KR101097045B1 - Thermosetting resin composition for protecting display color filter - Google Patents

Abstract

The present invention relates to a curable resin composition for display color filter protection, and more particularly, to (A) a curable resin containing norbornene or a derivative thereof, (B) an epoxy compound, (C) a thermal latent initiator, and (D) By preparing a curable resin composition containing a surfactant, it is excellent in storage stability as a one-part type, and even when a large amount of coating is required, the operability is not impaired and the display color filter for the improvement of physical properties such as alkali resistance, acid resistance and chemical resistance is also improved. It relates to a curable resin composition.

Norbornene, thermal latent initiator, display color filter

Description

Curable resin composition for display color filter protection {THERMOSETTING RESIN COMPOSITION FOR PROTECTING DISPLAY COLOR FILTER}

BRIEF DESCRIPTION OF THE DRAWINGS The schematic diagram which applied the hardness film of this invention to the color filter for TFT-LCD.

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

3 is a thermogravimetric decomposition of the hardness film after postbaking.

Description of the main parts of the drawing

DESCRIPTION OF SYMBOLS 1 Glass 2 Black matrix 3 Color filter 4 Hardness film 5 ITO

The present invention relates to a curable resin composition for display color filter protection, and more particularly, to (A) a curable resin containing norbornene or a derivative thereof, (B) an epoxy compound, (C) a thermal latent initiator, and (D) By preparing a curable resin composition containing a surfactant, it is excellent in storage stability as a one-part type, and even when a large amount of coating is required, the operability is not impaired and the display color filter for the improvement of physical properties such as alkali resistance, acid resistance and chemical resistance is also improved. It relates to a curable resin composition.

The display color filter protective film is used for liquid crystal display (LCD), charge coupled device (CCD) and the like. Physical properties required for the color filter protective film include heat resistance and chemical resistance, adhesion of the color filter to a glass substrate, flatness, high hardness, and the like. Particularly, in terms of heat resistance, when a transparent electrode such as indium tin oxide (ITO) is produced in a protective film by a sputtering method, the protective film is 200 ° C. or higher, and when firing a liquid crystal alignment film on ITO, it also corresponds to 250 ° C., and a ferroelectric liquid crystal. Since heating at 270 ° C. is required, it is required to be stable under the above temperature conditions.

Until now, as a material for forming such a protective film, an acrylic resin, a melamine resin, a polyimide resin (Japanese Patent Laid-Open No. Hei 1-156371), an epoxy resin (Japanese Patent Laid-Open No. Hei 4-170421) and the like have been proposed. However, none of these conventional resins for protective films completely satisfies the conditions required as protective films.

For example, melamine resin has a three-dimensional mesh structure, which has advantages of good heat resistance and less wrinkles or cracks during ITO sputtering, but poor wettability with glass substrates and color filters, and poor applicability. There was a problem that the flatness of the protective film was impaired.

In addition, the epoxy resin has a good adhesion to the glass substrate and provides a protective film having excellent transparency and chemical resistance, but has a problem in that pores are easily formed during application, resulting in poor applicability, resulting in difficulty in balancing flatness and heat resistance. .

The present inventors have studied and tried to solve the problems of the prior art, and as a result, instead of adopting a curing system using a radical initiator containing an unsaturated compound containing an epoxy group, an olefinically unsaturated compound, an unsaturated carboxylic anhydride, etc. Including a curable resin containing a norbornene having a cyclic structure or a derivative thereof in the main chain to improve the heat resistance and acid resistance, and introduced a small amount of epoxy groups to improve the chemical resistance and improve the adhesion to various hydroxyl groups, especially heat The present invention has been completed by using a latent initiator to obtain excellent coating film hardness even under extreme etching conditions without a curing aid.

Therefore, the present invention not only has excellent properties such as transparency, heat resistance, surface hardness, etc., but also has a high flattening performance, which is excellent in the ability to conceal surface irregularities generated in color filters, black matrices, etc. of substrates, and is excellent in storage stability even in a one-component type. And a curable resin composition for protecting display color filters.

The present invention (A) norbornene or derivatives thereof; A polymer obtained by addition polymerization of at least one of a monomer having an ether group with an olefin double bond or by addition polymerization of another monomer having no functional group capable of reacting with the monomer; And 60 to 98.8 mol% of curable resin, (B) 1 to 50 mol% of epoxy compound, (C) 0.1 to 10 mol% of thermal latent initiator, and (D) surfactant It is characterized by the curable resin composition for display color filter protection containing 0.1-1 mol%.

Referring to the present invention in more detail as follows.

The present invention provides a one-component form by preparing a curable resin composition containing a curable resin containing (A) norbornene or a derivative thereof, (B) an epoxy compound, (C) a thermal latent initiator, and (D) a surfactant. The present invention relates to a curable resin composition for display color filter protection, which has excellent storage stability and does not impair operability even when a large amount of coating is required and also improves physical properties such as alkali resistance, acid resistance, and chemical resistance.

Component (A) of the present invention is a) a monomer having a structure in which a cyclic structure is polymerized in a main chain, and b) at least one polymerized monomer having an ether group and an olefin double bond or reacts with the monomer and ether group. A polymer obtained by addition polymerization of another monomer having no functional group, and c) a polymer obtained by addition polymerization of a styrene-based monomer, wherein component (A) is 60 to 98.8 mol% of the total composition of the present invention and has a molecular weight of 2000 or more. It is preferable to have. If the component (A) is less than 60 mol% of the total composition of the present invention, the chemical resistance at the time of film formation is insufficient.

Component (A) of the present invention may be represented by the following formula (1).

In Formula 1, R, R ₃ and R ₅ are hydrogen atoms or alkyl having 1 to 2 carbon atoms, R ₁ is a direct bond or -C (= 0) O-, R ₂ is vinyl or allyl, R ₄ Is epoxy or alkyl having 1 to 3 carbon atoms, R ₆ is a benzene derivative including benzene and the like, a, b and d are integers of 1 to 2, and a, b and d may be in any order.

A) may be a monomer or an acrylic monomer having a structure obtained by polymerizing a cyclic structure in a main chain. A) is contained in the component (A) 30 to 80 mol%, preferably 50 to 70 mol%, and specific examples thereof include norbornene and norbornene derivatives. If the component (A) is less than 30 mol% in the component (A), chemical resistance may be a problem, and if it exceeds 80 mol%, adhesion is poor.

B) is a polymer obtained by addition polymerization of at least one monomer having an ether group and an olefin double bond or by addition polymerization of another monomer having no functional group capable of reacting the monomer with the ether group. 40 mol%, Preferably 20-30 mol% is included. If the component b) is less than 10 mol% in component (A), problems may occur in adhesion with the membrane, and in excess of 40 mol%, the permeability may be deteriorated.

Specific examples of b) include unsaturated glycidyl ethers such as allyl glycidyl ether and 2-methylallyl glycidyl ether; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate, glycidyl methacrylate and itaconic acid glycidyl ester; Glycidyloxyalkyl (meth) acrylates such as glycidyl oxyethyl (meth) acrylate and glycidyl oxybutyl (meth) acrylate; Epoxy group-containing cycloalkylalkyl (meth) acrylates such as 3,4-epoxycyclohexylmethyl acrylate and 3,4-epoxycyclohexylmethyl methacrylate; Oxetanyl (meth) acrylate, 3-oxetanylmethyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate, (3-ethyl-3-oxetanyl) (Substituted) oxetanyl (meth) acrylates, such as methyl (meth) acrylate, or (substituted) oxetanyl alkyl (meth) acrylate, etc. are mentioned. Among these, monomers having an epoxy group and an olefin double bond are particularly preferred, and unsaturated carboxylic acid glycidyl esters and epoxy group-containing cycloalkylalkyl (meth) acrylates are more preferred, glycidyl (meth) acrylates and 3 Most preferred is, 4-epoxycyclohexylmethyl acrylate.

C) is a polymer obtained by addition polymerization of a styrene monomer, and may contain 20 to 60 mol%, and preferably 30 to 40 mol% in component (A). If the above-mentioned c) component is less than 20 mol% in component (A), heat resistance may be poor, and if it exceeds 60 mol%, film hardness may fall.

Specific examples of the above c) include styrene, α-methylstyrene, divinyl benzene, and the like. Two or more kinds of styrene monomers may be used as the styrene monomers, of which styrene is most preferred.

In the present invention, the polymer resins can be easily obtained through radical polymerization, respectively, and these monomers can be prepared by adding an initiator and a solvent to a flask with a stirrer and a nitrogen inlet in a predetermined molar ratio. The initiator is preferably selected from the group consisting of azobis (isobutyronitrile), azobis (dimethyl valeronitrile), and azobis (cyano bareric acid), and 0.1 to the total amount of each monomer added. It is preferable to add -5 mol%.

(B) component of this invention is an epoxy compound and contains things other than curable resin (A). Specific examples of the component (B) include bisphenol A type epoxy resins, bisphenol F type epoxy resins, novolac type epoxy resins, and isocyanate epoxy resins. The bisphenol A type epoxy resin includes EPR 173,174,174S, 174C, 174HG, 175 (above, manufactured by Bakelite Co., Ltd.), and the bisphenol F type epoxy resin includes EPR 164,166,495 (above, manufactured by Bakelite Co., Ltd.), the novolac The type epoxy resin includes EPR 600,626,665,673,690 (above, manufactured by Bakelite Co., Ltd.), and examples of the isocyanate epoxy resin include EPR-05290-05293 (above, manufactured by Bakelite Co., Ltd.). Among these, a bisphenol A epoxy resin is preferable.

Although said (B) component can be used to 1-50 mol% of the whole composition of this invention, it is preferable to use 1-20 mol%. If the component (B) is less than 1 mol% of the total composition of the present invention, the chemical resistance is poor, and if it exceeds 50 mol%, the transmittance is remarkably poor.

Component (C) of the present invention is a stable thermal latent initiator that generates ions by heat, and an organic onium salt compound in which a cationic component and an anionic component are paired can usually be used.

The cationic component may be represented by the following Chemical Formulas 2a and 2b.

In Formulas 2a and 2b, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are hydrogen atoms or alkyl having 1 to 4 carbon atoms, and X ₁ , X ₂ and X ₃ include carbon, nitrogen, sulfur, and the like. It is an atom.

SbF ₆ as the anion component ^{_{-, AsF 6 -, PF 6}} -, BF 4 -, B (C 6 F 5) 4 - , etc. are included, among SbF ₆ ^- are preferred ^- or PF _6.

The component (C) may contain 0.1 to 10 mol% of the total composition of the present invention, preferably 1 to 5 mol%. When the component (C) is less than 0.1 mol% of the total composition of the present invention, coating film formation may be impossible, and when it exceeds 10 mol%, the film hardness may be deteriorated and chemical resistance may be poor.

The composition of the present invention includes a surfactant (D) which is usually included in addition to the above components. The surfactant of the present invention may contain 0.1 to 1 mol% of the total composition of the present invention. If the component (D) is less than 0.1 mol% of the total composition of the present invention, the flatness of the film becomes poor, and if it exceeds 1 mol%, problems may occur in the flatness.

Component (D) of the present invention is included for improving the coatability, and it is preferable to contain at least one surfactant selected from the group consisting of silicone-based surfactants, fluorine-based surfactants and silicone-based surfactants having fluorine atoms.

Examples of the silicone-based surfactants include trade names TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (manufactured by Jido Toshiba Silicone Co., Ltd.); Trade names KP321, KP322, KP323, KP324, KP326, KP340 and KP341 (manufactured by Shin-Etsu Silicone Co., Ltd.); SH-8400 (manufactured by Tresilicone Co., Ltd.); BYK-333, 358N, UV3500, 390, 306, 340 (made by BYK-Chemistry), etc. are mentioned.

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

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.).

The component (A) to (D) of the present invention may be used after being dissolved in a solvent. The solvent should be capable of dissolving each component uniformly, not reacting with a specific component, and a solvent capable of obtaining excellent coatability and transparent thin film. It is preferable to use a solvent 120-200 weight part with respect to 100 weight part of curable resin compositions of this invention.

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 Ryu; 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.

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

Synthesis Example 1 Preparation of Copolymer-1 (Component A)

5 parts by weight of 2,2'-azobis isobutyronitrile (AIBN) was dissolved in 200 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, 40 mol% of norbornene, 20 mol% of glycidyl methacrylate, 20 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 the temperature was increased. After the polymerization was performed for 3 hours, a copolymer-1 solution having a concentration of 30% (solvent) was obtained. The average molecular weight (Mw) of copolymer-1 was 10,000 (1-a), 20,000 (1-b), 30,000 (1-c).

Synthesis Example 2 Preparation of Copolymer-2 (Component A)

5 parts by weight of 2,2'-azobis isobutyronitrile (AIBN) was dissolved in 200 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, 40 mol% of norbornene, 15 mol% of glycidyl methacrylate, 25 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 the temperature was increased. After the polymerization was carried out for 3 hours to obtain a copolymer-2 solution having a concentration of 30% (relative to a solvent). The average molecular weight (Mw) of copolymer-2 was 10,000 (2-a), 20,000 (2-b), 30,000 (2-c).

Synthesis Example 3 Preparation of Copolymer-3 (Component A)

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 norbornene, 10 mol% of glycidyl methacrylate, 20 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 the temperature was increased. After the polymerization was carried out for 3 hours to obtain a copolymer-2 solution having a concentration of 30% (relative to a solvent). The average molecular weight (Mw) of copolymer-2 was 10,000 (3-a), 20,000 (3-b), 30,000 (3-c).

Comparative Synthesis Example 4 Preparation of Copolymer-4

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 for 3 hours. After the polymerization, a copolymer-4 solution having a concentration of 30% (solvent) was obtained. The average molecular weight (Mw) of copolymer-4 was 10,000.

Examples 1-9 and Comparative Examples

Using the samples obtained through Synthesis and Comparative Synthesis Examples, the compositions of Examples and Comparative Examples were prepared as follows. To nine copolymer solutions obtained through Synthesis Examples 1 to 3, an epoxy compound (B), a thermal latent initiator (C), a surfactant (D) and a solvent (E) were mixed in the amounts shown in Table 1 below, and sufficiently. The composition was prepared by stirring.

division Curable resin Epoxy compound Thermal Potential Initiator Surfactants solvent ingredient content ingredient content ingredient content ingredient content ingredient content Example 1 Copolymer 1-a 70 Bisphenol-A 20 Metal salt 3 PS 002 0.1 PGMEA 150 Example 2 Copolymer 1-b 70 Bisphenol-A 20 Metal salt 3 PS 002 0.1 PGMEA 150 Example 3 Copolymer 1-c 70 Bisphenol-A 20 Metal salt 3 PS 002 0.1 PGMEA 150 Example 4 Copolymer 2-a 70 Bisphenol-A 20 Metal salt 3 PS 002 0.1 PGMEA 150 Example 5 Copolymer 2-b 70 Bisphenol-A 20 Metal salt 3 PS 002 0.1 PGMEA 150 Example 6 Copolymer 2-c 70 Bisphenol-A 20 Metal salt 3 PS 002 0.1 PGMEA 150 Example 7 Copolymer 3-a 70 Bisphenol-A 20 Metal salt 3 PS 002 0.1 PGMEA 150 Example 8 Copolymer 3-b 70 Bisphenol-A 20 Metal salt 3 PS 002 0.1 PGMEA 150 Example 9 Copolymer 3-c 70 Bisphenol-A 20 Metal salt 3 PS 002 0.1 PGMEA 150 Comparative example Copolymer 4 70 Bisphenol-A 20 Metal salt 3 PS 002 0.1 PGMEA 150

Experimental Example

The compositions of Examples 1 to 9 and Comparative Examples were coated on a glass substrate using a spin coater (Mikasa Co., Ltd.) so as to have a film thickness of 1.5 um, which was preheated in a clean oven for 1 to 5 minutes to form a solvent. Was removed. Subsequently, it heated for 30 to 60 minutes in the heat-hardening furnace of 240 degreeC, and formed the hardness film. These formed hardness films were tested by the following physical property measurement methods and conditions.

<Evaluation of transmittance before and after heat resistance evaluation>

With reference to the same glass substrate to which the hardness film was applied, the hardness film formed at 240 ° C. after 30 to 60 minutes (post bake) was first applied to a wavelength ranging from 400 nm to 700 nm using a colorimeter (Olympus). The transmittance was measured. 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 transmittance before and after, a case of falling within 1% of the error range is regarded as a pass judgment (○).

<Heat resistance evaluation>

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 and quantifying it.

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

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

<Chemical Resistance Evaluation>

Chemical resistance is evaluated through the immersion method in the chemical solution under the conditions shown in Table 2.

In the said chemical resistance evaluation, the protective film damage and film thickness change before and after evaluation are confirmed. The change in the 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 the heat resistance evaluation).

<Adhesive evaluation>

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.

○: 100/100

△: 99/100 to 50/100

×: less than 50/100

<Surface hardness evaluation>

When a load of 1 Kg was applied to a hardness film formed through a heat curing furnace at 240 ° C. for 30 to 60 minutes, the hardness film was expressed as having the highest hardness that does not scratch the hardness film.

<Storage stability evaluation>

The hardness film formed by the above example was measured at 23 ° C. using a viscometer (TVE-30L, Tokimex). Thereafter, the container was kept sealed for 10 days at 23 ° C., and the viscosity after storage was 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.

Curable resin composition for display color filter protection of this invention is curable resin containing (A) norbornene or its derivative (s), (B) epoxy compound, (C) thermal latent initiator, (D) surfactant, and (E) solvent By preparing a curable resin composition comprising a superior storage stability as a one-component type, even when a large amount of application is not impaired operability, alkali resistance, acid resistance and polar solvents (N-methylpyrrolidone, etc.), photoresist stripping liquid It also has excellent physical properties such as chemical resistance.

The hardness film of the present invention can be used not only as a film for providing a protective film and flatness of a color filter, but also suitably used for electronic materials such as liquid crystal display devices, solid-state photographing devices, protective films, and other paints and adhesives. Can be.

Claims (3)

(A) norbornene or a derivative thereof, a polymer obtained by addition polymerization of at least one monomer having an ether group and an olefin double bond or by addition polymerization of another monomer having no functional group capable of reacting the monomer with the ether group, and styrene 60-98.8 mol% of curable resins containing the polymer which addition-polymerized the system monomer; (B) 1-50 mol% of an epoxy compound; (C) 0.1-10 mol% of a thermal latent initiator; And (D) 0.1-1 mol% of surfactant; Curable resin composition for display color filter protection comprising a. (A) 60-98.8 mol% of curable resin which has a structure of following General formula (1): [Formula 1]

(In Formula 1, R, R ₃ and R ₅ is a hydrogen atom or alkyl having 1 to 2 carbon atoms, R ₁ is a direct bond or -C (= O) O-, R ₂ is vinyl or allyl, R ₄ is epoxy or alkyl having 1 to 3 carbon atoms, R ₆ is a benzene derivative including benzene and the like, where a, b and d are integers of 1 to 2, and b, b and c may be in any order.) (B) 1-50 mol% of an epoxy compound; (C) 0.1-10 mol% of a thermal latent initiator; And (D) 0.1-1 mol% of surfactant; Curable resin composition for display color filter protection comprising a. The method according to claim 1 or 2, wherein the cationic component of the heat latent initiator is the following formula (2a) or (2b): (2a)

[Formula 2b]

(In Formulas 2a and 2b, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are hydrogen atoms or alkyl having 1 to 4 carbon atoms, and X ₁ , X ₂ and X ₃ represent carbon, nitrogen, sulfur, and the like. Is an atom containing), Anion component is ^{_{SbF 6 -, AsF 6 -,}} PF 6 -, BF 4 -, or _{B (C 6 F 5) 4} - a curable resin composition.

Images