KR20130092826A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE: A thermosetting resin composition is provided to have excellent mechanical property and heat resistance, and to offer a hardened film which does not have a yellowing phenomenon at a high temperature, and is suitable for an ingredient of optical device protection film. CONSTITUTION: A thermosetting resin composition comprises: copolymer [A] of unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride (a1), epoxy group contained unsaturated compound (a2), and olefin group unsaturated compound except for the (a1) and (a2); and a compound [B] having dioxolane group. The thermosetting resin composition comprises: less than 150 wt% of polymerizable compound having ethylenically unsaturated coupling, and less than 20 wt% of heat radical polymerization initiator to 100 wt% of the copolymer [A].

Description

Thermosetting resin composition

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

An optical device such as a liquid crystal display device is immersed in an organic solvent, an acid, an alkaline solution, or the like during the manufacturing process, or subjected to harsh processing such as high temperature heating locally on the surface by sputtering when forming a wiring electrode layer. Therefore, these devices may be provided with an overcoat on the surface in order to prevent the deterioration at the time of manufacture.

The 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 such that there is no alteration such as coloring, yellowing and whitening over a long period of time. What is excellent in chemical-resistance, such as 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 base substrate.

The protective film is a cured film of the curable resin composition, wherein the curable resin composition can be largely divided into thermosetting and photocurable (photosensitive). When the pattern formation of a protective film is needed, the photosensitive resin composition is calculated | required, otherwise a thermosetting resin composition is used. This is because the thermosetting resin composition is more convenient in the process than the photosensitive resin composition, the crosslinking density can be increased, and the mechanical properties and the heat resistance are excellent.

As an example of the technique related to the protective film manufactured from such a thermosetting resin composition, the technique of Unexamined-Japanese-Patent No. 2000103937, 2000119472, 2000143772 is mentioned.

As an example of the thermosetting resin composition used for forming a protective film, the composition containing the 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 are mainly used.

However, the conventional thermosetting resin composition having such a composition is not excellent in mechanical properties, in particular, the heat resistance is not good at high temperatures in many cases exhibited a yellowing phenomenon. In order to prevent such a phenomenon, the polyfunctional monomer containing an ethylenically unsaturated group may be excessively used, but such excessive use has a problem intensifying yellowing at a high temperature.

The present invention satisfies the characteristics required conventionally as a protective film, and effectively improves the crosslinking density, and thus is excellent in mechanical properties and heat resistance, and is very suitable as a protective film forming material for an optical device. To provide.

One embodiment of the present invention is a copolymer of [A] (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, (a2) epoxy group-containing unsaturated compound, (a3) olefinically unsaturated compounds other than (a1) and (a2) And; [B] a compound having a dioxolane group It is a thermosetting resin composition containing.

Another embodiment of the present invention is a thermosetting resin composition characterized in that the compound having a dioxolane group is any one or more selected from compounds represented by the following formula (1) to (7).

Formula 1

(2)

(3)

Formula 4

Formula 5

6

Formula 7

Another embodiment of the present invention is a thermosetting resin composition, characterized in that the compound having a dioxolane group is included in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the copolymer [A].

Another embodiment of the present invention, the thermosetting resin composition is 150 parts by weight or less based on 100 parts by weight of the polymerizable compound having an ethylenically unsaturated bond, 100 parts by weight of the copolymer [A] 100 parts by weight of the thermal radical polymerization initiator It is a thermosetting resin composition characterized by including 20 weight part or less with respect to a part.

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

In another embodiment of the present invention, the cured film is a color filter protective film of an optical device.

The thermosetting resin composition according to the present invention comprises a compound having a dioxolane group acting as a crosslinking agent together with a copolymer containing a carboxyl group or an epoxy group, so that its cured film satisfies the characteristics required in the past as a protective film, and also has a crosslinking density. Effectively improve the mechanical properties and heat resistance, there is no yellowing at high temperatures.

According to one embodiment of the invention, [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) copolymers of olefinically unsaturated compounds other than the above (a1) and (a2) (hereinafter referred to as compound (a3)); [B] a compound having a dioxolane group It is providing the thermosetting resin composition containing.

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

The copolymer [A] may contain the compound (a1) in an amount of 5 to 40% by weight, preferably 10 to 30% by weight, and this point means that the heat resistance, chemical resistance, surface hardness and copolymer of the resulting cured film It is preferable in consideration of storage stability.

As said compound (a1), For example, 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. Among these compounds can be used alone or in combination.

In addition, the copolymer [A] may contain 10 to 70% by weight of the compound (a2), preferably 20 to 60% by weight, which may take into account the heat resistance and surface hardness of the resulting cured film, or the storage stability of the copolymer. It may be desirable when considered.

Examples of the compound (a2) include glycidyl acrylate, glycidyl methacrylate, α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, 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 can be preferably used in view of increasing copolymerization reactivity and heat resistance and hardness of the resulting protective film. These compounds may be selected and used alone or in combination.

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

As said compound (a3), For example, Methacrylic acid alkyl esters, such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate; Acrylic acid alkyl esters such as methyl acrylate and isopropyl acrylate; Methacrylic acid cycloalkyl esters such as cyclohexyl methacrylate, 2-methyl cyclohexyl 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 petyl 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; Hydroxyalkyl 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, and the like. Among these, styrene, t-butyl methacrylate, dicyclopentenyl methacrylate, p-methoxy styrene, 2-methyl cyclohexyl acrylate, 1,3-butadiene, and the like may be preferable in terms of copolymerization reactivity and heat resistance. . Among these compounds, they may be used alone or in combination.

Such a copolymer [A] has a carboxyl group and / or a carboxylic anhydride group, and an epoxy group, and can harden | cure easily by heating, even without using a special hardening | curing agent.

As an example of the solvent which can be used for the synthesis | combination of the said copolymer [A], Alcohol, 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 a polymerization initiator which can be used for the synthesis | combination of the said 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 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, you may use it as a redox initiator by using a peroxide together with a reducing agent.

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

The compound having a dioxolane group is excellent in reactivity and the cured film obtained therefrom can secure a higher curing density, and as a result, the heat resistance, UV resistance, and chemical resistance of the cured film can be prevented.

The compound having such a dioxolane group is any one or more selected from the compounds represented by the following formulas (1) to (7).

Formula 1

(2)

(3)

Formula 4

Formula 5

6

Formula 7

The content of the compound [B] having the dioxolane group is 0.1 to 50 parts by weight, preferably 0.1 to 40 parts by weight based on 100 parts by weight of the copolymer [A] to form a cured film having a high crosslinking density or various resistance of the cured film. It can be advantageous in terms of preventing the problem that the properties of the cured film is unstable or the adhesion is reduced by preventing the remaining of the compound [B] having a dioxolane group in the side and satisfies the inside.

On the other hand, in another embodiment of the present invention, in addition to the copolymer [A] and the compound [B] having a dioxolane group, a polymerizable compound having an [C] ethylenically unsaturated bond (hereinafter referred to as a polymerizable compound [C]) And [D] thermal radical polymerization initiator (hereinafter referred to as thermal radical polymerization initiator [D]).

As said polymeric compound [C], monofunctional, bifunctional, or trifunctional or more than (meth) acrylate may be preferable from a viewpoint that a polymerizability is favorable and the heat resistance and surface hardness of the obtained cured film improve.

As said monofunctional (meth) acrylate, 2-hydroxy ethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxy butyl (meth) acryl And 2- (meth) acryloyl oxy ethyl-2-hydroxy propyl phthalate, and the like.

As said bifunctional (meth) acrylate, for example, ethylene glycol (meth) acrylate, 1,6-hexanediol (meth) acrylate, 1,9-nonanediol (meth) acrylate, propylene glycol ( Meta) acrylate, tetraethylene glycol (meth) acrylate, bisphenoxy ethyl alcohol fluorene diacrylate, and the like.

As said trifunctional or more than (meth) acrylate, for example, trishydroxyethyl isocyanurate tri (meth) acrylate, trimethyl propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol Tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned.

It can select from these monofunctional, bifunctional, or trifunctional or more (meth) acrylates, and can use individually or in combination.

When the polymerizable compound [C] is included in the thermosetting resin composition, the content thereof is 150 parts by weight or less, preferably 120 parts by weight or less, and more preferably 0.1 to 100 parts by weight based on 100 parts by weight of the copolymer [A]. It may be advantageous in terms of adhesion of the cured film.

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

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

The thermosetting resin composition of the present invention is prepared by uniformly mixing the above-mentioned copolymer [A] and compound [B] having a dioxolane group, polymerizable compound [C] and thermal radical polymerization initiator [D] as necessary. can do. 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 compound [B] having a dioxolane group, 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. It is prepared. The composition of this invention must contain the copolymer [A] and the compound [B] which has a dioxolane group.

As a solvent used for preparation of the thermosetting resin composition of this invention, each component of the copolymer [A], the compound [B] which has a dioxolane group, the polymeric compound [C], and the thermal radical polymerization initiator [D] is uniformly It can melt | dissolve and if it does not react with either component, it is all right. Specifically, For example, Alcohol, 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. Among these solvents, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate may be preferable 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.

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, and examples thereof include FC129, FC170C, FC430, and KP322, KP323, KP340, and KP341 manufactured by Shin-Etsu Silicone. Such surfactant is used in an amount of 5 parts by weight or less, preferably 2 parts by weight or less, and more preferably 0.1 to 1.5 parts by weight with respect to 100 parts by weight of the copolymer [A]. It may be advantageous in terms of prevention.

The composition solution prepared as described above may be 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, as follows, but the present invention is not limited by these Examples.

<Production Example>

2,2'-azo as a polymerization initiator based on 100 parts by weight of the total amount of monomers (compound (al), compound (a2), compound (a3)) used for the synthesis of the copolymer in a reaction vessel equipped with a cooling tube and a stirrer. 5 parts by weight of bis isobutyronitrile was dissolved in 200 parts by weight of diethylene glycol dimethyl ether as a solvent. Subsequently, 20 weight% of styrene, 30 weight% of methacrylic acid, 40 weight% of glycidyl methacrylate, and 10 weight% of dicyclopentenyloxyethyl methacrylate were added, nitrogen-substituted, and stirring was started gently.

The temperature of the solution was raised to 80 ° C. and maintained at this temperature for 4 hours to obtain a polymer solution containing a copolymer [A1]. Solid content concentration of the obtained polymer solution was 33 weight%.

&Lt; Example 1 >

100 parts by weight of the copolymer [A1] obtained in the preparation example (based on the solid content) and 100 parts by weight of the copolymer [A1] as a compound [B] having a dioxolane group as a mood, 20 parts by weight of the compound represented by the formula (1) And 0.1M by weight of 3M FC430 (fluorine-based surfactant) as a surfactant was mixed and dissolved in diethylene glycol dimethyl ether and N-methyl pyrrolidone mixed solvent (weight ratio 80:20) so that the solid content 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 (S1).

<Example 2>

100 parts by weight of the copolymer [A1] obtained in the preparation example (based on the solid content) and 100 parts by weight of the copolymer [A1] as a compound [B] having a dioxolane group as a mood, 20 parts by weight of the compound 0.1 parts by weight of Shin-Etsu Silicone KP341 (silicone-based surfactant) as a surfactant was dissolved in a mixed solvent of diethylene glycol dimethyl ether and N-methyl pyrrolidone (weight ratio 80:20), so that the solid content concentration was 25% by weight. It was. Then, it filtered by the filter of 0.45 micrometers of pore diameters, and prepared the thermosetting resin composition solution (S2).

<Example 3>

100 parts by weight of the copolymer [A1] obtained in the preparation example (based on the solid content) and 100 parts by weight of the copolymer [A1] as a compound [B] having a dioxolane group as a mood, 20 parts by weight of the compound 100 parts by weight of trimethylpropane trimethacrylate as the polymerizable compound [C], 5 parts by weight of benzoyl peroxide as the thermal radical polymerization initiator [D], and 3 parts by weight of FC430 (0.1 part by weight of fluorine-based surfactant) as a surfactant. After dissolving in a mixed solvent of glycol dimethyl ether and N-methyl pyrrolidone (weight ratio 80:20), the solid content concentration was 25% by weight, and then filtered through a filter having a pore diameter of 0.45 占 퐉 (S3). ) Prepared.

<Example 4>

100 parts by weight of the copolymer [A1] obtained in the preparation example (based on the solid content) and 100 parts by weight of the copolymer [A1] as a compound [B] having a dioxolane group as a mood, 20 parts by weight of the compound represented by the formula (4) 100 parts by weight of pentaerythritol tetramethacrylate as the polymerizable compound [C], 5 parts by weight of 1,1'-azobis-1-cyclohexylnitrile as the thermal radical polymerization initiator [D], and KP341 as a surfactant. (Silicon Surfactant) 0.1 weight part was mixed, and it melt | dissolved in the mixed solvent (weight ratio 80:20) of diethylene glycol dimethyl ether and N-methyl pyrrolidone, and made solid content concentration 25 weight%. Then, it filtered by the filter of 0.45 micrometers of pore diameters, and prepared the thermosetting resin composition solution (S4).

<Example 5>

100 parts by weight of the copolymer [A1] obtained in the preparation example (based on solids content) and 100 parts by weight of the copolymer [A1] as a compound [B] having a dioxolane group as a mood, 20 parts by weight of a compound represented by the formula (5) 100 parts by weight of dipentaerythritol pentamethacrylate as the polymerizable compound [C], 5 parts by weight of 1,1'-azobis-1-cyclohexylnitrile as the thermal radical polymerization initiator [D], and Shin-Etsu Silicone Co., Ltd. as a surfactant. 0.1 parts by weight of KP341 (silicone-based surfactant) was mixed and dissolved in a mixed solvent of diethylene glycol dimethyl ether and N-methyl pyrrolidone (weight ratio 80:20), so that the solid content 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 (S5).

&Lt; Comparative Example 1 &

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

Comparative Example 2

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

&Lt; Comparative Example 3 &

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

&Lt; Formation of cured film &

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

Evaluation methods for the aforementioned examples and comparative examples are as follows.

(1) Adhesiveness

According to the checkered tape method, using a cutter knife on the hard film , cut 11 rows of cuts of 1 mm apart to the upper surface of the glass substrate, and then cut 11 rows of cuts of 1 mm vertically to the upper depth of the glass substrate. After the checkered pattern was formed, an adhesive test (Elcometer, Part Number K0001539M001) was applied to the checkered pattern and then peeled off. The number of peeled checkered 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

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

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 the 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 α 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 (degree of yellowing)

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 for 60 minutes at 240 degreeC clean oven, and the transmittance | permeability was measured by the same method. 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

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

(8) alkali resistance

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

The evaluation results are shown in Table 1 below.

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

From the results of Table 1, it can be seen that when including a compound having a dioxolane group as the curable compound, by increasing the crosslinking density effectively, surface hardness is improved, planarization is improved, and UV resistance and heat resistance are also improved. .

When the compound having a polyfunctional ethylenically unsaturated group as in Comparative Example 3 is used in excess, the point of forming a cured film having a surface hardness of about 5H may be comparable, but the yellowing phenomenon is intensified due to poor heat resistance.

Claims (6)

[A] (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, (a2) epoxy group-containing unsaturated compound, (a3) copolymer of olefinically unsaturated compounds other than (a1) and (a2);
[B] a compound having a dioxolane group Thermosetting resin composition comprising. The thermosetting resin composition according to claim 1, wherein the compound having a dioxolane group is any one or more selected from compounds represented by the following Chemical Formulas 1 to 7.
Formula 1

(2)

(3)

Formula 4

Formula 5

6

Formula 7

The thermosetting resin composition according to claim 1, wherein the compound having a dioxolane group is contained in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the copolymer [A]. The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition is 150 parts by weight or less based on 100 parts by weight of the polymerizable compound having an ethylenically unsaturated bond, and 100 parts by weight of the thermal radical polymerization initiator is added to 100 parts by weight of the copolymer [A]. It contains less than 20 weight part with respect to the thermosetting resin composition characterized by the above-mentioned. The cured film manufactured from the thermosetting resin composition of any one of Claims 1-4. The cured film of claim 5, wherein the cured film is a color filter protective film of an optical device.