JPH11279259A - Curable resin composition and transparent base material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable resin composition with excellent coating performance on plastic plates such as of acrylics or polycarbonates or inorganic base materials such as glass, and curability, having high contamination resistance and postering-proofness, and capable of providing smooth and transparent coating film of high adhesiveness to base material, and to obtain a transparent base material coated with the above composition. SOLUTION: This curable resin composition comprises (a) an epoxy group- contg. resin composed essentially of a silicone-based block copolymer consisting of a polymer portion having a plurality of epoxy groups in the polymer chain and (b) a multifunctional amine compound. The objective transparent base material is such one as to be coated with the above resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a method for hardening at room temperature on a dry surface on an inorganic base material such as glass, concrete, mortar, ceramic, stone, metal plate or a plastic such as polyvinyl chloride, acrylic or polyester. Excellent protection against contamination by oil, dust, water-based or oil-based paints,
Also, to form a coating film having a surface property that can easily remove the artificially pasted posters such as posters,
Exterior material, and a curable resin composition useful as a coating,
The present invention relates to a transparent substrate such as glass or a transparent plastic plate coated with the curable resin composition on one or both sides.

[0002]

2. Description of the Related Art Exterior materials for civil engineering and construction materials represented by concrete and mortar and metal materials such as trains include:
Acrylic silicon, polyurethane, and the like are generally used, and it is known that a cured coating film having excellent weather resistance and strength can be obtained. Because these buildings are exposed to the outside world, the coatings must have protection properties against contamination by rain, oil, dust and the like. In addition, there are many cases in which sticking paper such as magic, paint, graffiti by spraying, posters, etc. significantly lowers the aesthetics of a building, and a coating film having excellent protection performance against these contaminants is desired.

As a coating agent for protecting the base material from such contamination, graffiti or sticking paper, a fluorine-based or silicone-based coating material is mainly used, but there are few which exhibit a sufficient effect continuously. Some of them often require a remover such as an organic solvent to remove graffiti. Therefore, a coating film that can easily remove graffiti contamination with water, an aqueous detergent, a dry cloth, or the like is required. Some silicone-containing antifouling paints have high water / oil repellency, but generally have poor compatibility with various resins such as acrylics and silicone, causing phase separation. There's a problem. In particular, it is difficult to incorporate a high-molecular-weight polysiloxane into the resin, and on a smooth surface such as glass, repelling and crater phenomena may occur during the drying process. For these reasons, it has been difficult to obtain a coating film having high water and oil repellency while maintaining transparency and smoothness on a transparent substrate such as glass or plastic.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to a curable composition which forms a transparent and smooth coating film having excellent curability and adhesiveness, and high water and oil repellency on architectural inorganic substrates and plastics. An object of the present invention is to provide a transparent base material having high water / oil repellency while maintaining transparency and smoothness with a resin composition.

[0005]

DISCLOSURE OF THE INVENTION The present inventors have developed an epoxy group-containing resin containing at least a silicone block copolymer having a polymer part having a plurality of epoxy groups in a polymer chain and a polyorganosiloxane part. By coating a curable resin composition containing a polyfunctional amine compound on an inorganic substrate or plastic, a transparent and smooth coating film having excellent stain resistance can be formed, and the magical graffiti on the coating film surface can be dried with a dry cloth. It can be easily removed, the adhesive film such as cellophane tape applied to the surface of the coating film can be easily peeled off, and the coated material applied to a transparent base material such as glass or transparent plastic has the transparency of the coated object. The present inventors have found that the above-mentioned performance can be obtained without causing any harm, and have reached the present invention.

[0006] The stain resistance of the surface of the cured coating film is determined by determining whether the component (a) has a polymer part having a plurality of epoxy groups in the polymer chain and an epoxy group containing at least a silicone block copolymer having a polyorganosiloxane part. The polyorganosiloxane portion of the contained resin is introduced into the crosslinked structure, and is manifested because the polyorganosiloxane portion is oriented on the surface due to low free energy. In addition, the transparency of the coating film depends on the component (a).
A polymer part having a plurality of epoxy groups in a polymer chain and a silicone-based block copolymer in an epoxy-containing resin containing at least a silicone-based block copolymer in which a polyorganosiloxane part is present are microscopically formed in a coating film. It can be obtained because of phase separation, and does not impair the transparency when applied to a transparent substrate.

That is, the first invention comprises (a) an epoxy group-containing resin containing at least a polymer block having a plurality of epoxy groups in a polymer chain, and a silicone block copolymer having a polyorganosiloxane block. And (b) a curable resin composition containing a polyfunctional amine compound. Second
The invention of (1) is that the component (a) has an α, β-
It is characterized by containing at least a silicone block copolymer in which a copolymer part of an ethylenically unsaturated monomer and another α, β-ethylenically unsaturated monomer and a polydimethylsiloxane part are bonded in a block polymer state. The curable resin composition according to the first invention, wherein

[0008] A third aspect of the present invention is that all or a part of the component (a) is a compound represented by the general formula:

[0009]

Embedded image

(Where x and n are integers, x = 10 to 300;
n = 1 to 20) and a radical polymerization initiator having a molecular weight of 1000 or less,
A first product produced by copolymerizing an α, β-ethylenically unsaturated monomer having an epoxy group with one or more other α, β-ethylenically unsaturated monomers.
A curable resin composition according to the invention or the second invention.
A fourth invention is the curable resin composition according to any one of the first invention and the third invention, which comprises a polyfunctional (meth) acrylate compound. A fifth invention is the curable resin composition according to either the first invention or the fourth invention, comprising a silane compound having an epoxy group or an amino group.

A sixth invention is a transparent substrate characterized in that the curable resin composition according to any one of the first invention to the fifth invention is applied on one surface or both surfaces. A seventh invention is the transparent substrate according to the sixth invention, which transmits 99% or more of light having a wavelength of 660 nm.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The curable resin composition of the present invention comprises
(A) a main component containing an epoxy group-containing resin containing at least a silicone block copolymer having a polymer part having a plurality of epoxy groups in a polymer chain and a polyorganosiloxane part; and (b) a polyfunctional amine compound. It is used as a two-pack type curable resin composition which is mixed with a curing agent at the time of use. The curable resin composition of the present invention may be in a liquid state in which the main agent and the curing agent are mixed, but in order to quickly and uniformly mix and obtain excellent cured physical properties, both the main agent and the curing agent are required. It is liquid and has a viscosity of 1000c in the mixed state
It is desirably not more than ps (25 ° C.).

The term "liquid" as used herein means not only a liquid in which two or more kinds of compounds are completely compatible with each other, but also a powdery compound in an emulsion, a forced emulsified liquid, a non-aqueous dispersion or a liquid compound. It also includes dispersed heterogeneous systems. As the compound contained in the curable resin composition of the present invention, any compound can be used as long as it is liquid at the time of mixing. (A) The epoxy group-containing resin containing at least a polymer block having a plurality of epoxy groups in the polymer chain and a silicone block copolymer having a polyorganosiloxane block is repellent while maintaining transparency in the present invention. It is indispensable to exhibit water and oil repellency. The silicone-based block copolymer may be a diblock type, a triblock type or a block copolymer having a repetition of more than that, and a polydimethylsiloxane portion and a polymer portion having a plurality of epoxy groups in a polymer chain. The structure of the bonding portion may be any structure as long as it is stable in a solution or a coating film for a long time.

As a method for producing the above silicone block copolymer, industrially, a polydimethylsiloxane compound having a group having a chain transfer ability at a terminal is prepared by polymerizing an α, β-ethylenically unsaturated monomer with a polymerization system. Using a polyorganosiloxane compound having a group that acts as a polymerization initiator such as an azo group, a peroxy group, or the like,
A method of polymerizing an α, β-ethylenically unsaturated monomer is simple and preferred. As a polydimethylsiloxane compound having a group that functions as a polymerization initiator, a general formula

[0015]

Embedded image

(Where x and n are integers, x = 10 to 300;
n = 1 to 20), and an epoxy group-containing α, β-ethylenically unsaturated monomer and other 1
By copolymerizing one or more kinds of α, β-ethylenically unsaturated monomers, the silicone-based block copolymer can be produced in one step. As the α, β-ethylenically unsaturated monomer having an epoxy group, glycidyl (meth) acrylate, glycidyl allyl ether,
2,3-Epoxy-2-methylpropyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, 4-vinyl-1-cyclohexene 1, epoxide and the like are included. Not limited.

Other α, β-ethylenically unsaturated monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n- Examples of non-butyl (meth) acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate and the like Alkyl esters of saturated monocarboxylic acids, nitriles such as (meth) acrylonitrile, styrenes such as styrene and α-methylstyrene, unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, fumaric acid, and itaconic acid; 2-hydroxyethyl (meth) acryl Over DOO, hydroxypropyl (meth) acrylate, hydroxyl group-containing monomers such as polyethylene glycol (meth) acrylate, (meth) acrylamide, N, N-dimethylacrylamide, N-IS
Amide group-containing monomers such as o-propylacrylamide and diacetone acrylamide; methylol group-containing monomers such as N-methylol (meth) acrylamide and dimethylol (meth) acrylamide; N-methoxymethyl (meth) acrylamide; N-butoxymethyl (meth) ) An alkoxymethyl group-containing monomer such as acrylamide, an amino group-containing monomer such as N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, ethylene, propylene,
Olefins such as isoprene, dienes such as chloroprene and butadiene, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, iso-propyl vinyl ether, n-butyl vinyl ether, is
Examples include vinyl ethers such as o-butyl vinyl ether and the like, and vinyl acetates and fatty acid vinyls such as vinyl propionate, but are not necessarily limited thereto. The α, β-ethylenically unsaturated monomers can be used alone or in combination of two or more.

Here, (meth) acrylate means methacrylate or acrylate, (meth) acrylonitrile means methacrylonitrile or acrylonitrile, (meth) acrylic acid means methacrylic acid or acrylic acid, and (meth) acrylic acid. Acrylamide refers to methacrylamide or acrylamide. In general, when polymerization is performed using only the high-molecular azo initiator, the amount of azo groups in the system is relatively small, and a decrease in polymerization conversion and an increase in molecular weight and an increase in viscosity occur. Problems arise in workability and the like. Therefore, by a method using a radical polymerization initiator having a molecular weight of 1000 or less, the polymerization conversion rate,
It is necessary to adjust the molecular weight and viscosity of the polymer. Molecular weight 1
Examples of the radical polymerization initiator having a molecular weight of 000 or less include peroxides such as dibutyl peroxide, benzoyl peroxide, and lauroyl peroxide, 2,2′-azobisisobutyronitrile, and 2,2 ′.
Examples thereof include azobis compounds such as -azobis-2,4-dimethylvaleronitrile, but are not limited to the above radical polymerization initiators, and any compounds may be used.

The polymer polymerized with the above-mentioned radical polymerization initiator having a molecular weight of 1,000 or less as a starting point can be obtained only from an α, β-ethylenically unsaturated monomer unless a bimolecular termination reaction or a chain transfer reaction to the polymer occurs. In this polymerization method, a polymer blend in which a polymer containing only α, β-ethylenically unsaturated monomers is present in addition to a block polymer starting from a high-molecular-weight azo-based initiator can be obtained. The thus obtained component (a) an epoxy group-containing resin containing at least a silicone-based block copolymer having a polyorganosiloxane portion and a polymer portion having a plurality of epoxy groups in the polymer chain is a compatibilizer. Since it contains a block copolymer having the function of, for example, it is compatible with other polymers of α, β-ethylenically unsaturated monomers, silicone resins, and the like, and these can be used as a mixture. .

Component (a) The epoxy group-containing resin containing at least a polymer part having a plurality of epoxy groups in the polymer chain and a silicone block copolymer having a polyorganosiloxane part is an epoxy group-containing α, β. 20 to 50% by weight of ethylenically unsaturated monomer, 1 to 50% by weight, preferably 3 to 30% by weight of polyorganosiloxane, and 1 to 79% by weight of other α, β-ethylenically unsaturated monomer %
It is desirable to be contained. This polymerization is usually performed by solution polymerization or non-aqueous dispersion polymerization. As the polymerization solvent, methanol, ethanol, isopropanol, butanol, alcohols such as isobutanol, acetone,
Ketones such as methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate, propyl acetate, isobutyl acetate and butyl acetate; aromatic hydrocarbons such as toluene and xylene; and aliphatic hydrocarbons such as hexane and heptane. These can be used alone or in a mixed system.

The component (b) polyfunctional amine compound includes:
A compound having two or more primary or secondary amino groups, and a liquid at room temperature can be suitably used. Considering the workability at the time of mixing, coating or pouring with the main agent, the viscosity is 5 to 5.
The flash point of 1000 cps (25 ° C) is 70-300 ° C in consideration of the working environment and safety.
It is desirable to use petroleum products and fourth petroleum products having low odor. Specifically, isophorone diamine (IP
DA), bis (4-amino-3-methylcyclohexyl) methane, 4,4′-bis (p-aminocyclohexyl) methane,
Or polyoxyalkyleneamines such as Jeffamine D-230, Jeffamine D-400, Jeffamine D-2000, and Jeffamine T-403 manufactured by Jefferson Chemical Co., but are not necessarily limited thereto. Absent.

The curable resin composition may contain a polyfunctional (meth) acrylate compound for adjusting the curing speed and adjusting the glass transition temperature of the cured product. The curing rate can be increased by utilizing the Michael addition reaction between the (meth) acryloyl group of the polyfunctional (meth) acrylate compound and the amine having active hydrogen as the first-stage crosslinking reaction. Examples of the polyfunctional (meth) acrylate compound include a compound obtained by esterifying a polyhydric alcohol having a valence of 3 or more, desirably 6 or less with (meth) acrylic acid, and an epoxy resin having two or more epoxy groups. Epoxy acrylate to which acrylic acid is added is used. Specifically, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, 3- (meth) acryloyloxyglycerin mono (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) A) 6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) ) Acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide-modified bisphenol A di (meth) acrylate, propylene oxide-modified bisphenol A di (meth) acrylate Rate, trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) Multifunctional (meth) such as acrylate and dipentaerythritol hexa (meth) acrylate
Examples include acrylates, polyvalent metal salts of (meth) acrylic acid, and mixtures thereof, but are not necessarily limited thereto. The resin composition of the present invention is a resin composition comprising a (meth) acryloyl group and an amine having active hydrogen.
Since the chael addition reaction is used as the first-stage crosslinking reaction, an acrylate compound having high reactivity is preferably used.

Further, the curable resin composition of the present invention may contain a silane compound having an epoxy group or an amino group in order to improve the adhesive strength with an inorganic material to be coated. It should be noted that those having an epoxy group are suitably mixed with the main agent, and those having an amino group are suitably mixed with the curing agent. As a silane compound having an epoxy group, β
-(3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane,
γ-glycidoxypropylmethyldimethoxysilane, γ
Epoxysilanes such as glycidoxypropylmethyldiethoxysilane, and silane compounds having an amino group include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-
Examples include, but are not necessarily limited to, aminosilanes such as (aminoethyl) -γ-aminopropyltrimethoxysilane and N-β- (aminoethyl) -γ-aminopropyltriethoxysilane.

The silane compound having an epoxy group or an amino group is determined by the number of epoxy groups in the silane compound or the active hydrogen in the amino group relative to the total number of epoxy groups in the epoxy resin and (meth) acryloyl groups in the polyfunctional (meth) acrylate compound. It is desirable to mix them so that the ratio of numbers is 0.01 to 0.3. If it is less than 0.01, the effect of improving the adhesion performance to the inorganic base material is low. If it exceeds 0.3, the condensation of the alkoxysilyl groups promoted by the alkali and moisture of the substrate occurs preferentially over the Michael addition reaction, the curing reaction of the epoxy resin, and the reaction of the alkoxysilyl group on the substrate, The siloxane bond becomes dense, the film becomes brittle, and the impact resistance deteriorates.

The curable resin composition of the present invention has a ratio of the sum of the number of epoxy groups and the number of acrylate groups in the main component to the number of active hydrogens of amino groups in the curing agent of 0.8 to 1.25, preferably equivalent. It is desirable to mix them. When the number of amino group active hydrogens is small, the crosslinking density decreases, and the coating film hardness and antifouling property decrease. When the amino group active hydrogens are large, weather resistance, water resistance and acid resistance deteriorate. Various additional components can be added to the curable resin composition of the present invention for various purposes. For example, fillers, diluents or resin components are added for improving the cured physical properties, viscosity adjustment or cost reduction, and antibacterial agents, antifungal agents or preservatives are added to give added value, and for coloring. A pigment may be added, and a polymerization inhibitor may be added to suppress radical polymerization of the (meth) acryloyl group. In addition, by adding an additional component that reacts with the main component essential component but does not react with the curing agent essential component to the curing agent, and an additional component that reacts with the curing agent essential component but does not react with the main component essential component to the main component, Storage stability and reactivity after mixing and cured physical properties can be improved. Further, in addition to the above-mentioned additive components, an adhesive area reducing agent such as plastic beads, urethane beads, and silica beads may be added to improve the ability to prevent sticking.

The viscosity of the main agent and the curing agent is 1000 cp
s (25 ° C.) or less is desirable. When the viscosity is higher than 1000 cps, the workability at the time of mixing the main agent and the curing agent and applying to the base material is deteriorated. The viscosity can be adjusted by selecting the material. When the viscosity is reduced to facilitate the coating operation, it is preferable to use an organic solvent. Examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol and isobutanol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate, propyl acetate, isobutyl acetate and butyl acetate; toluene; Examples thereof include aromatic hydrocarbons such as xylene and aliphatic hydrocarbons such as hexane and heptane, and these can be used alone or in a mixed system.

The transparent substrate on which the curable resin composition is applied includes, for example, glass, acrylic resin, polyester, polyvinyl chloride, polycarbonate, polyethylene terephthalate, polyethylene naphthalate and the like. It is desirable to apply about 0.1 μm.

[0028]

The present invention will be described in more detail with reference to examples. Production Example 1 [Synthesis of Epoxy Group-Containing Silicone Block Copolymer: Resin Solution A] 50 parts of methyl isobutyl ketone was charged into a 1000 ml flask equipped with a stirrer, thermometer, condenser, and nitrogen inlet tube, and the temperature was raised to 90 ° C. Then, separately prepared 40 parts of glycidyl methacrylate, 40 parts of methyl methacrylate, and 2-hydroxyethyl methacrylate 1
0 parts, VPS-0501 (manufactured by Wako Pure Chemical Industries, Ltd .: polydimethylsiloxane polymer azo initiator, the molecular weight of the polydimethylsiloxane part is about 5000, the number average molecular weight is about 2)
-30,000) 10 parts, azobisisobutyronitrile 0.5
Part, a mixture of 50 parts of methyl isobutyl ketone was added dropwise over 2 hours using a dropping funnel. One hour later, 0.5 parts of azobisisobutyronitrile was added, and the mixture was stirred at the same temperature for 3 hours and then polymerized. finished. As described above, the solid content 52
By weight, an epoxy group-containing silicone block copolymer was obtained. This is designated as a resin solution A.

Production Example 2 [Synthesis of Epoxy Group-Containing Silicone Block Copolymer: Resin Solution B] VPS-0501 was converted to VPS-1001 (Wako Pure Chemical Industries, Ltd.) using the same equipment as used when Resin Solution A was synthesized. Manufactured by: Polydimethylsiloxane-based polymeric azo initiator, molecular weight of polydimethylsiloxane part about 1000
0, a number average molecular weight of about 70 to 90,000), and an epoxy group-containing silicone-based block copolymer having a solid content of 52% by weight was obtained by the same blending and operation. This is designated as a resin solution B. Production Example 3 [Synthesis of Epoxy Group-Containing Silicone-Based Graft Copolymer: Resin Solution C] VPS-0501 was converted to FM-0721 (manufactured by Chisso Corporation: methacryloxyorganopoly) using the same equipment as used when resin solution A was synthesized. Siloxane, trade name: Silaplane FM-0721, molecular weight about 500
Except that the procedure was changed to 0), an epoxy group-containing silicone graft copolymer having a solid content of 54% by weight was obtained by the same blending and operation. This is designated as a resin solution C.

Production Example 4 [Synthesis of Epoxy Group-Containing Acrylic Resin: Resin Solution D] VPS-05 was prepared using the same equipment as used when Resin Solution A was synthesized.
An epoxy group-containing acrylic resin having a solid content of 51% by weight was obtained by the same blending and operation except that 01 was changed to isobutyl methacrylate. This is designated as a resin solution D. Abbreviations used in Examples and Comparative Examples are shown below. [Polyfunctional amine compound] D-400: polyoxypropylenediamine ("Jeffamine D-400" manufactured by San Techno Chemical Co., Ltd., active hydrogen equivalent: 100) [Polyfunctional (meth) acrylate compound] SR-355: ditrimethylol Propane tetraacrylate (SR-355 manufactured by Sartomer, acryloyl equivalent 116.5) [Silane compound having epoxy group or amino group] S510: γ-glycidoxypropyltrimethoxysilane (Silaace S510 manufactured by Chisso Corporation, epoxy equivalent) 236.3) S330: γ-aminopropyltriethoxysilane (Silaace S330 manufactured by Chisso Corporation, epoxy equivalent 2)
21.4) [Diaminoorganopolysiloxane] FM-3321: Diaminoorganopolysiloxane ("Silaprene FM-3321, active hydrogen equivalent 1250" manufactured by Chisso Corporation) Examples and Comparative Examples Examples 1 to 5 and Comparative Examples 1 to 1 With respect to 2, in accordance with the formulation in Table 1, the main agent and the curing agent were mixed so that the ratio of the sum of the number of epoxy groups and the number of acrylate groups in the main agent to the number of active hydrogen atoms of the amino groups in the curing agent was equivalent, and ethyl acetate or The active ingredient was diluted to 30% with methyl ethyl ketone to obtain a curable resin composition.Even if dilution with ethyl acetate or methyl ethyl ketone was performed for each of the main ingredients and the curing agent before mixing, the coating film form and physical properties differed. There was no.

The main agent and the curing agent were stored in a separate container and sealed at 25 ° C. for a long period of time without increasing the viscosity or gelling. Also,
The curable resin composition obtained by mixing the main agent and the curing agent is 24 at room temperature.
After hours could be used.

[0032]

[Table 1]

The curable resin compositions obtained in Examples and Comparative Examples were applied to an acrylic plate, a polycarbonate plate or a glass plate at a film thickness of 10 μm, and dried at room temperature for one week. And a removal test, a cellophane tape specific adhesion test, and an evaluation of transparency. Test methods used in Examples and Comparative Examples are shown below. Table 2 shows the results. [Graffle antifouling and removal test after application] Active ingredient 30%
Curable resin composition of glass plate or acrylic plate or polycarbonate plate (all 15cm x 7cm x 2mm)
Was coated with a bar coater to give a one week cure time at room temperature. Graffiti was performed on the surface of the coating film with an oil-based magic, and non-adhesion was evaluated.

Evaluation ：: Hardly adhered Δ: Slightly hardly adhered ×: Adhered Also, after 24 hours had elapsed, the film was rubbed with a dry cloth to evaluate the removability. ：: Easily removable, no abnormality in the coating film △: Removable but traces left ×: Unremovable [Cellophane tape adhesion test after application of glass plate] In the same manner as above, the curable resin composition was applied. Allowed one week cure time at room temperature. A commercially available cellophane tape was stuck on the surface of a smooth shape, and the peelability was examined.

：: easily peeled off ：: slightly resistant ×: similar resistance to untreated glass plate [Evaluation of transparency of coated transparent substrate] As described above, curable resin composition was coated The transparent substrate thus obtained was visually observed. ：: Transparent coating film X: Cloudy coating film In addition, light having a wavelength of 660 nm was transmitted perpendicularly to the coated surface by an absorptiometer, and the transmittance to an uncoated substrate was measured.

[0036]

[Table 2]

[0037]

The curable resin composition of the present invention is cured on an inorganic substrate such as a plastic plate such as acrylic or polycarbonate or glass, and has high stain resistance and anti-sticking properties, and is adhered to the substrate. It is useful as an antifouling paint in the fields of construction and civil engineering because it forms a smooth coating film with excellent properties. In addition, the transparent substrate coated with the curable resin composition expresses the above performance without impairing its transparency.
It is useful as a part of civil engineering structures.

Claims (7)

[Claims] 1. An epoxy group-containing resin containing at least a polymer part having a plurality of epoxy groups in a polymer chain and a silicone block copolymer having a polyorganosiloxane part, and (b) a polyfunctional resin. A curable resin composition containing an amine compound. 2. The composition according to claim 1, wherein component (a) is an α, β having an epoxy group.
-That at least a silicone-based block copolymer in which a copolymer portion of an ethylenically unsaturated monomer and another α, β-ethylenically unsaturated monomer and a polydimethylsiloxane portion are bonded in a block polymer form. Claim 1.
The curable resin composition according to the above. (3) All or a part of the component (a) is represented by the following general formula: (Where x and n are integers, x = 10 to 300, n = 1 to 20)
And a molecular weight of 100.
Copolymerizing an α, β-ethylenically unsaturated monomer having an epoxy group with one or more other α, β-ethylenically unsaturated monomers using a radical polymerization initiator of 0 or less in combination. 3. The method according to claim 1, wherein
3. The curable resin composition according to item 1. 4. The curable resin composition according to claim 1, further comprising a polyfunctional (meth) acrylate compound. 5. The curable resin composition according to claim 1, further comprising a silane compound having an epoxy group or an amino group. 6. A transparent substrate, characterized in that the curable resin composition according to claim 1 is applied on one or both sides. 7. The transparent substrate according to claim 6, which transmits 99% or more of light having a wavelength of 660 nm.