KR101292385B1 - Curing resin composition - Google Patents

Abstract

The present invention includes conventional epoxy groups containing unsaturated compounds, olefinically unsaturated compounds, unsaturated carboxylic anhydrides, and the like, and instead of adopting a curing system using a radical initiator, anhydrides are introduced into the main chain to provide heat resistance, alkali resistance and acid resistance. To improve the chemical resistance such as heat resistance, alkali resistance and acid resistance by introducing an epoxy group or an oxetane group as a crosslinking agent, and to provide a curable resin composition for a display color filter protective film that can obtain excellent coating hardness even under extreme etching conditions.

Curable Resin, Display Color Filter, Curable

Description

Curing resin composition

1 is a graph of the transmittance of the hardness film of Comparative Example 1 after the post-baking.

2 is a graph of the transmittance of the hardness film of Example 2 after the post-baking.

The present invention relates to a curable resin composition for a display color filter protective film. More particularly, the present invention relates to a curable resin composition for forming a protective film, which is preferable as a material for forming a protective film used for a color filter for a liquid crystal display device (LCD) and a protective film for a color filter for a charge coupled device (CCD) on a resin substrate. will be.

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 them, the heat resistance is 250 ° C. or higher when the protective film is baked at 200 ° C. or higher and ITO when a transparent electrode such as ITO (Indium Tin Oxide) is produced by the sputtering method. 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 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 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.

On the other hand, epoxy resins provide a protective film with good adhesion to glass substrates and excellent transparency and chemical resistance, but have a problem in that holes are easily formed during application, resulting in poor applicability, resulting in difficulty in balancing flatness and heat resistance. .

An object of the present invention is to solve the problems of the prior art as described above not only has excellent characteristics such as transparency, heat resistance, surface hardness, etc., but also has an 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 high flattening performance and excellent storage stability even in a one-component type.

The present invention includes conventional epoxy groups containing unsaturated compounds, olefinically unsaturated compounds, unsaturated carboxylic anhydrides and the like, and instead of adopting a curing system using a radical initiator, anhydrides are introduced into the main chain to provide heat resistance, alkali resistance and The present invention provides a resin composition for forming a hardness film which improves acid resistance, improves chemical resistance by introducing epoxy groups and oxetane groups, and obtains excellent coating film hardness even under extreme etching conditions.

In order to achieve the above object, the present invention relates to a curable resin composition for a display color filter protective film comprising the following components [A] to [D].

[A] 35 to 90% by weight of a curable resin having a molecular weight of 800 or more, comprising (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 anhydrides; And

[C] 0.1 to 10 wt% of a heat latent initiator that generates ions by heat

It provides a curable resin composition for a display color filter protective film comprising a.

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.

Moreover, this invention provides the 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, preferably 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. The structural unit derived from this monomer is 5 to 80 mol % based on 100% of the total polymer structural units, and is preferably 20 to 60%.

Component (b) is a styrene-based monomer, wherein the structural unit is 20 to 95% and preferably 40 to 80% when the total structural unit is 100%. As a specific example, styrene, (alpha) -methylstyrene, hydroxyl benzene, etc. are mentioned. As the styrene monomer, one or 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 should have a molecular weight of 800 or more, but if the molecular weight is less than 800, there is a problem that the curing degree after curing is lowered and the mechanical properties are poor. 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. .

As component [B], a lesosine type oxetane resin, a trifunctional or tetrafunctional epoxy resin, a bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, a novolak-type epoxy resin, and an isocyanate epoxy resin can be used. For example, trifunctional or tetrafunctional epoxy resins include YH-300, KDT-4400, 4342, 434 (manufactured by Kukdo Chemical Co., Ltd.), and EPR173, 174, 174S, 174C, and 174HG as bisphenol A epoxy resins. , 175 (above, manufactured by Bakelite Co., Ltd.), and the bisphenol F-type epoxy resins include EPR164, 166, and 495 (above, manufactured by Bakelite Co., Ltd.), and novolak-type epoxy resins, such as EPR600, 626, 665, 673, and 690 (above, Bakelite Co., Ltd.) and an isocyanate epoxy resin can mention EPR-05290-05293 (above, Bakelite Co., Ltd. make). Among these, preferred are trifunctional or tetrafunctional epoxy resins and bisphenol A epoxy resins.

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 preferable example of the carboxylic acid dianhydride is a compound represented by the following formula (Epiclon B-4400, manufactured by Dainippon Ink and Chemicals Co., Ltd.).

[Formula 2]

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 it is less than 5% by weight, there is a problem that the hardness is lowered, and if it is more than 60% by weight, there is a problem of surface stickiness.

Component [C] is a thermal latent initiator that generates ions by heat, and an organic onium salt compound in which a cationic component and an anionic component are usually used as a pair is used. The cationic component presented in the present invention can be represented by the following formula (3-) to 3- (c).

,

,

[Formula 3- (a)] [Formula 3- (b)]

[Formula 3- (c)]

Where

R ₁ , R ₂ , R ₃ , R ₄ And R ₅ is a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms, respectively

X 1 is nitrogen, X 2 is nitrogen or CH, and X 3 is nitrogen.

SbF ₆ as an anion component in the component ^{_{[C] -, AsF 6 -}} , PF 6 -, BF 4 - there are such, particularly ^{_{SbF 6 - -, B (C}} 6 F 5) 4 is preferred ^-, PF _6.

The ratio of component [C] used as a heat latent 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 thermal latent initiator is less than 0.1% by weight, there is a problem in that the degree of curing is lowered, and if it is more than 10% by weight, the initiator may cause particle problems.

A solvent may be used to prepare the resin composition of the present invention as described above. The solvent may dissolve each component uniformly, and the solvent may not only react with any of the components but also obtain excellent coating properties and a transparent thin film. Should be used. Specific examples 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.

The resin composition of the present invention may contain at least one surfactant from the group consisting of silicone-based surfactants, fluorine-based surfactants and silicone-based surfactants having fluorine atoms in order to improve applicability.

As silicone type surfactant which can be used among the said surfactant, brand names TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 [made by Chitoshiba 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 and saffron SC105 (manufactured by Asahi Glass Co., Ltd.); Trade name E5844 [manufactured by Shadakikin 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 Industries, 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.

Examples 1 to 10

The binder polymer (component [A]) and monomer (component [B]), the thermal latent initiator [C], other surfactants, and a solvent which have a structure which polymerized an anhydride structure in the main chain are mixed, and agitation is carried out as shown in Table 1 below. A resin composition for forming a hardness film was prepared. In the examples, "parts" means "parts by weight" unless otherwise specified. The average molecular weight (Mw) of this polymer was 7,500.

As a heat latent initiator, in the formula 3- (c), R ₃ , R ₄ And R ₅ are each hydrogen atom, X3 is nitrogen and PF ₆ ⁻ as anion component.

Comparative Example 1

5 parts by weight of 2,2'-azobis isobutyronitrile (AIBN) was dissolved in 200 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, 50 mol% of glycidyl methacrylate, 30 mol% of 2-hydroxyethyl methacrylate, and 20 mol % of styrene were added, and then the temperature of the solution was raised to 95 DEG C and maintained at this temperature for 3 hours to polymerize. After that, a solution of Copolymer-1 having a concentration of 30% by weight (solvent) was obtained. The average molecular weight (Mw) of copolymer-1 was 10,000.

 [Table 1]

Binder polymer Monomer Heat potential initiator Surfactants menstruum ingredient ratio content
(Parts by weight) ingredient Content (parts by weight) Content (parts by weight) ingredient Content (parts by weight) ingredient Example 1 (A)-(a)
(A)-(b) 0.5
0.5 100 Bisphenol-A 50 4 SH-8400 0.1 PGMEA Example 2 (A)-(a)
(A)-(b) 0.5
0.5 100 YH-300 50 4 SH-8400 0.1 PGMEA Example 3 (A)-(a)
(A)-(b) 0.5
0.5 100 Oxetane 50 4 SH-8400 0.1 PGMEA Example 4 (A)-(a)
(A)-(b) 0.5
0.5 100 YH-300
Oxetane 25
25 4 PGMEA Example 5 (A)-(a)
(A)-(b) 0.5
0.5 100 YH-300
Epi-b 4400 70
20 4 PGMEA
/ GBL Example 6 (A)-(a)
(A)-(b) 0.33
0.67 100 Bisphenol-A 50 4 SH-8400 0.1 PGMEA Example 7 (A)-(a)
(A)-(b) 0.33
0.67 100 YH-300 50 4 SH-8400 0.1 PGMEA Example 8 (A)-(a)
(A)-(b) 0.33
0.67 100 Oxetane 50 4 SH-8400 0.1 PGMEA Example 9 (A)-(a)
(A)-(b) 0.33
0.67 100 YH-300
Oxetane 25
25 4 PGMEA Example 10 (A)-(a)
(A)-(b) 0.33
0.67 100 YH-300
Epi-b 4400 70
20 4 PGMEA
/ GBL Comparative Example 1 Copolymer-1 100 Bisphenol-A 50 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 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. When the transmittance before and after is compared and it falls within 1% of an error range, it is set as the pass judgment (O), and when it exceeds this, it is set as rejection judgment (x).

&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 the 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 the evaluation, a pass judgment (O) is made, and if it is out of range, a fail judgment (×) is performed.

<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 film thickness change 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 in 23 degreeC of the hardness film formed by the said Example is measured using a viscometer (TVE-30L, Tokimec). Thereafter, the container is kept sealed for 10 days at 23 ° C., and the viscosity after storage is measured using the same method and the same viscometer that were measured initially.

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 Post-baking 96% 96% 96% 97% 97% 96% 99% 99% 99% 97% 94% 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 Preservation stability ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○

  The curable resin composition for display color filter protective film of this invention is excellent in storage stability as a one-component type compared with the two-component composition which currently forms the mainstream, and is also equivalent in performance. In addition, the resin composition of the present invention is excellent in alkali resistance and acid resistance, and also excellent in chemical resistance to chemicals such as polar solvents (N-methylpyrrolidone and the like), photoresist stripping liquid and the like. Moreover, since curable resin composition of this invention is excellent in storage stability, even when a large application | coating is required, operability is not impaired. In addition, the curable composition of the present invention is not only used as a film for the purpose of providing a protective film and flatness of the color filter from its excellent properties, but also suitably for electronic materials such as liquid crystal display devices, solid-state imaging devices, protective films, and other paints, adhesives, and the like. Can be used.

Claims (10)

[A] 35 to 90% by weight of a curable resin having a molecular weight of 800 or more, comprising (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 anhydrides; And [C] 0.1 to 10 wt% of a heat latent initiator that generates ions by heat / RTI &gt; Curable resin composition for a display color filter protective film, characterized in that the component [C] is at least one selected from the group consisting of the following general formulas 3- (b) and 3- (c). ,

[Formula 3- (b)]

[Formula 3- (c)] Where R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each represent a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms, X ₁ is nitrogen and X ₃ is nitrogen. The curable resin composition according to claim 1, further comprising a monomer having a carboxylic acid anhydride group as a 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. delete 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.

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