KR20070096343A - Thermosetting resin composition - Google Patents

Abstract

A thermosetting resin composition and a protective film for an optical device formed by using the composition are provided to improve surface hardness, smoothness, mechanical properties, UV resistance and heat resistance and to prevent yellowing even at a high temperature. A thermosetting resin composition comprises 100 parts by weight of a copolymer of an unsaturated carboxylic acid or its anhydride, an unsaturated compound containing an epoxy group, and an olefin-based unsaturated compound; 1-10 parts by weight of a urethane oligomer containing an acryl terminal group having a number average molecular weight of 1,000-5,000 as a curing compound; optionally 150 parts by weight or less of a polymerizable compound containing an ethylenically unsaturated bond; and optionally 20 parts by weight or less of a thermal radical polymerization initiator.

Description

Thermosetting resin composition

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin composition and a protective film made of the composition, and more particularly to a thermosetting composition and a protective film made of the composition as a material for forming a protective film used for a color filter for an optical device.

Optical devices such as liquid crystal display devices (LCDs) are subjected to harsh processing such as immersion treatment with organic solvents, acids, alkaline solutions, etc. during the manufacturing process, or localized high temperature heating of the surface by sputtering when forming wiring electrode layers. Will receive. Therefore, in order to prevent the deterioration at the time of manufacture, these elements may provide a protective film in the surface.

The protective film protects the colored layer and serves to planarize the color filter. Therefore, the protective film must withstand such harsh treatments and at the same time have excellent adhesion to the substrate or lower layer, and have high smoothness, surface hardness, transparency, and excellent heat resistance and light resistance without deterioration such as coloring, yellowing and whitening over a long period of time. do. Moreover, what is excellent in chemical-resistance, such as solvent resistance, acid resistance, and alkali resistance, and water resistance 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 board | substrate.

The protective film composition is manufactured in the form of a curable resin composition so as to satisfy the above conditions, and 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 Application Laid-Open Nos. 2000-103937, 2000-119472 and 2000-143772 describe thermosetting resin compositions as compositions constituting a protective film. That is, the composition which consists of an acrylic resin containing a carboxyl group or an epoxy group, the polyfunctional monomer containing the ethylenically unsaturated group which functions as a crosslinking agent, and a thermal polymerization initiator is used.

However, when the protective film is prepared using these compositions, mechanical properties are not excellent, and in particular, yellowing phenomenon is often exhibited due to poor heat resistance at high temperatures. In consideration of the mechanical properties, the polyfunctional monomer containing an ethylenically unsaturated group can be used excessively. In this case, there is a problem that the yellowing phenomenon at a high temperature becomes more severe.

The present invention is to solve such a problem, a number average molecular weight of 1000 to 5000 as a crosslinking agent, using a urethane oligomer having an acrylic group as a terminal group effectively improves the crosslinking density to excellent mechanical properties and heat resistance thermosetting resin composition and The purpose is to provide a protective film made of this composition.

In addition, an object of the present invention is to provide a thermosetting resin composition and a protective film made of the composition which does not appear yellowing even at high temperatures.

The present invention for achieving the above object is a thermosetting resin composition comprising a copolymer [A] of (a1) unsaturated carboxylic acid or its anhydride, (a2) epoxy group-containing unsaturated compound, (a3) olefinically unsaturated compound, As curable compound [B], the number average molecular weight is 1000-5000, The thermosetting resin composition characterized by including the urethane oligomer which has an acryl group as a terminal group.

The curable compound [B] is characterized by containing 1 to 10 parts by weight based on 100 parts by weight of the copolymer [A].

The thermosetting resin composition is characterized by further comprising a polymerizable compound [C] having an ethylenically unsaturated bond in an amount of 150 parts by weight or less based on 100 parts by weight of the copolymer [A].

The thermosetting resin composition is characterized in that it further comprises 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].

The present invention also provides a protective film formed of the thermosetting resin composition.

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

Curable compound [B] used by this invention acts as a hardening | curing agent with respect to copolymer [A]. The said copolymer [A] is mentioned later.

The curable compound [B] may have a number average molecular weight of 1000 to 5000, and may be selected from urethane oligomers having an acrylic reactive group as a terminal group. If the number average molecular weight is less than 1000, it is difficult to obtain a cured film with sufficient curing density, and there is a problem that surface hardness, heat resistance, and UV resistance may deteriorate. If the number average molecular weight is more than 5000, compatibility with other components is insufficient. Therefore, it is difficult to obtain a cured film having a sufficient curing density, and there is also a problem that surface hardness, heat resistance, and UV resistance may decrease. On the other hand, when there is no acryl-reactive group in the terminal group, there is a problem that hardening reaction does not occur and a cured film having a sufficient curing density is hardly obtained, and surface hardness, heat resistance, and UV resistance may also decrease.

Specific examples of such acryl terminated urethane oligomers include EB-1290, EB-9260, EB-230, EB-6700, and EB-8800, which are commercially available from SK-UCB.

It is preferable to contain 1-10 weight part with respect to 100 weight part of copolymers [A], and, as for the said curable compound [B], it is good to contain 3-10 weight part more preferably. When content of curable compound [B] contains less than 1 weight part with respect to 100 weight part of copolymers [A], it is difficult to obtain the protective film which has a sufficiently high crosslinking density, and there exists a problem that the various resistance of a protective film may fall. When the amount exceeds 10 parts by weight, a large amount of unreacted curable compound [B] is likely to remain in the film of the protective film to be obtained, and as a result, the property of the protective film is unstable or the adhesiveness tends to be lowered.

The said copolymer [A] is obtained by the conventionally well-known polymerization method, ie, compound (a1), (a2), and (a3) can be synthesize | combined by performing radical polymerization in presence of a polymerization initiator in a solvent.

The copolymer [A] preferably contains 5 to 40% by weight, more preferably 10 to 30% by weight of the structural unit derived from the compound [a1]. When this structural unit is less than 5 weight%, the heat resistance, chemical resistance, and surface hardness of the protective film manufactured later tend to fall, and when it exceeds 40 weight%, there exists a problem that storage safety falls. 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, and one or more selected from these can be used in combination. Among them, acrylic acid, methacrylic acid, maleic anhydride and the like are mainly used because of their excellent copolymerization reactivity and heat resistance and easy availability.

The copolymer [A] preferably contains 10 to 70% by weight, more preferably 20 to 60% by weight of the structural unit derived from the compound [a2]. When this structural unit is less than 10 weight%, the heat resistance and surface hardness of the protective film produced later tend to fall, and when it exceeds 70 weight%, storage safety tends to fall. 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 It is used alone or in combination of two or more selected from -vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether to improve the copolymerization reactivity and the heat resistance and hardness of the resulting protective film. It is preferably used in that point.

The copolymer [A] preferably contains 10 to 70% by weight, more preferably 20 to 50% by weight of the structural unit derived from the compound [a3]. When this structural unit is less than 10 weight%, storage stability tends to fall, and when it exceeds 70 weight%, the heat resistance and surface hardness of the protective film produced later tend to fall. 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; Acrylic acid alkyl esters such as methyl acrylate and isopropyl acrylate; Methacrylic acid cycloalkyl esters such as cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate and isoboroyl methacrylate; Acrylic acid cycloalkyl esters such as cyclohexyl acrylate, 2-methyl cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate and isoboroyl acrylate; Methacrylic acid aryl esters such as phenyl 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 itaconic acid; Hydroxy alkyl esters such as 2-hydroxy ethyl methacrylate and 2-hydroxy propyl methacrylate; And styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p-methoxy styrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, Vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, or a combination of two or more thereof. Among them, styrene, t-butyl methacrylate, dicyclopentenyl methacrylate, p-methoxy styrene, 2-methyl cyclohexyl acrylate, 1,3-butadiene, and the like are preferable in terms of copolymerization reactivity and heat resistance.

The copolymer [A] used in the present invention has a carboxyl group and / or a carboxylic anhydride and an epoxy group, and although it is possible to easily cure by heating without using a special curing agent, it is difficult to obtain sufficient crosslinking density, as described above. When using one curable compound [B], crosslinking density can fully be raised.

Although the molecular weight of copolymer [A] is not specifically limited, It is suitably selected according to the thickness of the film | membrane formed, the solution coating conditions of a curable composition, the objective, etc .. It is preferable that the number average molecular weight of copolymer [A] exists in the range of 3,000-100,000 in consideration of the surface smoothness of the protective film manufactured later, More preferably, it is 3,000-50,000.

As a solvent used for the synthesis | combination of copolymer [A], Alcohol, such as methanol and ethanol; Ethers such as tetrahydrofuran, diethylene glycol dimethyl ether and diethylene glycol diethyl ether; One or a combination of two or more selected from 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 is preferred.

As a polymerization initiator used for the synthesis | combination of a 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-2,4- Azo compounds such as dimethylvaleronitrile); Organic peroxides such as benzoyl peroxide, t-butyl peroxy pibarate, 1,1'-bis- (t-butyl peroxy) cyclohexane; And hydrogen peroxide. When a peroxide is used as a radical polymerization initiator, a peroxide can be used together with a reducing agent as a redox type initiator.

On the other hand, the thermosetting resin composition of the present invention may further include a polymerizable compound [C] having an ethylenically unsaturated bond in addition to the co-polymer [A] and the curable compound [B].

The said polymeric compound [C] is preferable from a viewpoint that a monofunctional, bifunctional, or trifunctional or more (meth) acrylate has favorable polymerizability, and the heat resistance and surface hardness of the protective film obtained later improve.

As said monofunctional (meth) acrylate, 2-hydroxy ethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2- (meth) acryloyloxy ethyl 2-hydroxy propyl phthalate etc. are mentioned.

As said bifunctional (meth) acrylate, ethylene glycol (meth) acrylate, 1, 6- hexanediol (meth) acrylate, 1, 9- nonanediol (meth) acrylate, propylene glycol (meth) acryl The rate, tetraethylene glycol (meth) acrylate, bisphenoxy ethyl alcohol fluorene diacrylate, etc. are mentioned.

As said trifunctional or more than (meth) acrylate, a tris hydroxyethyl isocyanurate tri (meth) acrylate, a trimethyl propane tri (meth) acrylate, a pentaerythritol tri (meth) acrylate, pentaerythritol tetra ( Meta) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

It can be used as a polymeric compound [C] by 1 type or in combination of 2 or more types selected from such monofunctional, bifunctional, or trifunctional or more than (meth) acrylate.

The polymerizable compound [C] is preferably contained in an amount of 150 parts by weight or less with respect to 100 parts by weight of the copolymer [A], and more preferably 120 parts by weight or less. When content of polymeric compound [C] exceeds 150 weight part with respect to 100 weight part of copolymers [A], the adhesiveness of the protective film obtained will fall easily.

In addition, the thermosetting resin composition of the present invention may further contain a thermal radical polymerization initiator, but is contained in a proportion of 20 parts by weight or less, more preferably 15 parts by weight or less, based on 100 parts by weight of the copolymer [A]. When the thermal radical polymerization initiator exceeds 20 parts by weight, the heat resistance and planarization property of the protective film obtained later are likely to be lowered.

The thermal radical polymerization initiator may be generally used as a radical polymerization initiator, and may be used a polymerization initiator used for the polymerization of the copolymer [A] described above.

The thermosetting resin composition of this invention can be manufactured by melt | dissolving a polymeric compound [C] and a thermal radical polymerization initiator in a solvent selectively with the copolymer [A] and curable compound [B] mentioned above. The solvent used at this time does not react with any component. For example, a solvent used for the polymerization of the copolymer [A] can be used, and among them, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and propylene glycol methyl ether in view of solubility, reactivity, and convenience of coating film formation. Acetate is preferred. It is also possible to use a high boiling point solvent together with the solvent. As the high boiling point solvent, for example, N-methyl formamide, N, N-dimethyl formamide, N-methyl acetamide, N, N-dimethyl acetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzylethyl ether Etc. can be mentioned. When using such a high boiling point solvent together, it is preferable that the mixing ratio with the said solvent is "(the said solvent): (high boiling point solvent) = 50-100: 50-0".

In addition, the thermosetting resin composition of this invention may contain another component as needed within the scope of the technical idea of this invention. Other components herein include, for example, a surfactant for improving applicability. As surfactant, a fluorine or silicone type surfactant is mentioned, for example, 3M's FC-129, FC-170C, FC-430, etc. are mentioned. It may be used in an amount of 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 using surfactant more than 5 weight part with respect to 100 weight part of copolymers [A], there exists a problem which foams easily at the time of application | coating.

The thermosetting resin composition mixed as described above may be used after filtering using a filter having a diameter of about 0.1 ~ 5㎛.

The thermosetting resin composition of this invention can form a protective film by the following method, for example.

After applying a thermosetting resin composition to a board | substrate, removing a solvent and forming the coating film of a thermosetting resin composition, it can heat-process and can obtain a protective film.

As the substrate, for example, glass, quartz, silicone, resin, etc. may be used, and the resin may be a ring-opening polymer of polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide, and cyclic olefin. And its hydrogenated substance.

It does not specifically limit as a coating method of the said thermosetting resin composition solution, For example, a spray method, a roll coating method, a rotary coating method, etc. can be used.

The removal of the solvent is preferably carried out by heat treatment (pre-firing). Although the conditions of such preliminary baking differ with kinds, ratios, etc. of each component of a composition solution, it is preferable to bake about 0.5 to 20 minutes at 60-120 degreeC.

Subsequent heat treatment, the treatment temperature at this time can be treated for 10 to 100 minutes at 150 ~ 300 ℃ to produce a protective film for an optical device.

The thickness of the protective film formed as described above is preferably 0.1 to 6.0 µm, and when the unevenness is formed on the substrate forming the protective film, the value should be understood as the value at the top of the unevenness.

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

<Example 1>

5 parts by weight of 2,2'-azobis isobutyronitrile and 200 parts by weight of diethylene glycol dimethyl ether were added to 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 replacement, and stirring was gradually started. The temperature of the solution was raised to 80 ° C. and maintained at this temperature for 4 hours to obtain a polymer solution containing the copolymer [A1]. Solid content concentration of the obtained copolymer solution was 33.0 weight%.

100 parts by weight (solid content) of the obtained copolymer [A1], 5 parts by weight of EB-1290 (acrylic urethane resin, number average molecular weight 1000) manufactured by SK-UCB Corporation as the curable compound [B], and 3M FC as a surfactant. 0.1 parts by weight of -430 (fluorine-based surfactant) was mixed and dissolved in diethylene glycol dimethyl ether to obtain a solid concentration of 25%. Then, it filtered by the filter of 0.45 micrometers of pore diameters, and manufactured the thermosetting resin composition solution.

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

<Example 2>

In Example 1, 5 parts by weight of SK-UCB's EB-9260 (acrylic urethane resin, number average molecular weight 1500) as the curable compound [B] and 0.1 parts by weight of KP341 (silicone-based surfactant) from Shin-Etsu Silicone as a surfactant were mixed. A thermosetting resin composition solution was prepared in the same manner except for one, and a protective film was formed on the glass substrate in the same manner.

<Example 3>

In Example 1, 5 parts by weight of SK-UCB's EB-230 (acrylic urethane resin, number average molecular weight 5000) as the curable compound [B], 100 parts by weight of trimethylpropane trimethacrylate as the polymerizable compound [C], A thermosetting resin composition solution was prepared in the same manner except for mixing 5 parts by weight of benzoyl peroxide as a thermal radical polymerization initiator and 0.1 part by weight of FC430 (fluorine-based surfactant) manufactured by 3M as a surfactant, and a protective film on the glass substrate by the same method. Formed.

<Example 4>

In Example 1, 5 parts by weight of SK-UCB's EB-6700 (acrylic urethane resin, number average molecular weight 1500) as the curable compound [B], and 100 parts by weight of pentaerythritol tetramethacrylate as the polymerizable compound [C] Thermosetting resin composition in the same manner except that 5 parts by weight of 1,1′-azobis-1-cyclohexylnitrile as a thermal radical polymerization initiator and 0.1 parts by weight of KP341 (silicone surfactant) manufactured by Shin-Etsu Silicone Co., Ltd. were used as a surfactant. The solution was prepared, and a protective film was formed on the glass substrate in the same manner.

Example 5

In Example 1, 5 parts by weight of SK-UCB's EB-8800 (acrylic urethane resin, number average molecular weight 1700) as the curable compound [B], and 100 parts by weight of pentaerythritol tetramethacrylate as the polymerizable compound [C] Thermosetting resin composition in the same manner except that 5 parts by weight of 1,1′-azobis-1-cyclohexylnitrile as a thermal radical polymerization initiator and 0.1 parts by weight of KP341 (silicone surfactant) manufactured by Shin-Etsu Silicone Co., Ltd. were used as a surfactant. The solution was prepared, and a protective film was formed on the glass substrate in the same manner.

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, and a protective film was formed on the glass substrate by the same method.

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, and a protective film was formed on the glass substrate by the same method.

Comparative Example 3

A thermosetting resin composition solution was prepared in the same manner as in Comparative Example 2, except that the content of pentaerythritol tetraacrylate was increased to 150 parts by weight as the polymerizable compound [C], and a protective film was formed on the glass substrate by the same method. .

<Comparative Example 4>

A thermosetting resin composition solution was prepared in the same manner as in Example 1, except that Ebecryl 9970 (acrylic urethane resin, number average molecular weight 600) of SK-UCB was used as the curable compound [B]. A protective film was formed.

Comparative Example 5

Except that AK POL-2001 (polyol-based non-acrylic urethane resin) of Aekyung Petrochemical Co., Ltd. was used as the curable compound [B] in Example 1, a thermosetting resin composition solution was prepared in the same manner, and a protective film on the glass substrate in the same manner. Formed.

Evaluation method for the protective film used in the present invention is as follows, the evaluation results for the protective film prepared in Examples and Comparative Examples are shown in Table 1.

(1) adhesion

According to the checkered tape method (ASTM D3359), 100 checker marks were formed in a protective film by a cutter knife, and the adhesive test was done. The number of the checkerboard scales which peeled was measured, and the adhesiveness of a protective film was evaluated by the following reference | standard.

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

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

×: 50 or more pieces of checkered patterns

(2) surface hardness

According to the pencil hardness method (ASTM D3363), the pencil hardness test method was performed on the protective film to evaluate the surface hardness of the protective film.

(3) transparency

The transmittance of the protective film was measured at 400-700 nm using a spectrophotometer (UV-VIS spectrophotometer UV-3101PC of SHIMADZU), and the transparency of the protective film was evaluated according to the following criteria.

○: 95% minimum transmittance

△: 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 (2000mJ / cm 2). The transmission spectrum of the protective film before and after UV irradiation was measured, and UV resistance of the protective film was evaluated by 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, the transmission spectrum before and after heating was measured, and the heat resistance and the degree of yellowing of the protective film were evaluated by the following criteria.

○: Change in transmission spectrum is less than 1% (no yellowing)

X: 1% or more of change in transmission spectrum (with yellowing)

(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 a 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.

division Adhesion Surface hardness Transparency Leveling property UV resistance Heat resistance Acid resistance Alkali resistance Example 1 ○ 5H ○ 0.1 μm ○ ○ No change No change Example 2 ○ 5H ○ 0.1 μm ○ ○ No change No change Example 3 ○ 5H ○ 0.1 μm ○ ○ No change No change Example 4 ○ 5H ○ 0.1 μm ○ ○ No change No change Example 5 ○ 5H ○ 0.1 μm ○ ○ No change No change Comparative Example 1 ○ 3H ○ 0.3 μm × × No change No change Comparative Example 2 ○ 3H ○ 0.3 μm × × No change No change Comparative Example 3 ○ 3H ○ 0.3 μm × × No change No change Comparative Example 4 ○ 3H ○ 0.3 μm × × No change No change Comparative Example 5 ○ 3H ○ 0.3 μm × × No change No change

As a result of the physical property measurement, when the thermosetting resin of the present invention is used to form the color filter protective film on the substrate, it can be seen that the planarization, mechanical properties, UV resistance and heat resistance are particularly superior to the comparative example.

As described above, the thermosetting resin of the present invention has excellent planarization and mechanical properties, has UV resistance and heat resistance, and does not exhibit yellowing at high temperatures, and at the same time, a protective film having sufficient adhesion with a substrate, acid resistance and alkali resistance. Can be manufactured, and the thermosetting resin composition which is highly suitable as a protective film formation material for optical devices can be provided.

Claims (5)

In the thermosetting resin composition containing the copolymer [A] of (a1) unsaturated carboxylic acid or its anhydride, (a2) epoxy group containing unsaturated compound, and (a3) olefinic unsaturated compound, It is a curable compound [B], The number average molecular weight is 1000-5000, The thermosetting resin composition characterized by including the urethane oligomer which has an acryl group as a terminal group. The method of claim 1, The said curable compound [B] contains 1-10 weight part with respect to 100 weight part of said copolymers [A], The thermosetting resin composition characterized by the above-mentioned. The method of claim 1, The thermosetting resin composition further comprises a polymerizable compound [C] having an 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 of claim 1, The thermosetting resin composition further comprises 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]. The protective film for optical devices formed from the composition of any one of Claims 1-4.