KR20120078500A - Setting resin composition and overcoat layer - Google Patents

Abstract

PURPOSE: A curable resin composition is provided to improve chemical resistance and adhesion by comprising a compound having an oxetane group. CONSTITUTION: A curable resin composition comprises a copolymer, a curable compound, and a compound having oxetane group. The copolymer consists of an unsaturated carboxylic acid, or carboxylic anhydride, and an epoxy group-containing unsaturated compound, and olefin based unsaturated compound except the unsaturated carboxylic acid, the carboxylic anhydride, and the epoxy group-containing unsaturated compound. The resin composition comprises 100.0 parts by weight comprises 1-50 parts by weight of a curable compound, 1-50 parts by weight of a compound having an oxetane group.

Description

Curable resin composition {Setting resin composition and overcoat layer}

The present invention relates to a curable resin composition.

Optical devices such as liquid crystal display elements are subjected to harsh processing such as immersion treatment with organic solvents, acids, alkali solutions, etc. during the manufacturing process, or locally heated to the surface by sputtering when forming wiring electrode layers. . 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 various treatments as described above, and has excellent adhesion with the substrate or lower layer, high smoothness, surface hardness, and transparency, and excellent heat resistance and light resistance without deterioration such as coloring, yellowing, and whitening over the long term. What is excellent in chemical-resistance, such as alkali resistance, water resistance, etc. is calculated | required.

In particular, when the etching process is involved in the manufacture of optical devices, excellent acid resistance and adhesion are required to protect the substrate from strong acids and to improve processability.

That is, as a protective film, a material that satisfies the above characteristics, in particular, is excellent in acid resistance and adhesion, which protects a color filter, which is a base material, and improves etching processability.

The present invention provides a curable resin composition having improved chemical resistance properties.

One embodiment of the present invention is a-1) unsaturated carboxylic acid or unsaturated carboxylic anhydride, a-2) epoxy group-containing unsaturated compound, a-3) copolymers of olefinically unsaturated compounds other than a-1) and a-2) It is a curable resin composition containing the compound which has a curable compound and an oxetane group.

Another embodiment of the present invention is a curable resin composition containing 1 to 50 parts by weight of the curable compound and 1 to 50 parts by weight of the compound having an oxetane group based on 100 parts by weight of the copolymer.

Curable resin composition of this invention can obtain the effect that a chemical-resistance characteristic and adhesiveness improve.

According to one embodiment of the present invention, a-1) unsaturated carboxylic acid or unsaturated carboxylic anhydride, a-2) epoxy group-containing unsaturated compound, a-3) of olefinically unsaturated compounds other than a-1) and a-2) It is providing the curable resin composition containing the compound which has a copolymer, a curable compound, and an oxetane group.

The present invention will be described in more detail as follows.

(1) copolymer A

Curable resin composition according to an embodiment of the present invention is a-1) unsaturated carboxylic acid or unsaturated carboxylic anhydride, a-2) epoxy group-containing unsaturated compound, a-3) olefins other than a-1) and a-2) Copolymers of unsaturated compounds. In the present invention, the copolymer is referred to as copolymer A.

Copolymer A used in the present invention contains 10 to 40% by weight, preferably 10 to 30% by weight of structural units derived from compound a-1, in terms of heat resistance, chemical resistance, surface hardness and storage stability. Can be. Specific examples of the compound a-1 include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; And anhydrides of these dicarboxylic acids. Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used in view of copolymerization reactivity, heat resistance and easy availability. These compounds a-1 can be used individually or in combination.

In addition, the copolymer A may be advantageous in terms of heat resistance, surface hardness and storage stability of the cured film to contain 20 to 70% by weight, preferably 20 to 60% by weight of structural units derived from compound a-2. Specific examples of the compound a-2 include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 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 copolymerization reactivity and heat resistance and hardness of the resulting protective film. These compounds a-2 can be used alone or in combination.

On the other hand, the copolymer A may be advantageous in terms of storage stability, heat resistance and surface hardness to contain 20 to 70% by weight, preferably 20 to 50% by weight of structural units derived from compound a-3. Specific examples of the compound a-3 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-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 isobononyl 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 fmarate 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. Dual styrene, t-butyl methacrylate, dicyclopentenyl methacrylate, p-methoxy styrene, 2-methyl cyclohexyl acrylate, 1,3-butadiene and the like are preferred in view of copolymerization reactivity and heat resistance. These compounds a-3 can be used alone or in combination.

Copolymer A obtained from the above compounds a-1, a-2 and a-3 has a carboxyl group or a carboxylic anhydride group and an epoxy group, and can be easily cured by heating without using a special curing agent.

As a solvent which can be used for the synthesis | combination of copolymer A, Alcohol, such as methyl alcohol and ethyl alcohol; Ethers such as tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol ethyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol ethyl methyl ether; Propylene glycol alkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether and propylene glycol butyl ether; 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; Propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, and methyl isoamyl ketone; And methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxy propionate, methyl 2-hydroxy-2-methyl propionate, ethyl 2-hydroxy-2-methyl propionate, methyl hydroxy acetate, hydroxy acetate Ethyl, hydroxy butyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxy propionate methyl, 3-hydroxy ethyl propionate, 3-hydroxy propionic acid propyl, 3-hydroxy butyl propionate, 2-hydroxy Methyl oxy-3-methyl butyrate, methyl methoxy acetate, methoxy ethyl acetate, methoxy propyl acetate, methoxy butyl acetate, ethoxy methyl acetate, ethoxy ethyl acetate, ethoxy propyl acetate, butyl ethoxy acetate, pro Methyl Foxoxy Acetate, Propoxy Ethyl Acetate, Propoxy Acetate, Butyl Propoxy Acetate, Methyl Butoxy Acetate, Butoxy Ethyl Acetate, Butoxy Propyl Acetate, Butyl Propoxy Acetate, Butoxy Methyl Acetate, Butoxy ethyl acetate, butoxy propyl acetate, butyl butoxy acetate, methyl 2-methoxy propionate, ethyl 2-methoxy propionate, propyl 2-methoxy propionic acid, butyl 2-methoxy propionate, methyl 2-ethoxy propionate, Ethyl 2-ethoxy propionate, propyl 2-ethoxy propionate, butyl 2-ethoxy propionate, methyl 2-butoxy propionate, ethyl 2-butoxy propionate, propyl 2-butoxy propionate, butyl 2-butoxy propionate, 3 -Methoxypropionate, 3-methoxy ethylpropionate, 3-methoxy propionic acid propyl, 3-methoxy propionic acid butyl, 3-ethoxy propionic acid methyl, 3-ethoxy propionic acid, 3-ethoxy propionic acid propyl, 3- Butyl ethoxy propionate, methyl 3-propoxy propionate, ethyl 3-propoxy propionate, propyl 3-propoxy propionate, butyl 3-propoxy propionate, 3-butoxy propionic acid Butyl, can be given a 3-butoxy-ethyl, 3-butoxy-propionic acid propyl esters such as 3-butoxy-propionic acid butyl.

In addition, as a polymerization initiator which can be used for the synthesis | combination of copolymer A, as long as it is generally known as a radical polymerization initiator, any 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 using a peroxide as a radical polymerization initiator, you may use as a redox initiator by using a peroxide together with a reducing agent.

(2) curable compound

The present invention includes a curable compound as a compound that acts as a curing agent for curing the copolymer A as described above, and examples thereof include a compound represented by the following formula (1).

Formula 1

In the above formula, X is a monovalent amine group or an isocyanate group, and Y is one or two or more divalent groups selected from the following general formulas (2) or (3).

Formula 2

(In Formula 2, n is an integer of 1 to 15.)

Formula 3

In the present invention, the compound represented by Formula 1 may act as a curing agent for the copolymer A.

The curable compound may be one or two or more selected from compounds represented by the following Chemical Formulas 4 to 9.

Formula 4

Wherein R ₁ is — (CH ₂ ) ₆ —.

Formula 5

이다.Wherein R ₂ is

to be.

6

Wherein R ₁ is — (CH ₂ ) ₆ —.

Formula 7

이다.
Wherein R ₂ is

to be.

Formula 8

이다.
Wherein R ₃ is

to be.

Formula 9

Wherein R ₁ is — (CH ₂ ) ₆ —.

In addition, bisphenol A alcohols represented by the following formula (10) and methacrylates or epoxy derived therefrom; Alternatively, one or two or more compounds selected from phenols represented by the following formula (11) may be included as the curable compound.

Formula 10

Where R ₁ is -H, -OH,-(CH ₂ ) n-OH (n is an integer from 1 to 5),-(CH ₂ ) n-CH ₃ (n is an integer from 0 to 5),-(CH ₂ ) n-CH = CH ₂ (n is an integer of 1 to 5),-(CH ₂ ) n-CH = CH- (CH ₂ ) n'-CH ₃ (n is an integer of 1 to 5, n 'is an integer of 0 to 5) .

Formula 11

,

,

(n은 1~5의 정수),

(n은 1~5의 정수),

(n은 1~5의 정수),

,

,

,

(n은 0~5의 정수),

(n은 1~5의 정수),

(n은 1~5의 정수) 또는

(n은 0~5의 정수)이다.
In Formula 11, R ₁ , R _2, and R ₃ are -H, -OH,-(CH ₂ ) n -OH (n is an integer of 1 to 5),-(CH ₂ ) n-CH ₃ (n is An integer of 0 to 5),-(CH ₂ ) n-CH = CH ₂ (n is an integer of 1 to 5),-(CH ₂ ) n-CH = CH- (CH ₂ ) n'-CH ₃ (n Is an integer of 1 to 5, n 'is an integer of 0 to 5),

,

,

(n is an integer from 1 to 5),

(n is an integer from 1 to 5),

(n is an integer from 1 to 5),

,

,

,

(n is an integer from 0 to 5),

(n is an integer from 1 to 5),

(n is an integer from 1 to 5) or

(n is an integer of 0-5).

The curable compound is preferably contained 1 to 50 parts by weight, preferably 5 to 20 parts by weight based on 100 parts by weight of copolymer A. When the curable compound is in the above range, an effect of improving hardness, heat resistance, and acid resistance can be obtained.

If the curable compound is not included or is added in a small amount below the above range, the curing density is lowered. Therefore, the hardness and heat resistance is poor, and also has an adverse effect on the acid resistance (etch resistance). In the case of including the compound having an oxetane group according to the present invention, the chemical resistance and adhesion are remarkably improved, but the curable compound is contained in a predetermined amount or more so that the curing density is secured to a certain level to obtain the effect of obtaining the compound having the oxetane group. have.

(3) a compound having an oxetane group

The compound having an oxetane group according to the present invention increases the degree of curing of the epoxy compound and serves to improve the electrical properties due to its good water resistance. Specifically, bis [1-Ethyl (3-oxetanyl)] methyl ether may be mentioned. .

The compound having the oxetane group is preferably contained 1 to 50 parts by weight, preferably 5 to 20 parts by weight based on 100 parts by weight of copolymer A. When the compound having the oxetane group is in the above range, it is possible to obtain an effect of improving acid resistance (etch resistance) and adhesion.

When including the above-mentioned configuration, the curable resin composition according to the present invention can obtain the effect of improving the chemical resistance.

Specifically, in the present invention, by increasing the curing density and introducing a compound having an oxetane group, the effect of improving the chemical resistance can be obtained.

(4) other

The curable resin composition according to an embodiment of the present invention may contain a polymerizable compound having an ethylenically unsaturated bond and / or a thermal radical polymerization initiator in addition to the copolymer A, the curable compound, and the compound having an oxetane group. .

As said polymeric compound, a monofunctional, bifunctional, or trifunctional or more than methacrylate is preferable from a viewpoint that a polymerizability is favorable and the heat resistance and surface hardness of the protective film obtained are improved.

Examples of monofunctional methacrylates include 2-hydroxy ethyl methacrylate, carbitol methacrylate, isobornyl methacrylate, 3-methoxy butyl methacrylate, 2-methacryloyl oxy ethyl 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, and propylene glycol (meth) acryl The rate, 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, 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 is included in the curable resin composition, the content thereof may be 50 parts by weight or less, preferably 30 parts by weight or less, and more preferably 10 to 20 parts by weight, based on 100 parts by weight of copolymer A. have.

On the other hand, as the thermal radical polymerization initiator, 2,2'-azobis isobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4- Azo compounds such as 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 curable resin composition of the present invention may be prepared by uniformly mixing each of the above-mentioned copolymer A, the curable compound, the compound having an oxetane group or the polymerizable compound, and the thermal radical polymerization initiator, and usually, the curable resin of the present invention. The composition is dissolved in a suitable solvent and used in solution. That is, copolymer A, a curable compound, a compound having a polymerizable compound and an oxetane group, a thermal radical polymerization initiator, and other additives are mixed at a predetermined ratio to prepare a curable resin composition in a solution state.

As a solvent which can be used for preparation of curable resin composition, each component which comprises curable resin composition can be melt | dissolved uniformly, and what does not react with any component can be used. Specifically, Alcohol, such as methyl alcohol and ethyl alcohol; Ethers such as tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol ethyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol ethyl methyl ether; Propylene glycol alkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propylether and propylene glycol butyl ether; 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; Propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, and methyl isoamyl ketone; And methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxy propionate, methyl 2-hydroxy-2-methyl propionate, ethyl 2-hydroxy-2-methyl propionate, methyl hydroxy acetate, hydroxy acetate Ethyl, hydroxy butyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxy propionate methyl, 3-hydroxy propionate ethyl, 3-hydroxy propionic acid propyl, 3-hydroxy propionate butyl, 2-hydroxy Methyl oxy-3-methyl butyrate, methyl methoxy acetate, methoxy ethyl acetate, methoxy propyl acetate, methoxy butyl acetate, ethoxy methyl acetate, ethoxy ethyl acetate, ethoxy propyl acetate, ethoxy butyl acetate, pro Methyl Foxoxy Acetate, Propoxy Ethyl Acetate, Propoxy Acetate, Butyl Propoxy Acetate, Methyl Butoxy Acetate, Butoxy Ethyl Acetate, Butoxy Propyl Acetate, Butyl Propoxy Acetate, Butoxy Methyl Acetate, Butoxy ethyl acetate, butoxy propyl acetate, butyl butoxy acetate, methyl 2-methoxy propionate, ethyl 2-methoxy propionate, propyl 2-methoxy propionic acid, butyl 2-methoxy propionate, methyl 2-ethoxy propionate, Ethyl 2-ethoxy propionate, propyl 2-ethoxy propionate, butyl 2-ethoxy propionate, methyl 2-butoxy propionate, ethyl 2-butoxy propionate, propyl 2-butoxy propionate, butyl 2-butoxy propionate, 3 Methyl methoxy propionate, 3-methoxy ethyl propionate, 3-methoxy propionic acid propyl, 3-methoxy propionic acid butyl, 3-ethoxy propionic acid methyl, 3-ethoxy propionic acid, 3-ethoxy propionic acid propyl, 3- Butyl ethoxy propionate, methyl 3-propoxy propionate, ethyl 3-propoxy propionate, propyl 3-propoxy propionate, butyl 3-propoxy propionate, 3-butoxy propionic acid Ester, such as methyl, 3-butoxy ethyl propionate, 3-butoxy propyl propionate, and 3-butoxy butyl butyl propionate, is mentioned. Among these solvents, glycol ethers, ethylene glycol alkyl ether acetates, esters, and diethylene glycol ethers are 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, N-methylformamide, N, N-dimethyl formamide, N-methyl acetamide, N, N-dimethyl acetamide, N-methyl pyrrolidone, dimethyl sulfoxide, benzyl ethyl ether Etc. can be mentioned.

In addition, the curable resin composition of the present invention may include an adhesion aid to improve the adhesion to the substrate. A functional silane coupling agent is preferably used as the adhesion aid, for example trimethoxy silyl benzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ- Isocyanate propyl triethoxysilane, (gamma)-glycidoxy propyl trimethoxysilane, etc. are mentioned. Such adhesion aid may be used in an amount of 20 parts by weight or less, preferably 10 parts by weight or less, based on 100 parts by weight of copolymer A. When the amount of the adhesion aid exceeds 20 parts by weight, the heat resistance tends to be lowered.

The composition solution prepared as described above is used after filtering using a Millipore filter having a pore diameter of about 0.2 to 0.5 μm.

The target protective film can be obtained by apply | coating curable resin composition of this invention to a base base material, and processing it for 10 to 80 minutes at 160-260 degreeC in oven.

The curable protective film thus obtained has a haze of 5.0 or less, and preferably a haze of an ITO deposited film of 2.0 or less, formed on the protective film at 250 占 폚 at a thickness of 1500 kPa.

In order to satisfy such a haze, when a curable protective film also evaluates the adhesive force with an ITO vapor deposition film, it is preferable that the number of the checkerboard patterns peeled off is five or less.

Such a curable protective film is useful as a color filter protective film, and can be applied to both an IPS method or a TN method, and may be particularly useful for fabricating a liquid crystal display device having a structure for forming a color filter on a thin film transistor substrate, that is, an array substrate. have.

Hereinafter, preferred embodiments and comparative examples of the present invention will be described. However, the following embodiments are merely preferred embodiments of the present invention, and the present invention is not limited to the following embodiments.

≪ 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, 10 parts by weight of styrene, 15 parts by weight of methacrylic acid, 55 parts by weight of glycidyl methacrylate, and 20 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 22 weight%.

100 parts by weight (based on solids content) of the obtained copolymer [A-1], 10 parts by weight of a urethane curable compound represented by the formula (8) as a curable compound, and a compound having an oxetane group (bis [1-Ethyl (3-oxetanyl)] methyl ether) was mixed with 10 parts by weight of a mixture of diethylene glycol dimethyl ether and diethylene glycol methyl ethyl ether (90:10) to obtain a solid content of 23% 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, 10 parts by weight of styrene, 15 parts by weight of methacrylic acid, 55 parts by weight of glycidyl methacrylate, and 20 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 22 weight%.

100 parts by weight (based on solids content) of the obtained copolymer [A-1], 10 parts by weight of a urethane curable compound represented by the formula (8) as a curable compound, and a compound having an oxetane group (bis [1-Ethyl (3-oxetanyl)] methyl ether) 10 parts by weight and 10 parts by weight of a polymerizable compound (bisphenol A acrylate) having an ethylenically unsaturated bond were mixed and dissolved in a mixed solvent of diethylene glycol dimethyl ether and diethylene glycol methyl ethyl ether (90:10). After the solid content concentration was 23% 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, 10 parts by weight of styrene, 15 parts by weight of methacrylic acid, 55 parts by weight of glycidyl methacrylate, and 20 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 22 weight%.

100 parts by weight (based on solids content) of the obtained copolymer [A-1], 1 part by weight of a urethane curable compound represented by the formula (8) as a curable compound, and a compound having an oxetane group (bis [1-Ethyl (3-oxetanyl)] methyl ether) 10 parts by weight and 10 parts by weight of a polymerizable compound (bisphenol A acrylate) having an ethylenically unsaturated bond were mixed and dissolved in a mixed solvent of diethylene glycol dimethyl ether and diethylene glycol methyl ethyl ether (90:10). After the solid content concentration was 23% by weight. 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, 10 parts by weight of styrene, 15 parts by weight of methacrylic acid, 55 parts by weight of glycidyl methacrylate, and 20 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 22 weight%.

100 parts by weight (based on solids content) of the obtained copolymer [A-1], 20 parts by weight of a urethane curable compound represented by the formula (8) as a curable compound, and a compound having an oxetane group (bis [1-Ethyl (3-oxetanyl)] methyl ether) 10 parts by weight and 10 parts by weight of a polymerizable compound (bisphenol A acrylate) having an ethylenically unsaturated bond were mixed and dissolved in a mixed solvent of diethylene glycol dimethyl ether and diethylene glycol methyl ethyl ether (90:10). After the solid content concentration was 23% 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, 10 parts by weight of styrene, 15 parts by weight of methacrylic acid, 55 parts by weight of glycidyl methacrylate, and 20 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 22 weight%.

100 parts by weight (based on solids content) of the obtained copolymer [A-1], 50 parts by weight of a urethane curable compound represented by the formula (8) as a curable compound, and a compound having an oxetane group (bis [1-Ethyl (3-oxetanyl)] methyl ether) 10 parts by weight and 10 parts by weight of a polymerizable compound (bisphenol A acrylate) having an ethylenically unsaturated bond were mixed and dissolved in a mixed solvent of diethylene glycol dimethyl ether and diethylene glycol methyl ethyl ether (90:10). After the solid content concentration was 23% by weight. Then, it filtered by the filter of 0.45 micrometers of pore diameters, and prepared the thermosetting resin composition solution (S-5).

<Example 6>

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, 10 parts by weight of styrene, 15 parts by weight of methacrylic acid, 55 parts by weight of glycidyl methacrylate, and 20 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 22 weight%.

100 parts by weight (based on solids content) of the obtained copolymer [A-1], 10 parts by weight of a urethane curable compound represented by the formula (8) as a curable compound, and a compound having an oxetane group (bis [1-Ethyl (3-oxetanyl)] methyl ether) 1 part by weight and 10 parts by weight of a polymerizable compound (bisphenol A acrylate) having an ethylenically unsaturated bond were dissolved in a mixed solvent of diethylene glycol dimethyl ether and diethylene glycol methyl ethyl ether (90:10). After the solid content concentration was 23% by weight. Then, it filtered by the filter of 0.45 micrometers of pore diameters, and prepared the thermosetting resin composition solution (S-6).

<Example 7>

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, 10 parts by weight of styrene, 15 parts by weight of methacrylic acid, 55 parts by weight of glycidyl methacrylate, and 20 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 22 weight%.

100 parts by weight (based on solids content) of the obtained copolymer [A-1], 10 parts by weight of a urethane curable compound represented by the formula (8) as a curable compound, and a compound having an oxetane group (bis [1-Ethyl (3-oxetanyl)] methyl ether) 20 parts by weight and 10 parts by weight of a polymerizable compound having a ethylenically unsaturated bond (bisphenol A acrylate) were mixed and dissolved in a mixed solvent of diethylene glycol dimethyl ether and diethylene glycol methyl ethyl ether (90:10). After the solid content concentration was 23% by weight. Then, it filtered by the filter of 0.45 micrometers of pore diameters, and prepared the thermosetting resin composition solution (S-7).

&Lt; Example 8 >

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, 10 parts by weight of styrene, 15 parts by weight of methacrylic acid, 55 parts by weight of glycidyl methacrylate, and 20 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 22 weight%.

100 parts by weight (based on solids content) of the obtained copolymer [A-1], 10 parts by weight of a urethane curable compound represented by the formula (8) as a curable compound, and a compound having an oxetane group (bis [1-Ethyl (3-oxetanyl)] methyl ether) 50 parts by weight and 10 parts by weight of a polymerizable compound having a ethylenically unsaturated bond (bisphenol A acrylate) were mixed and dissolved in a mixed solvent of diethylene glycol dimethyl ether and diethylene glycol methyl ethyl ether (90:10). After the solid content concentration was 23% by weight. Then, it filtered by the filter of 0.45 micrometers of pore diameters, and prepared the thermosetting resin composition solution (S-8).

&Lt; Example 9 >

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, 10 parts by weight of styrene, 15 parts by weight of methacrylic acid, 55 parts by weight of glycidyl methacrylate, and 20 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 22 weight%.

100 parts by weight (based on solids content) of the obtained copolymer [A-1], 10 parts by weight of the urethane curable compound represented by the formula (8) as the curable compound [B], and a compound having an oxetane group (bis [1-Ethyl (3-oxetanyl 10 parts by weight of methyl ether) and 1 part by weight of a polymerizable compound (bisphenol A acrylate) having an ethylenically unsaturated bond were mixed with diethylene glycol dimethyl ether and diethylene glycol methyl ethyl ether (90:10). After dissolving in, the solid content concentration was 23% by weight. Then, it filtered by the filter of 0.45 micrometers of pore diameters, and prepared the thermosetting resin composition solution (S-9).

<Example 10>

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, 10 parts by weight of styrene, 15 parts by weight of methacrylic acid, 55 parts by weight of glycidyl methacrylate, and 20 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 22 weight%.

100 parts by weight (based on solids content) of the obtained copolymer [A-1], 10 parts by weight of a urethane curable compound represented by the formula (8) as a curable compound, and a compound having an oxetane group (bis [1-Ethyl (3-oxetanyl)] methyl ether) 10 parts by weight and 20 parts by weight of a polymerizable compound (bisphenol A acrylate) having an ethylenically unsaturated bond were dissolved in a mixed solvent of diethylene glycol dimethyl ether and diethylene glycol methyl ethyl ether (90:10). After the solid content concentration was 23% by weight. Then, it filtered by the filter of 0.45 micrometers of pore diameters, and prepared the thermosetting resin composition solution (S-10).

<Example 11>

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, 10 parts by weight of styrene, 15 parts by weight of methacrylic acid, 55 parts by weight of glycidyl methacrylate, and 20 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 22 weight%.

100 parts by weight (based on solids content) of the obtained copolymer [A-1], 10 parts by weight of a urethane curable compound represented by the formula (8) as a curable compound, and a compound having an oxetane group (bis [1-Ethyl (3-oxetanyl)] methyl ether) 10 parts by weight, and 50 parts by weight of a polymerizable compound (bisphenol A acrylate) having an ethylenically unsaturated bond were dissolved in a mixed solvent of diethylene glycol dimethyl ether and diethylene glycol methyl ethyl ether (90:10). After the solid content concentration was 23% by weight. Then, it filtered by the filter of 0.45 micrometers of pore diameters, and prepared the thermosetting resin composition solution (S-11).

&Lt; Comparative 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, 10 parts by weight of styrene, 15 parts by weight of methacrylic acid, 55 parts by weight of glycidyl methacrylate, and 20 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 22 weight%.

100 parts by weight (based on solids content) of the obtained copolymer [A-1], 10 parts by weight of a compound having an oxetane group (bis [1-Ethyl (3-oxetanyl)] methyl ether) and a polymerizable compound having an ethylenically unsaturated bond 10 parts by weight of (bisphenol A acrylate) was mixed and dissolved in a mixed solvent of diethylene glycol dimethyl ether and diethylene glycol methyl ethyl ether (90:10), so that the solid content concentration was 23% by weight. Then, it filtered by the filter of 0.45 micrometers of pore diameters, and prepared the thermosetting resin composition solution (S-12).

Comparative 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, 10 parts by weight of styrene, 15 parts by weight of methacrylic acid, 55 parts by weight of glycidyl methacrylate, and 20 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 22 weight%.

100 parts by weight of the obtained copolymer [A-1] (based on the solid content), 10 parts by weight of the urethane-based curable compound represented by the formula (8) as the curable compound, and 10 parts by weight of the polymerizable compound [D] having an ethylenically unsaturated bond, After dissolving in ethylene glycol dimethyl ether and diethylene glycol methyl ethyl ether mixed solvent (90:10), the solid content concentration was 23% by weight. Then, it filtered by the filter of 0.45 micrometers of pore diameters, and prepared the thermosetting resin composition solution (S-13).

Experimental Example

Example 1 to the above The curable resin composition obtained from 11 and Comparative Examples 1 and 2 was applied on the substrate using a spin coater so as 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 substrate (protective film thickness 1.5). Μm).

After forming the protective film, etchant resistance, etching margin, surface hardness, transparency, adhesion, and heat resistance were measured in the following manners, and the results are shown in Table 2 below.

1) Etchant resistance: The substrate with the protective film was immersed in an etchant (47.5% hydrochloric acid, 5% nitric acid, 47.5% water) solution at 80 ° C. for 120 minutes, and then the change in appearance of the protective film was observed to evaluate the etchant resistance. . The change in the appearance of the protective film was quantified by the change in the thickness of the protective film before and after the etchant immersion.

○-Less than 5% change in protective film thickness

△-protective film thickness change rate 5% or more and less than 10%

×-Protective film thickness change rate 10% or more

2) Etch margin: After the ITO deposition process is performed on the substrate on which the protective film is formed, a pattern is formed through an etching process and a stripping process. Etch margin was quantified by the ratio of the size of the actual pattern to the lattice size of the mask used for pattern formation.

○-95% or more etching margin

△-etching margin 85% or more and less than 95%

×-Etching margin less than 85%

3) Surface Hardness: According to the pencil hardness method, the surface hardness of the protective film was evaluated by performing a pencil hardness test on the protective film.

4) Transparency: The transmittance of the protective film was measured at 400 to 700 nm using a spectrophotometer (UV-3101PC, manufactured by Shimadzu), and the transparency of the protective film was evaluated according to the following criteria.

○-minimum transmittance of more than 97%

△-minimum transmittance exceeding 95 to 97%

×-minimum transmittance of less than 95%

5) Adhesion: According to the checkered tape method (ASTM D3359), 100 checker marks were formed on the protective film with a cutter knife to perform an adhesion test. The number of the checkerboard scales which peeled was measured, and the adhesiveness of a protective film was evaluated by the following criteria.

○-5 or less peeled checkerboard

△-6 to 49 peeled checkered patterns

×-Number of peeled checkered tiles 50 or more

6) Heat resistance: About the protective film, the light transmittance in 400 nm wavelength was measured using the spectrophotometer (UV-3101PC, the Shimadzu Corporation).

The protective film was then heated in a clean oven at 240 ° C. for 60 minutes. Then, the light transmittance at 400 nm wavelength was measured using the spectrophotometer.

The heat resistance of the cured film was evaluated as follows for each light transmittance value.

○-Change in light transmittance value is within 2%

×-change of light transmittance value is 2% or more

Item Furtherance Copolymer Curable compound Compound having oxetane group Polymerizable Compounds Having Ethylenically Unsaturated Bonds Example 1 100 10 10 0 Example 2 100 10 10 10 Example 3 100 One 10 10 Example 4 100 20 10 10 Example 5 100 50 10 10 Example 6 100 10 One 10 Example 7 100 10 20 10 Example 8 100 10 50 10 Example 9 100 10 10 One Example 10 100 10 10 20 Example 11 100 10 10 50 Comparative Example 1 100 0 10 10 Comparative Example 2 100 10 0 10

division Etchant resistance Etch Margin Hardness Transparency Adhesion Heat resistance Example 1 O O 5H O O O Example 2 O O 5H O O O Example 3 O O 5H O O O Example 4 O O 5H O O O Example 5 O O 5H O O O Example 6 O O 5H O O O Example 7 O O 5H O O O Example 8 O O 5H O O O Example 9 O O 5H O O O Example 10 O O 5H O O O Example 11 O O 5H O O O Comparative Example 1 △ △ H X O X Comparative Example 2 X X 5H O X O

As a result of measuring the physical properties, when the protective film is formed using the thermosetting resin composition prepared in Example, the etchant resistance, the etching margin, the hardness, the transparency, the adhesion, and the heat resistance are all satisfied, and in particular, the etchant resistance compared to the comparative example. And it was found that the etching margin is excellent.

From these results, it can be seen that the protective film formed from the curable resin composition according to one embodiment of the present invention may be particularly useful in processes requiring high acid resistance.

Claims (2)

a-1) unsaturated carboxylic acid or unsaturated carboxylic anhydride, a-2) epoxy group-containing unsaturated compound, a-3) copolymers of olefinically unsaturated compounds other than a-1) and a-2), curable compounds and oxetane groups Curable resin composition containing the compound which has. The curable resin composition according to claim 1, comprising 1 to 50 parts by weight of the curable compound and 1 to 50 parts by weight of the compound having an oxetane group, based on 100 parts by weight of the copolymer.