance. These compounds (a3) are used alone or in combination.

The copolymer [A] used in the present invention has a carboxyl group and / or a carboxylic anhydride group and an epoxy group, and can be easily cured by heating even without using a special curing agent.

As a solvent used for the synthesis of the copolymer [A], ethers such as alcohols such as methanol and ethanol, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and the like propylene glycol methyl ether acetate and propylene glycol ethyl ether Propylene glycol alkyl ether acetates such as acetate, propylene glycol propyl ether acetate and propylene glycol butyl ether acetate are preferred.

As a polymerization initiator used for the synthesis | combination of copolymer [A], what is generally known as a radical polymerization initiator can be used. For example, 2,2'-azobis isobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2, Azo compounds such as 4-dimethylvaleronitrile); Organic peroxides and hydrogen peroxide, such as benzoyl peroxide, t-butyl peroxy pibarate and 1,1'-bis- (t-butyl peroxy) cyclohexane. When a peroxide is used as a radical polymerization initiator, you may use as a redox initiator by using a peroxide together with a reducing agent.

2) Curable Compound B

Curable compound [B], which is an epoxy compound in the form of a resin used in the present invention, acts as a curing agent for copolymer [A]. The epoxy compound in the resin form is selected from the above [Formula 1].

The thermosetting resin composition of this invention contains 1-10 weight part of curable compounds [B] with respect to 100 weight part of copolymers [A], and more preferably 3-10 weight part. When curable compound [B] is less than 1 weight part, the protective film which has a sufficiently high crosslinking density is hard to be obtained, and the various tolerances of a protective film may fall. When the curable compound [B] exceeds 10 parts by weight, a large amount of unreacted curable compound [B] is likely to remain in the film of the resulting protective film, and as a result, the properties of the protective film tend to become unstable or the adhesiveness tends to decrease.

On the other hand, in addition to the copolymer [A], the curable compound [B], a polymerizable compound having an [C] ethylenically unsaturated bond (hereinafter referred to as the polymerizable compound [C]), and a [D] thermal radical polymerization initiator (hereinafter referred to as thermal radical polymerization) Initiator (D)).

3) polymeric compounds [C]

As the polymerizable compound [C] used in the present invention, monofunctional, bifunctional, or trifunctional or higher (meth) acrylate is preferable from the viewpoint of good polymerizability and improved heat resistance and surface hardness of the resulting protective film.

As monofunctional (meth) acrylate, 2-hydroxy ethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxy butyl (meth) acrylate, for example , 2- (meth) acryloyl oxyethyl 2-hydroxy propyl phthalate, and the like.

As a bifunctional (meth) acrylate, for example, ethylene glycol (meth) acrylate, 1,6-hexanediol (meth) acrylate, 1,9-nonanediol (meth) acrylate, propylene glycol (meth) ) Acrylate, tetraethylene glycol (meth) acrylate, bisphenoxy ethyl alcohol fluorene diacrylate, etc. are mentioned.

As (meth) acrylate more than trifunctional, for example, tris hydroxyethyl isocyanurate tri (meth) acrylate, trimethyl propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerytate Lithol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned.

Such mono-, bi-, or tri- or more (meth) acrylates are used alone or in combination.

The thermosetting resin composition of this invention contains 150 weight part or less of polymerizable compounds [C] with respect to 100 weight part of copolymers [A], and more preferably 120 weight part or less. When polymeric compound [C] exceeds 150 weight part, the adhesiveness of the protective film obtained will fall easily.

4) Thermal radical polymerization initiator                     

The thermal radical polymerization initiator [D] used in the present invention is 2,2'-azobis isobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azo Azo compounds benzoyl peroxide, t-butyl peroxide, 1,1'-, such as bis- (4-methoxy-2,4-dimethylvaleronitrile) and 1,1'- azobis-1-cyclohexylnitrile Organic peroxides, such as bis- (t-butyl peroxy) cyclohexane, etc. are mentioned.

The thermosetting resin composition of the present invention preferably contains a thermal radical polymerization initiator [D] at 20 parts by weight or less and more preferably 15 parts by weight or less with respect to 100 parts by weight of the copolymer [A]. When thermal radical polymerization initiator [D] exceeds 20 weight part, the heat resistance, planarization property, etc. of a protective film tend to fall.

The thermosetting resin composition of this invention is manufactured by uniformly mixing each component of said copolymer [A], curable compound [B], polymeric compound [C], and thermal radical polymerization initiator [D]. Usually, the thermosetting resin composition of this invention is melt | dissolved in a suitable solvent, and is used in a solution state. That is, a copolymer [A], a curable compound [B], a polymerizable compound [C], a thermal radical polymerization initiator [D], and other additives are mixed at a predetermined ratio to prepare a thermosetting resin composition in a solution state. The composition of this invention must contain copolymer [A] and curable compound [B].

As a solvent used for preparation of the thermosetting resin composition of this invention, each component of a copolymer [A], a curable compound [B], a polymerizable compound [C], and a thermal radical polymerization initiator [D] can be melt | dissolved uniformly. It is used that does not react with either component. Specifically, for example, alcohols such as methanol and ethanol, ethers such as tetrahydrofuran, diethylene glycol dimethyl ether and diethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl Propylene glycol alkyl ether acetates, such as ether acetate and a propylene glycol butyl ether acetate, etc. are mentioned. Among these solvents, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate are preferably used in view of solubility, reactivity with each component, and convenience of coating film formation.

Moreover, it is also possible to use a high boiling point solvent together with the said solvent. As a high boiling point solvent which can be used together, it is N-methyl formamide, N, N-dimethyl formamide, N-methyl acetamide, N, N-dimethyl acetamide, N-methyl pyrrolidone, dimethyl sulfoxide, for example. And benzyl ethyl ether.

5) Other

The thermosetting resin composition of this invention may contain other components of that excepting the above as needed in the range which does not impair the objective of this invention.

Here, as another component, surfactant for improving applicability | paintability is mentioned. Examples of the surfactant include fluorine and silicone-based surfactants, for example, 3M's FC-129, FC-170C, FC-430, Shin-Etsu Silicone's KP322, KP323, KP340, and KP341. Such surfactant is used in an amount of preferably 5 parts by weight or less, more preferably 2 parts by weight or less, based on 100 parts by weight of the copolymer [A]. When the amount of the surfactant exceeds 5 parts by weight, bubbles are likely to occur during application.

The composition solution prepared as described above is used after filtration using a filter having a pore diameter of about 0.1 to 5 μm.

The target protective film can be obtained by apply | coating the thermosetting resin composition of this invention to a base substrate, and processing it for 10 to 100 minutes at 150-300 degreeC in oven.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the Examples.

&Lt; Example 1 >

5 parts by weight of 2,2'-azobis isobutyronitrile was dissolved in 200 parts by weight of diethylene glycol dimethyl ether in a reaction vessel equipped with a cooling tube and a stirrer. Subsequently, 20 parts by weight of styrene, 30 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, and 10 parts by weight of dicyclopentenyloxyethyl methacrylate were added thereto, followed by nitrogen substitution, followed by gentle stirring. The temperature of the solution was raised to 80 ° C. and maintained at this temperature for 4 hours to obtain a polymer solution containing copolymer [A-1]. Solid content concentration of the obtained polymer solution was 33 weight%. 100 parts by weight (solid content) of the obtained copolymer [A-1], 5 parts by weight of Nippon Kayaku Co., Ltd. EOCN-1020 as the curable compound [B], and 0.1 parts by weight of FC-430 (3M) as the surfactant were mixed with diethylene glycol dimethyl. After dissolving in ether and N-methyl pyrrolidone, the solid concentration was 25% by weight. Then, it filtered by the filter of 0.45 micrometers of pore diameters, and prepared the thermosetting resin composition solution (S-1).

<Example 2>

5 parts by weight of 2,2'-azobis isobutyronitrile was dissolved in 200 parts by weight of diethylene glycol dimethyl ether in a reaction vessel equipped with a cooling tube and a stirrer. Subsequently, 20 parts by weight of styrene, 30 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, and 10 parts by weight of dicyclopentenyloxyethyl methacrylate were added thereto, followed by nitrogen substitution, followed by gentle stirring. The temperature of the solution was raised to 80 ° C. and maintained at this temperature for 4 hours to obtain a polymer solution containing copolymer [A-1]. Solid content concentration of the obtained polymer solution was 33 weight%. 100 parts by weight (solid content) of the obtained copolymer [A-1], 5 parts by weight of Nippon Kayaku Co., Ltd. EOCN-4500 as the curable compound [B], and 0.1 parts by weight of KP341 (Shin-Etsu Silicone) as a surfactant were mixed with diethylene glycol dimethyl ether. And dissolved in N-methyl pyrrolidone to a solid content concentration of 25% by weight. Then, it filtered by the filter of 0.45 micrometers of pore diameters, and prepared the thermosetting resin composition solution (S-2).

<Example 3>

5 parts by weight of 2,2'-azobis isobutyronitrile was dissolved in 200 parts by weight of diethylene glycol dimethyl ether in a reaction vessel equipped with a cooling tube and a stirrer. Subsequently, 20 parts by weight of styrene, 30 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, and 10 parts by weight of dicyclopentenyloxyethyl methacrylate were added thereto, followed by nitrogen substitution, followed by gentle stirring. The temperature of the solution was raised to 80 ° C. and maintained at this temperature for 4 hours to obtain a polymer solution containing copolymer [A-1]. Solid content concentration of the obtained polymer solution was 33 weight%. 100 parts by weight of the obtained copolymer [A-1] (solid content), 5 parts by weight of Nippon Kayaku Co., Ltd. XD-1000 as the curable compound [B], 100 parts by weight of trimethylpropane trimethacrylate as the polymerizable compound [C], heat 5 parts by weight of benzoyl peroxide as radical polymerization initiator [D] and 0.1 parts by weight of FC-430 (3M) as surfactants were dissolved in diethylene glycol dimethyl ether and N-methyl pyrrolidone and the solid content was 25% by weight. Was made. Then, it filtered by the filter of 0.45 micrometers of pore diameters, and prepared the thermosetting resin composition solution (S-3).

<Example 4>

5 parts by weight of 2,2'-azobis isobutyronitrile was dissolved in 200 parts by weight of diethylene glycol dimethyl ether in a reaction vessel equipped with a cooling tube and a stirrer. Subsequently, 20 parts by weight of styrene, 30 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, and 10 parts by weight of dicyclopentenyloxyethyl methacrylate were added thereto, followed by nitrogen substitution, followed by gentle stirring. The temperature of the solution was raised to 80 ° C. and maintained at this temperature for 4 hours to obtain a polymer solution containing copolymer [A-1]. Solid content concentration of the obtained polymer solution was 33 weight%. 100 parts by weight of the obtained copolymer [A-1] (solid content), 5 parts by weight of Nippon Kayaku Co., Ltd. NC-3000 as the curable compound [B], 100 parts by weight of pentaerythritol tetramethacrylate as the polymerizable compound [C], Diethylene glycol dimethyl ether and N-methyl pyrrolidone were mixed by mixing 5 parts by weight of 1,1'-azobis-1-cyclohexylnitrile as a thermal radical polymerization initiator [D] and 0.1 parts by weight of KP341 (Shin-Etsu Silicone) as a surfactant. After dissolving in, the solid concentration was 25% by weight. Then, it filtered by the filter of 0.45 micrometers of pore diameters, and prepared the thermosetting resin composition solution (S-4).

Example 5

5 parts by weight of 2,2'-azobis isobutyronitrile was dissolved in 200 parts by weight of diethylene glycol dimethyl ether in a reaction vessel equipped with a cooling tube and a stirrer. Subsequently, 20 parts by weight of styrene, 30 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, and 10 parts by weight of dicyclopentenyloxyethyl methacrylate were added thereto, followed by nitrogen substitution, followed by gentle stirring. The temperature of the solution was raised to 80 ° C. and maintained at this temperature for 4 hours to obtain a polymer solution containing copolymer [A-1]. Solid content concentration of the obtained polymer solution was 33 weight%. 100 weight part (solid content) of the obtained copolymer [A-1], 5 weight part of Nippon Kayaku Co., Ltd. EPPN-501H as a curable compound [B], and 100 weight part of dipentaerythritol pentamethacrylate as a polymeric compound [C] 5 parts by weight of 1,1'-azobis-1-cyclohexylnitrile as a thermal radical polymerization initiator [D] and 0.1 parts by weight of KP341 (Shin-Etsu Silicone) as a surfactant were mixed with diethylene glycol dimethyl ether and N-methyl pyrroli. After dissolving in pigs, the solid concentration was 25% by weight. Then, it filtered by the filter of 0.45 micrometers of pore diameters, and prepared the thermosetting resin composition solution (S-5).

Comparative Example 1                     

A thermosetting resin composition solution was prepared in the same manner as in Example 1, except that the curable compound [B] was not used.

Comparative Example 2

A thermosetting resin composition solution was prepared in the same manner as in Example 3, except that the curable compound [B] was not used.

<Formation of protective film>

Using a spin coater, the thermosetting resin composition was coated on the glass substrate so that the film thickness was 2 μm, and then fired at 220 ° C. for 30 minutes in a clean oven to form a protective film on the glass substrate.

<Evaluation Method>

After the protective film was formed, adhesion, surface hardness, transparency, planarization, UV resistance, heat resistance, acid resistance, and alkali resistance were measured in the following manners, and are shown in [Table 1].

(1) adhesion

According to the checkered tape method, 100 checkers were formed on the protective film with a cutter knife, and the adhesion test was carried out to measure the number of peeled checkered patterns and to evaluate the adhesion of the protective film according to the following criteria.

(Circle): The number of the peeled checkerboard patterns 5 or less

(Triangle | delta): The number of the peeled checkerboard patterns 6-49 pieces

×: 50 or more pieces of checkered patterns

(2) surface hardness                     

The surface hardness of the protective film was evaluated by performing a pencil hardness test method on the protective film according to the pencil hardness method.

(3) transparency

The transmittance of the protective film was measured at 400 to 700 nm using a spectrophotometer, and the transparency of the protective film was evaluated according to the following criteria.

(Circle): More than 95% of minimum transmittance | permeability

△: minimum transmittance of 90 to 95%

X: less than 90% of the lowest transmittance

(4) flatness

The surface irregularities of the protective film were irradiated using the α step, and the step difference of the substrate was measured.

(5) UV resistance

The protective film was irradiated with UV. The transmission spectrum of the protective film was measured before and after UV irradiation, and the UV resistance of the protective film was evaluated according to the following criteria.

(Circle): The change of a transmission spectrum is within 1%.

X: 1% or more of change in transmission spectrum

(6) Heat resistance (degree of yellowing)

The protective film was heated in a clean oven at 240 ° C. for 60 minutes, and the transmission spectrum was measured before and after heating, and the heat resistance of the protective film was evaluated according to the following criteria.

(Circle): The change of a transmission spectrum is within 1%.                     

X: 1% or more of change in transmission spectrum

(7) acid resistance

After the glass substrate on which the protective film was formed was immersed in a 25 wt% aqueous hydrochloric acid solution for 30 minutes at 30 ° C., the appearance change of the protective film was observed to evaluate the acid resistance of the protective film.

(8) alkali resistance

After the glass substrate on which the protective film was formed was immersed in 10 wt% sodium hydroxide aqueous solution for 30 ° C. for 60 minutes, the appearance change of the protective film was observed to evaluate the alkali resistance of the protective film.

Evaluation properties of the Examples and Comparative Examples are shown in Table 1 below.

TABLE 1

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Adhesion ○ ○ ○ ○ ○ ○ ○ Surface hardness 5H 5H 5H 5H 5H 3H 3H Transparency ○ ○ ○ ○ ○ ○ ○ Flatness 0.1㎛ less than 0.1㎛ less than 0.1㎛ less than 0.1㎛ less than 0.1㎛ less than Less than 0.3㎛ Less than 0.3㎛ UV resistance ○ ○ ○ ○ ○ × × Heat resistance
(Yellowing degree) ○ ○ ○ ○ ○ × × Acid resistance 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

When forming a protective film by coating the composition of the embodiment of the present invention containing a epoxy compound in the form of a resin from the results of Table 1, not only the UV resistance and heat resistance are improved, but also the surface hardness and planarization properties are improved, which is required as a protective film. At the same time, it is possible to effectively improve the crosslinking density and to produce a protective film having excellent mechanical properties and heat resistance and no yellowing at high temperatures.

 The thermosetting resin composition using a epoxy compound in the form of a resin as a crosslinking agent in an epoxy group-containing resin commonly used according to the present invention is a base substrate while satisfying adhesion to the substrate, surface hardness, transparency, heat resistance, UV resistance, chemical resistance, and the like. Since the level difference of the color filter can be flattened, it is very suitable as a protective film forming material for an optical device.

Claims (5)

(A) (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, (a2) epoxy group-containing unsaturated compound, (a3) copolymers of olefinically unsaturated compounds other than (a1) and (a2), [B] A thermosetting resin composition for forming an optical device protective film, comprising an epoxy compound in the form of one or two or more resins selected from formula (1). [Formula 1]

In the above formula, A is -H, -CH ₃ , B is

to be. The method of claim 1, [B] The thermosetting resin composition for forming an optical device protective film, wherein the epoxy compound in the form of one or two or more resins selected from the general formula (1) is contained in an amount of 1 to 10 parts by weight based on 100 parts by weight of the copolymer [A]. The method of claim 1, A thermosetting resin composition for forming an optical device protective film, further comprising a polymerizable compound having an [C] ethylenically unsaturated bond in an amount of 150 parts by weight or less based on 100 parts by weight of the copolymer [A]. The method according to claim 1 or 3, A thermosetting resin composition for forming an optical device protective film, further comprising [D] a thermal radical polymerization initiator in an amount of 20 parts by weight or less based on 100 parts by weight of the copolymer [A]. (A) (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, (a2) epoxy group-containing unsaturated compound, (a3) copolymers of olefinically unsaturated compounds other than (a1) and (a2), [B] an epoxy compound in the form of one or two or more resins selected from Formula 1, and [C] A thermosetting resin composition for forming an optical device protective film, comprising a polymerizable compound having an ethylenically unsaturated bond. [Formula 1]

In the above formula, A is -H, -CH ₃ and B is selected from the following compounds.

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