KR101308236B1 - Curing resin compositing having excellent hardeness - Google Patents

Abstract

The present invention is a copolymer containing anhydride; And a curable resin composition comprising a monomer containing an epoxy group, an oxetane group or an anhydride and improving chemical resistance and heat resistance such as alkali resistance and acid resistance by using a tertiary amine or quaternary ammonium salt as a reaction accelerator. This system has a low heat generation during curing, which can promote the stability of protective materials such as color filters, and can be used as a very excellent protective material due to its low shrinkage rate, good thermal stability and chemical resistance.

Curing, Curing Accelerators, Display Color Filters

Description

Curing resin compositing having excellent hardeness}

FIELD OF THE INVENTION The present invention relates to curable resin compositions, in particular curable resin compositions for display color filter protective films, and more particularly to color filters for protective films and charge coupled devices (CCDs) used in color filters for liquid crystal display devices (LCDs) on resin substrates. It relates to a curable composition for forming a protective film, which is preferable as a material for forming a protective film used in the present invention.

As performance required for a color filter protective film, besides heat resistance and chemical resistance, adhesiveness with the glass substrate of a color filter, etc., flatness, high hardness, etc. are mentioned. Among these, when the transparent electrode such as ITO (indium tin oxide) is produced in the protective film by sputtering method, the protective film supports at least 200 ° C and 250 ° C when firing the liquid crystal alignment film on the ITO. In this case, heating at 270 ° C. is required and it is required to be stable under these temperature conditions.

As resins for forming such a protective film, acrylic resins, melamine resins, polyimide resins (Japanese Patent Laid-Open Publication No. Hei 1-156371), epoxy resins (Japanese Patent Laid-Open Publication No. Hei 4-170421), and the like are proposed. It is. However, none of these conventional resins for protective films satisfies all of the conditions required for the protective film. For example, melamine resin has a three-dimensional network structure, and thus has good heat resistance and wrinkles during ITO sputtering. Although there is an advantage that the cracks are less likely to occur, there is a problem that the wettability with the glass substrate or the color filter is poor and the coating property is poor, and the flatness of the resulting protective film is impaired.

In addition, the epoxy resin provides a protective film having good adhesion to the glass substrate and excellent transparency and chemical resistance, but has a problem in that it is difficult to balance flatness and heat resistance as a result of poor porosity at the time of application, resulting in poor applicability. .

On the other hand, the inventors of the present invention is a curable resin composition for a color filter protective film excellent in storage stability even in one-component in order to solve the problems of the prior art as described above, specific as a curing agent that can react with the copolymer and anhydride having an anhydride structure in the main chain The curable resin composition containing the monomer of has been developed. The present invention has completed the present invention by discovering that the physical properties of the hardness film obtained when using a specific accelerator in the curable resin composition are further improved by the extension of such development.

An object of the present invention is to solve the problems of the prior art, and not only has excellent characteristics such as transparency, heat resistance, surface hardness, etc., but also has a high leveling performance with excellent ability to conceal surface irregularities generated in color filters, black matrices, etc. of the substrate. The present invention provides a curable resin composition for a color filter protective film having excellent storage stability even in a one-component type .

That is, the present invention provides a resin composition having a high degree of curing, and when forming a film, it is intended to provide a curable resin composition which can obtain excellent coating film hardness even under extreme etching conditions by improving chemical resistance and heat resistance such as alkali resistance and acid resistance. It is. Particularly, the amount of heat generated during curing can be used to improve stability of protective materials such as color filters. The shrinkage ratio of the obtained hardness film is low, thermal stability and chemical resistance can be used as a very excellent protective material, and a high degree of curing is also provided.

In order to achieve the above object, the present invention uses a trivalent amine or a tetravalent ammonium salt as a reaction accelerator in a curable resin composition comprising the following component [A] and component [B]. The curable resin composition for this is provided.

In other words, the present invention

[A] 35 to 90% by weight of a curable resin having a molecular weight of 800 or more, including (a) a monomer having a structure of polymerizing an anhydride structure in the main chain and (b) a polymer obtained by addition polymerization of a styrene monomer;

[B] 5 to 60% by weight of at least one selected from the group consisting of monomers or resins having an epoxy function and monomers or resins having an oxetane function as a curing agent capable of reacting with anhydride; And

The curable resin composition for display color filter protective film containing 0.1-10 weight% of trivalent amine or tetravalent ammonium salt as a reaction initiator [C] is provided.

Moreover, this invention provides the curable resin composition for display color filter protective films which further contains the monomer which has a carboxylic acid anhydride group as a hardening | curing agent.

This invention also provides curable resin composition for display color filter protective films which further contains surfactant.

The present invention also provides a color filter protective film, characterized in that formed by the curable resin composition.

The present invention also provides a display including a color filter protective film formed by the curable resin composition.

Hereinafter, the present invention will be described in detail.

Component [A] in the present invention includes a polymer obtained by addition polymerization of (a) a monomer having a structure in which anhydrides are polymerized in a main chain, (b) a styrene monomer and, if necessary, other monomers. 1).

[Formula 1]

Where

R 1 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms.

R2 is a hydroxyl group, a hydrogen atom or an alkyl group having 1 to 2 carbon atoms,

R3 is a hydrogen atom or an alkyl group of 1 carbon atom,

a and b mean the mole fraction of each monomer in a polymer, a is 0.05-0.8, and b is 0.2-0.95.

Component (a) is a monomer having a structure in which an anhydride structure is polymerized in a main chain. As for the structural unit derived from this monomer, when the total polymer structural unit is 100%, 5 to 80 mol%, Preferably 20 to 60% is suitable.

Component (b) is a polymer obtained by addition polymerization of a styrene monomer, and the constitutional unit is 20 to 95% and preferably 40 to 80% when the total constitutional unit is 100%. As a specific example, styrene, (alpha) -methylstyrene, hydroxyl benzene, etc. are mentioned. As the styrene monomer, two or more styrene monomers may be used, of which styrene is most suitable.

Component [A] of the present invention may further copolymerize (meth) acrylic monomers if necessary.

Component [A] polymer included in the curable resin composition of the present invention has a molecular weight of 800 or more, but when the molecular weight is less than 800, there is a problem that the degree of curing after curing is lowered. In addition, the content of component [A] in the curable resin composition of the present invention is preferably 35 to 90% by weight, but if less than 35% by weight, there is a problem that the hardness is lowered. .

In the present invention, the component [B] may be a resorcin type oxetane resin, a trifunctional or tetrafunctional epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a novolac type epoxy resin, or an isocyanate epoxy resin. For example, the trifunctional and tetrafunctional epoxy resins are YH-300, KDT-4400, 4342, 434 (manufactured by Kukdo Chemical Co., Ltd.), and the bisphenol A epoxy resins are EPR173, 174, 174S, 174C, 174HG, and 175. (Above, manufactured by Bakelite Co., Ltd.), and as bisphenol F type epoxy resin, EPR164, 166, 495 (above, manufactured by Bakelite Co., Ltd.), and novolak-type epoxy resin by EPR600, 626, 665, 673, 690 (above, manufactured by Bakelite Co., Ltd.) ) And an isocyanate epoxy resin include EPR-05290 to 05293 (above, manufactured by Bakelite Co., Ltd.). Among them, trifunctional and tetrafunctional epoxy resins and bisphenol A epoxy resins are preferable. Preferred examples of the epoxy containing a trifunctional alkyl epoxy group are represented by the following Chemical Formula 2 (YH-300 (manufactured by Kukdo Chemical Co., Ltd.)).

[Formula 2]

In addition, component [B] may further use carboxylic anhydride. Examples of such carboxylic anhydrides include maleic acid, dicarboxylic acid, maleic anhydride, acrylic acid, maleic acid monomethyl ester, maleic acid monoethyl ester, and the like. On the other hand, a preferred example of the carboxylic acid dianhydride is a compound of formula (Epiclon B-4400, manufactured by Dainippon Ink and Chemicals, Inc.).

(3)

The content of component [B] in the curable resin composition of the present invention is preferably 5 to 60% by weight, more preferably 20 to 50% by weight. If less than 5% by weight, there is a problem that the hardness is lowered, if more than 60% by weight there is a problem that the surface stickiness occurs.

The resin composition of the present invention may contain a solvent. The solvent must dissolve each component uniformly, and not only react with any of the components, but also use a solvent capable of obtaining excellent coatability and transparent thin film.

Specific examples of the solvent include alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol or cyclohexanol; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone or cyclohexanone; Ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, Ethers such as diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol monomethyl ether, 3-methoxy-1-butanol or 3-methyl-3-methoxy-1-butanol ; Ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxybutyl acetate, 3-methyl-3-methoxy-1-butyl acetate, ethylene glycol monoacetate, ethylene glycol di Acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl Esters such as ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate or butyrolactone; Aromatic hydrocarbons, such as toluene or xylene, etc. are mentioned. Moreover, such a solvent can be used together 2 or more types according to the objective.

Component [C] may use a trivalent amine or a tetravalent ammonium salt as a reaction initiator. According to the present invention, by using the reaction initiator, the amount of heat generated during curing can be reduced and stability of protective materials such as color filters can be achieved. The shrinkage rate of the obtained hardness film is low, and the thermal stability and chemical resistance can be used as a very excellent protective material. There is also a high advantage. The trivalent amines presented herein are preferably compounds of the formulas 4- (a), 4- (b), 4- (c) or 4- (d) below, and the tetravalent ammonium salts are preferably of formula ( 5) is a compound.

[Formula 4- (a)]

Wherein,

R ₁ , R ₂ And R ₃ is independently C 1-20 alkyl, C 6-20 aryl, benzyl, alkylbenzyl, arylbenzyl, cyclo, C 3-20 cycloalkyl or arylcyclo trivalent amine.

[Formula 4- (b)]

In the formula,

R ₁ is a C3-20 alkyl, C6-20 aryl, benzyl, alkylbenzyl, arylbenzyl, cyclo, C3-20 cycloalkyl or arylcyclo trivalent amine.

[Formula 4- (c)]

The compound is a trivalent amine having n = 0 to 1 and m = 1 to 10 by attaching a hydroxyl group to the carbon chain for affinity with an epoxy group and an anhydride.

[Formula 4- (d)]

Trivalent amine with n = 1-5 containing a methoxy or ethoxy group.

[Chemical Formula 5]

In the formula,

R ₁ is a trivalent amine which is C 1-10 alkyl, C 6-20 aryl, benzyl, alkylbenzyl, arylbenzyl, cyclo, cycloalkyl or arylcyclo.

The ratio of component [C] used as a reaction initiator in the resin composition of this invention is 0.1 to 10 weight% normally in the whole composition, Preferably it is 1 to 5 weight%. If the content of the reaction initiator is less than 0.1% by weight, there is a problem that the degree of curing is lowered, and if it is more than 10% by weight, there is a problem of stability over time.

The resin composition of the present invention preferably contains at least one surfactant from the group consisting of a silicone-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom in order to improve applicability.

Among the surfactants described above, silicone surfactants include trade names TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (manufactured by Chisodo Silicone Co., Ltd.); Trade names KP321, KP322, KP323, KP324, KP326, KP340 and KP341 (manufactured by Shin-Etsu Silicone Co., Ltd.); SH-8400 [manufactured by Tresilicon Co., Ltd.]; BYK-333,358N, UV3500,390,306,340 (manufactured by BYK-Chemie).

Examples of the fluorine-based surfactants include Florinate® FC430 and Florinate FC431 (manufactured by Sumitomo Chemical Co., Ltd.); MegaPak® F142D, MegaPak F171, MegaPak F172, MegaPak F173, MegaPak F177, MegaPak F183 or MegaPak R30 (manufactured by Dainiphon Ink Chemical Co., Ltd.); F-top (trademark) EF301, F-top EF303, F-top EF351, and F-top EF352 (made by Shin-Akiga Chemical Co., Ltd.); Saffron (registered trademark) S381, saffron S382, saffron SC101 or saffron SC105 (manufactured by Asahi Glass Co., Ltd.); Trade name E5844 [manufactured by Daikin Chemical Co., Ltd.]; Trade names BM-1000 and BM-1100 (manufactured by BM Chemie).

Examples of the silicone-based surfactant having a fluorine atom include MegaPak (registered trademark) R08, MegaPark BL20, and MegaPak F443 (manufactured by Dainiphon Ink Chemical Co., Ltd.).

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. These examples are intended to illustrate the invention and do not limit the scope of the invention in any way. In the examples, "parts" means "parts by weight" unless otherwise specified.

Examples 1 to 10 and Comparative Example 1

The anhydride and epoxy resin compositions [A, B], reaction initiators, other surfactants, and solvents were mixed and sufficiently stirred to prepare resins for the respective hardness films as [Comparative Examples] and [Examples] as shown in Table 1 below. The composition was prepared.

In the binder polymers of Examples and Comparative Examples, the ratio of styrene and anhydride was 1: 1, 1: 2, and the average molecular weight (Mw) of the polymer was 7,500. As an initiator of the comparative example, R ₃ , R ₄ And R ₅ are each hydrogen atom, X3 is nitrogen and PF ₆ ⁻ as anion component.

[Formula 6]

Examples of reaction initiators

[Formula 4- (a)]

Wherein,

R ₁ , R ₂ Is C1, R ₃ is used to be the C16 alkyl group.

[Formula 4- (b)]

In the formula,

R _{1 used} was an alkyl group having carbon C1.

[Formula 4- (c)]

In the above formula, n = 1 and m = 1 were used.

 [Formula 4- (d)]

In the formula, n = 2 was used.

[Chemical Formula 5]

In the formula,

R ₁ used an alkyl group which is C4.

[Table 1]

Binder polymer Monomer Reaction Initiator Surfactants menstruum ingredient ratio Content (parts by weight) ingredient content
(Parts by weight) ingredient content
(Parts by weight) ingredient content
(Parts by weight) ingredient Example 1 (A)-(a)
(A)-(b) 0.5
0.5 100 YH-300 50 4- (a) type 4 SH-8400 0.1 PGMEA Example 2 (A)-(a)
(A)-(b) 0.5
0.5 100 YH-300 50 4- (b) type 4 SH-8400 0.1 PGMEA Example 3 (A)-(a)
(A)-(b) 0.5
0.5 100 YH-300 50 4- (c) type 4 SH-8400 0.1 PGMEA Example 4 (A)-(a)
(A)-(b) 0.5
0.5 100 YH-300
50
4- (d) type 4 PGMEA Example 5 (A)-(a)
(A)-(b) 0.5
0.5 100 YH-300
50
5 type 4 PGMEA
Example 6 (A)-(a)
(A)-(b) 0.33
0.67 100 YH-300 50 4- (a) type 4 SH-8400 0.1 PGMEA Example 7 (A)-(a)
(A)-(b) 0.33
0.67 100 YH-300 50 4- (b) type 4 SH-8400 0.1 PGMEA Example 8 (A)-(a)
(A)-(b) 0.33
0.67 100 YH-300 50 4- (c) type 4 SH-8400 0.1 PGMEA Example 9 (A)-(a)
(A)-(b) 0.33
0.67 100 YH-300
50
4- (d) type 4 PGMEA Example 10 (A)-(a)
(A)-(b) 0.33
0.67 100 YH-300
50
5 type 4 PGMEA
Comparative Example 1 (A)-(a)
(A)-(b) 0.5
0.5 100 YH-300
50 Heat potential system 4 SH-8400 0.1 PGMEA

The composition for forming a hardness film as shown in [Table 1] was coated on a glass substrate using a spin coater (Mikasa Co., Ltd.) so as to have a thickness of 1.5 μm, which was then preheated at 110 ° C. for 1 to 5 minutes in a clean oven. To remove the solvent. Subsequently, it heats for 30 to 60 minutes in the heat-hardening furnace of 240 degreeC, and forms a hardness film. These formed hardness films are performed by the following physical property measuring methods and conditions.

<Evaluation of transmittance before and after heat resistance evaluation>

Referring to the same glass substrate coated with the hardness film, first, the transmittance of the hardness film formed at 240 ° C. after 30 to 60 minutes (post bake) was measured using a colorimeter (Olympus) for wavelengths from 380 nm to 700 nm. Measure Thereafter, the transmittance was measured in the same manner as before for the hardness film heat-cured at 250 ° C. for 1 hour. By comparing the transmittances before and after, the case of falling within 1% of the error range is regarded as the pass judgment (O).

&Lt; Evaluation of heat resistance &

The formed hardness film was heat treated at 250 ° C. for 1 hour, and then the film thickness of the hardness film was measured. The film thickness measurement method evaluates heat resistance by quantifying the difference between the film thickness before heating and after heating.

Film thickness change (%) = [film thickness after heating / film thickness before heating] X 100

If it falls within 2% after evaluation, pass judgment (O) is made. If it is out of range, fail judgment (×) is made.

<Chemical Resistance Evaluation>

Chemical resistance evaluation is performed through the immersion method in the chemical solution under the following conditions.

[Table 2]

Evaluation item Use chemicals Temperature (℃) Immersion time Acid resistance MA-SO2
(ITO Etchant manufactured by Dongwoo Fine-Chem Co., Ltd.) 45 15 minutes Alkali resistance 5% sodium hydroxide solution 30 30 minutes Solvent resistance N-methyl-2-pyrrolidone (NMP) 40 40 minutes Peeling resistance PRS-2000
(Photoresist stripping solution from Dongwoo Fine Chem Co., Ltd.) 70 10 minutes

In the above chemical resistance evaluation, the protective film damage and the film thickness change before and after the evaluation are confirmed. The change in film thickness is evaluated by confirming the difference by measuring the film thickness before and after and percentage it (refer to the film thickness measurement formula and evaluation method in heat resistance evaluation).

&Lt; Evaluation of adhesion &

For each sample subjected to chemical resistance evaluation, 100 checkerboard eyes were made, and cellophane tape peeling evaluation was performed to check the remaining number of 100 graduations to evaluate adhesion to the substrate. Evaluation is based on the following conditions.

O: 100/100

△: 99 / 100-50 / 100

×: less than 50/100

<Surface hardness evaluation>

When 1 kg of load was applied to the hardness film formed through 240 degreeC and the heat-hardening furnace for 30 to 60 minutes using the pencil hardness meter, it displayed with the highest hardness value that a scratch does not appear in a hardness film.

&Lt; Evaluation of storage stability &

The viscosity film at 23 degreeC is measured for the hardness film formed by the said Example using the viscometer (TVE-30L, Tokimec Co., Ltd.). Thereafter, the container is kept sealed for 10 days in a clean oven at 23 ° C., and the viscosity after storage is measured using the same method and the same viscometer as initially measured.

The results of the evaluation using the evaluation conditions as described above are shown in Table 3 below.

[Table 3]

Evaluation item Example
One Example
2 Example
3 Example
4 Example
5 Example
6 Example
7 Example
8 Example
9 Example 10 Comparative Example
One Transmittance After post-baking 99% 99% 99% 99% 99% 97% 99% 99% 99% 98% 96% 250 ° C, after 1 hour ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Heat resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Chemical resistance Acid resistance ○ ○ ○ ○ ○ △ ○ ○ ○ △ △ Alkali resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Solvent resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Peeling resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ △ Adhesiveness Acid resistance ○ ○ ○ ○ ○ △ ○ ○ ○ △ ○ Alkali resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ △ Solvent resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Peeling resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Surface hardness 7H 7H 7H 7H 7H 7H 7H 7H 7H 7H 7H

The curable resin composition for a display color filter protective film of the present invention uses a trivalent amine and a tetravalent ammonium salt in the composition of a copolymer containing an anhydride and a monomer having an epoxy group and an oxetane group, so that the amount of heat generated during curing is small to protect color filters and the like. Water stability can be achieved, shrinkage rate is low, and heat stability and chemical resistance are excellent. In addition, the resin composition of the present invention has alkali resistance and excellent acid resistance, and also has excellent chemical resistance to chemicals such as polar solvents (N-methylpyrrolidone and the like), photoresist stripping liquid and the like. Since curable resin composition of this invention is excellent in storage stability, even when large application | coating is required, operability is not impaired. The hardness film of the present invention is not only used as a film for providing a protective film and flatness of a color filter from its excellent characteristics, but also suitably used for electronic materials such as liquid crystal display devices, solid-state imaging devices, protective films, and other paints and adhesives. Can lose.

Claims (10)

[A] 35 to 90% by weight of a curable resin having a molecular weight of 800 or more, including (a) a monomer having a structure of polymerizing an anhydride structure in the main chain and (b) a polymer obtained by addition polymerization of a styrene monomer; [B] 5 to 60% by weight of at least one selected from the group consisting of monomers or resins having an epoxy function and monomers or resins having an oxetane function as a curing agent capable of reacting with anhydride; And [C] The curable resin composition for display color filter protective film containing 0.1-10 weight% of trivalent amine or tetravalent ammonium salt as a thermosetting reaction initiator. The curable resin composition for display color filter protective films of Claim 1 which further contains the monomer which has a carboxylic acid anhydride group as a hardening | curing agent. The curable resin composition according to claim 1, wherein the component [A] is represented by the following general formula (1). [Chemical Formula (1)

In this formula, R 1 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms. R <2> is a hydroxyl group, a hydrogen atom, or a C1-C2 alkyl group. R3 is a hydrogen atom or an alkyl group of 1 carbon atom, a and b mean the mole fraction of each monomer in a polymer, a is 0.05-0.8, and b is 0.2-0.95. The curable resin composition according to claim 3, wherein the styrene-based monomer is at least one member selected from the group consisting of styrene, α-methylstyrene, and hydroxyl benzene. The method of claim 1, wherein component [B] is a lysosin type oxetane resin, a trifunctional or tetrafunctional epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a novolak type epoxy resin, an isocyanate, an epoxy, maleic acid, Curable resin composition, characterized in that at least one selected from the group consisting of dicarboxylic acid, maleic anhydride, acrylic acid, maleic acid monomethyl ester and maleic acid monoethyl ester. The curable resin composition according to claim 1, wherein the component [C] is represented by the following formulas 4- (a), 4- (b), 4- (c), 4- (d) or formula (5). [Formula 4- (a)]

In the formula, R ₁ , R ₂ and R ₃ are each alkyl having 1 to 20 carbon atoms, aryl, benzyl, alkylbenzyl, arylbenzyl, cycloalkyl or arylcycloalkyl; [Formula 4- (b)]

In the formula, R ₁ is alkyl having 1 to 20 carbon atoms, aryl, benzyl, alkylbenzyl, arylbenzyl, cycloalkyl or arylcycloalkyl; [Formula 4- (c)]

Wherein n = 1 to 5 and m = 1 to 10; [Formula 4- (d)]

Wherein n = 1 to 5; or [Chemical Formula 5]

In the formula, R ₁ is alkyl having 1 to 10 carbon atoms, aryl, benzyl, alkylbenzyl, arylbenzyl, cycloalkyl or arylcycloalkyl. The curable resin composition according to claim 1, further comprising a surfactant. The curable resin composition according to claim 7, wherein the surfactant is at least one selected from the group consisting of silicone surfactants, fluorine-based surfactants and silicon-based surfactants having fluorine atoms. It is formed with the curable resin composition of Claim 1, The color filter protective film characterized by the above-mentioned. A display comprising a color filter protective film formed by the curable resin composition of claim 1.