KR101350050B1 - Curing lesin composition for formming transparent protective layer - Google Patents

Abstract

According to the present invention,

(A) 100 weight of curable resin which has a molecular weight of 800-20,000 obtained by addition-polymerizing the monomer which has an anhydride structure in (a) main chain, and (b) monomer containing styrene-based monomer;

[B] 5 to 70 parts by weight of at least one monomer or resin having an epoxy functional group, and at least one monomer or resin having an oxetane functional group as a curing agent capable of reacting with anhydride;

[C] 5 to 70 parts by weight of one or more monomers having a carboxylic anhydride group;

[D] 5 to 70 parts by weight of one or more monomers having an acrylic group

[E] The present invention relates to a curable resin composition for forming a transparent protective film containing 0.1 to 10 parts by weight of a monovalent amine as a reaction initiator.

Curable Resin, Transparent Protective Film, Color Filter, Display

Description

Curable resin composition for transparent protective film formation {CURING LESIN COMPOSITION FOR FORMMING TRANSPARENT PROTECTIVE LAYER}

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows that the hardness film was used for the color filter for TFT-LCD.

2 is a graph showing the storage stability of the resin composition of Example 1. FIG.

Name of reference numeral

1: Glass 2: Black Matrix 3: Color Filter 4: Hard Film 5: ITO

The present invention relates to a curable resin composition for forming a transparent protective film. In particular, the present invention relates to a curable resin composition for a color filter protective film of a display, and more particularly, to form a protective film used for a color filter for a liquid crystal display device (LCD) and a color filter for a charge coupling device (CCD) on a resin substrate. It is related with the curable composition preferable as a material for following.

As the performance required for the color filter protective film, in addition to heat resistance and chemical resistance, adhesion of the color filter to a glass substrate and the like, flatness, high hardness, and the like can be given. Among them, 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 baking a liquid crystal alignment film on ITO, it also corresponds to a ferroelectric liquid crystal. In this case, since heating at 270 ° C. is required, 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 currently proposed. . However, none of these conventional resins for protective films completely satisfies the conditions required for the protective film. For example, the melamine resin has a three-dimensional network structure, and thus has good heat resistance. There is an advantage that wrinkles and cracks are less likely to occur during ITO sputtering, but 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 that holes are easily formed during application, resulting in poor applicability, resulting in difficulty in balancing flatness and heat resistance. .

The present invention, in order to solve the above problems of the prior art, not only has excellent characteristics in 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. It is an object of the present invention to provide a curable resin composition for forming a transparent protective film having high flattening performance, particularly excellent in storage stability even in a one-component type, and in which an excellent coating film hardness can be obtained even in an extreme etching process.

In order to achieve the above object,

[A] 100 parts by weight of a curable resin having a molecular weight of 800 to 20,000 obtained by addition polymerization of monomers having an anhydride structure in the main chain (a) and monomers comprising (b) a styrene monomer;

[B] 5 to 70 parts by weight of at least one monomer or resin having an epoxy functional group, and at least one monomer or resin having an oxetane functional group as a curing agent capable of reacting with anhydride;

[C] 5 to 70 parts by weight of one or more monomers having a carboxylic anhydride group;

[D] 5 to 70 parts by weight of one or more monomers having an acrylic group; And

[E] A curable resin composition for forming a transparent protective film containing 0.1 to 10 parts by weight of a monovalent amine as a reaction initiator is provided.

Component [A] used as the binder resin in the present invention includes a polymer obtained by addition polymerization of (a) a monomer having an anhydride structure in the main chain, (b) a styrene monomer, and, if necessary, other monomers.

As shown in Formula 1, (a) is anhydride, and examples of the styrene monomer in (b) include styrene, o-methylstyrene, o-hydroxystyrene, and the like. Acrylic monomers etc. are mentioned. Two or more kinds of the styrene-based units may be used, and styrene is most preferably used.

Preferred component [A] in the present invention may be represented by the following formula (1).

delete

In this formula,

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

n and m mean the mole fraction of each monomer in a copolymer, n is 0.05-0.8, m is 0.2-0.95.

Component [A] represented by Chemical Formula 1 in the present invention is 5 to 70 parts by weight, preferably 20 to 60 parts by weight, based on 100 parts by weight of the entire polymer structural unit.

In the present invention, the polymer corresponding to component [A] can be used by purchasing a commercially available SMA resin manufactured by SATOMER Co., Ltd ..

Component [A] polymer included in the composition of the present invention has a problem that the molecular weight of 800 ~ 20,000 is preferred, but the molecular weight is less than 800, the degree of curing after curing is lowered, and if it exceeds 20,000, the molecular weight control becomes difficult as well as the product May cause solubility problems in manufacturing.

In the present invention, component [B] may cause a curing reaction between component [A] or component [B]. As for component [B], the monomer or resin which has an epoxy functional group is a trifunctional or tetrafunctional epoxy resin, bisphenol-A epoxy resin, bisphenol F-type epoxy resin, a novolak-type epoxy resin, and an isocyanate epoxy resin, Among these, 1 or more types can be used.

For example, YH-300, KDT-4400, 4342, 434 (above Kukdo Chemical Co., Ltd.) are mentioned as a trifunctional and tetrafunctional epoxy resin, and bisphenol A epoxy resin is EPR173,174,174S, 174C. And 174HG, 175 (above, manufactured by Bakelite Co., Ltd.), and bisphenol F-type epoxy resins include EPR164,166 and 495 (above, manufactured by Bakelite Co., Ltd.), and novolak-type epoxy resins include EPR600,626,665,673,690 ( As mentioned above, Bakelite Co., Ltd. can be mentioned, As an isocyanate epoxy resin, EPR-05290-05293 (above, Bakelite Co., Ltd.) is mentioned. Among these, preferred are trifunctional and tetrafunctional epoxy resins and bisphenol A epoxy resins. For example, the epoxy resin containing a trifunctional alkyl epoxy group may include a compound represented by the following formula (2), and commercially available YH-300 (manufactured by Kukdo Chemical Co., Ltd.) may be purchased and used.

Moreover, as for the monomer or resin which has an oxetane functional group, a lesocin type oxetane resin is preferable, and 1 or more types of these can be used. For example, 1,3-bis (3-ethyloxetan-3-yl) methoxybenzene, which is commercially available as the compound of formula 3, is R-SOX.

The epoxy monomer or the resin and the oxetane monomer or the resin can be used up to 5 to 70 parts by weight based on 100 parts by weight of the binder resin, but it is preferable to use 20 to 50 parts by weight. If the resin is used below 5 parts by weight, the problem of lowering the degree of curing occurs-and when used in excess of 70 parts by weight, the problem of decktack occurs. The sticking problem occurs due to the inconsistent reaction ratio in the curing system, which is a problem in the color filter process that the protective film must protect.

Component [C] is used in the present invention as one capable of causing a curing reaction with component [D]. Examples of the carboxylic acid anhydride include maleic acid, dicarboxylic acid, maleic anhydride, acrylic acid, maleic acid monomethyl ester, maleic acid monoethyl ester, and the like, and one or more of them may be used. For example, the carboxylic acid dianhydride is represented by Chemical Formula 4 below, and commercially available SR 525 (manufactured by Satomo Co., Ltd.) may be purchased and used.

In the present invention, the carboxylic acid anhydride can be used up to 5 to 70 parts by weight with respect to 100 parts by weight of the binder resin, but it is preferable to use 20 to 50 parts by weight. When the resin is used in less than 5 parts by weight, a problem of lowering the degree of curing occurs, and when used in excess of 70 parts by weight, a problem of lowering the residual film ratio occurs.

In the present invention, as the monomer having an acrylic group of component [D], which serves to improve the curing density resulting from further storage stability by further increasing the degree of curing, a monomer having three or more acrylic groups is preferable, and isocyanurate type compound group One or more compounds selected from can be used. For example, trihydroxy ethylisocyanurate triacrylate.

Although the monomer which has an acryl group in this invention can be used from 5 to 70 weight part with respect to 100 weight part of binder resin, It is preferable to use 10-30 weight part. When the resin is used in less than 5 parts by weight, a problem of lowering the degree of curing occurs, and when used in excess of 70 parts by weight, a problem of lowering thermal stability occurs.

Preferred embodiments of component [E] used as a reaction initiator in the present invention are represented by the following general formula (5).

In the formula,

R is C1-C20 alkyl, C1-C20 aryl, benzyl, C6-C16 alkylbenzyl, C6-C16 arylbenzyl, cyclo, C6-C16 cycloalkyl, C6-C16 arylcyclo.

Component [E] in the present invention serves to improve the storage stability, it is preferably included in 0.1 to 10 parts by weight, more preferably in 1 to 5 parts by weight with respect to 100 parts by weight of the binder resin. If the content of component [E] is less than 0.1 part by weight, there is a problem that the degree of curing decreases, and if it is more than 10 parts by weight, there is a problem of stability over time.

The solvent that can be used in the preparation of the resin composition of the present invention should be capable of dissolving each component uniformly and not only reacting with any of the components but also obtaining excellent coating properties and a transparent thin film. 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 further contain 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 to improve coatability, and with respect to 100 parts by weight of the binder resin. It is preferably included in 0.05 to 5 parts by weight.

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 [made by BYK- Chemie] is mentioned.

Examples of the fluorine-based surfactants include Florinate FC430 and Florinate FC431 (manufactured by Sumitomo Chemical Co., Ltd.); MegaPac ™ F142D, MegaPac F171, MegaPac F172, MegaPac F173, MegaPac F177, MegaPac F183 or MegaPac R30 (manufactured by Dainiphon Ink Chemical Co., Ltd.); F-top (trade name) EF301, F-top EF303, F-top EF351, and F-top EF352 (made by Shin-Akiga Chemical Co., Ltd.); Saffron (trade name) S381, saffron S382, saffron SC101 and saffron SC105 (manufactured by Asahi Glass Co., Ltd.); Trade name E5844 [manufactured by Daikai 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 MegaPac R08, MegaPac BL20, and MegaPac 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, but are not intended to limit the scope of the invention alone. In the Examples, "parts" means "parts by weight" unless otherwise specified.

Example  1-8 and Comparative Example  1-2.

Each resin composition for hardness film formation was prepared by mixing the components of the following Table 1 by the said composition ratio, and fully stirring.

As the binder polymer as the component [A], a styrene of which R is H in Formula 1 below was used.

(One)

 * Content unit: parts by weight

* CMA: n-Methyldicyclohexylamine

* 3-Acryl: Tri-hydroxy ethyl isocianurate triacrylate

Test Example  One.

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 were tested by the following physical property measurement methods and conditions.

Evaluation of storage stability

The viscosity in 23 degreeC of the hardness film formed by the said comparative example is measured using a viscometer (TVE-30L, the product made by Tokimec). After 20 days sealed in an incubator at 10 ℃ and the viscosity measured after the storage using the same method and the same viscometer was measured initially. When the w viscosity change rate does not change within 10% of the initial viscosity value, the pass judgment (○) is used, and when it is out of this, a fail judgment (×) is performed.

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) using a colorimeter measuring instrument (manufactured by Olympus) for a wavelength of 380 nm to 700 nm was measured. Measure After that, the transmittance was measured in the same manner as before for the hardness film heat-cured at 250 ℃ 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 (○).

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 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 (○) is made, and if out of range, fail judgment (×) is performed.

Chemical resistance evaluation

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

In the above chemical resistance evaluation, the protective film damage before and after the evaluation, the film thickness change and the transmittance change before and after the etching test 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 film thickness measurement formula and evaluation method and transmittance measurement method in heat resistance evaluation).

Adhesion 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 among 100 graduations to evaluate adhesion with the substrate. Evaluation is based on the following conditions.

○: 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 tester, it displayed with the highest hardness value that a scratch does not get in a hardness film.

The results of evaluation using the above evaluation conditions and the like are shown in the following [Table 3] and [Table 4].

Curable resin composition for forming a transparent protective film of the present invention is less calorific value at the time of curing, it is possible to achieve the stability of protective materials such as color filters, less shrinkage rate and excellent thermal stability and chemical resistance. In addition, the resin composition of the present invention has alkali resistance and excellent acid resistance, and is excellent in chemical resistance, such as a polar solvent (N-methylpyrrolidone and the like), a photoresist stripper, and the like. Moreover, since the hardness film resin composition of this invention is excellent in storage stability, even when a large application | coating is required, operability is not impaired.

The hardness film 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 such 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 (9)

[A] 100 parts by weight of a curable resin having a weight average molecular weight of 800 to 20,000 obtained by addition polymerization of monomers (a) having an anhydride structure in the main chain and (b) monomers comprising a styrene monomer; [B] 5 to 70 parts by weight of at least one monomer or resin having an epoxy functional group, and at least one monomer or resin having an oxetane functional group as a curing agent capable of reacting with anhydride; [C] 5 to 70 parts by weight of one or more monomers having a carboxylic anhydride group; [D] 5 to 70 parts by weight of one or more monomers having an acrylic group; And [E] a reaction initiator comprising 0.1 to 10 parts by weight of a monovalent amine, Curable resin composition for forming a transparent protective film, wherein the component [A] is represented by the following general formula (1):

(One) In this formula, R is a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, or a hydroxy group, n and m mean the mole fraction of each monomer in a copolymer, n is 0.05-0.8, m is 0.2-0.95. The transparent monomer according to claim 1, wherein the monomer of (a) is selected from the group consisting of anhydrides, and the styrene monomer of (b) is selected from the group consisting of styrene, o-methylstyrene, and o-hydroxystyrene. Hard resin composition for forming a protective film. delete The curable resin composition for forming a transparent protective film according to claim 1, wherein the component [A] represented by the formula (1) is 5 to 70 parts by weight based on 100 parts by weight of the entire polymer structural unit. The method according to claim 1, wherein at least one monomer or resin having an epoxy functional group of component [B] is a trifunctional or tetrafunctional epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a novolac type epoxy resin, And an isocyanate epoxy resin, and at least one monomer or resin having an oxetane functional group is selected from a resorcin type oxetane resin. Curable resin composition for forming a transparent protective film. The method according to claim 1, wherein at least one monomer having a carboxylic anhydride group of component [C] is selected from the group consisting of maleic acid, dicarboxylic acid, maleic anhydride, acrylic acid, maleic acid monomethyl ester and maleic acid monoethyl ester. Curable resin composition for forming a transparent protective film. The curable resin composition for forming a transparent protective film according to claim 1, wherein at least one monomer having an acrylic group of component [D] is selected from the group consisting of isocyanurate type compounds.  The curable resin composition for forming a transparent protective film according to claim 1, wherein the component [E] is represented by the following general formula (5):

(5) In the formula, R is C1-C20 alkyl, C1-C20 aryl, benzyl, C6-C16 alkylbenzyl, C6-C16 arylbenzyl, C6-C16 cycloalkyl, or C6-C16 arylcyclo. The curable resin composition for forming a transparent protective film according to claim 1, further comprising at least one surfactant selected from the group consisting of a silicone-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom.

Images