JPH10251598A - Cureable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cureable resin composition excellent in coating properties to an inorganic substrate for a building, and hardenability, and capable of providing a coating film having highly water-repellent and oil-repellent properties by adding a specific organopolysiloxane to a polyfunctional (meth)acrylate compound and a polyfunctional amine compound. SOLUTION: This cureable resin composition comprises (A) a polyfunctional (meth)acrylate compound, (B) an organopolysiloxane having a (meth)acryloyl group, an epoxy group or an amino group, and (C) a polyfunctional amine compound (e.g. isophoronediamine). For example, pentaerythritol di(meth) acrylate, triethylene glycol di(meth)acrylate, etc., are used as the component A. The component B containing the (meth)acryloyl group or the epoxy group is preferably formulated with a principal ingredient containing the component A, and the component B containing the amino group is preferably formulated with a hardening agent containing the component C. An epoxy resin for improving the hardness of the coating film and a silane containing the epoxy group or the amino group for improving adhesive strength is preferably formulated therewith.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an inorganic substrate such as concrete, mortar, ceramic, stone, metal plate, etc., which cures at room temperature on dry and wet surfaces and contaminates with rain, oil, dust, water-based or oil-based paint. The present invention relates to a curable resin composition useful as an exterior material, a repair material, a floor coating agent, and a coating material, for forming a coating film having excellent protection properties against water.

[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 where graffiti by magic or paint spray significantly reduces 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 the graffiti contamination, a fluorine-based or silicone-based paint is mainly used. In many cases, a removing agent such as an organic solvent is required for removal. Therefore, a coating film that can easily remove graffiti contamination with water or a dry cloth is required. Some silicone-containing antifouling paints have high water / oil repellency, but generally cause phase separation due to the low compatibility of silicone with various resin solutions such as acrylic. There is a problem. In particular, it has been difficult to incorporate a high molecular weight polysiloxane into the resin.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to a curable resin composition which is excellent in application performance and curability to an inorganic substrate for construction such as concrete and forms a coating film exhibiting high water / oil repellency. For the purpose of providing.

[0005]

Means for Solving the Problems The present inventors have found that a curable resin composition containing a polyfunctional (meth) acrylate compound and a polyfunctional amine compound has a (meth) acryloyl group,
By adding an organopolysiloxane having an epoxy group or an amino group, a coating film having excellent stain resistance can be formed on an inorganic substrate, and the graffiti by magic on the coating film surface can be easily removed with a dry cloth. This has led to the present invention. The stain resistance of the surface of the cured coating film is determined as follows: during the Michael reaction between a) a polyfunctional (meth) acrylate compound and c) a polyfunctional amine compound, b) a (meth) acryloyl group which is a high water / oil repellent component; It is expressed by incorporating an organopolysiloxane having an epoxy group or an amino group and introducing it into a crosslinked structure.

That is, the present invention relates to a) polyfunctional (meth)
The present invention relates to a curable resin composition containing an acrylate compound, b) an organopolysiloxane having a (meth) acryloyl group, an epoxy group, or an amino group, and c) a polyfunctional amine compound. The present invention also relates to the curable resin composition containing an epoxy resin. The present invention also relates to the curable resin composition containing a silane compound having an epoxy group or an amino group. The present invention also relates to the curable resin composition containing a monofunctional (meth) acrylate compound having a fluoroalkyl group.

[0007] The present invention also relates to the above curable resin composition containing a monofunctional epoxy compound having a fluoroalkyl group. Further, the present invention provides Xa, wherein the number of (meth) acryloyl groups contained in the curable resin composition is Xa, the number of epoxy groups is Xe, and the number of active hydrogens of amino groups is Y.
The present invention relates to the curable resin composition, wherein ≦ Y ≦ (Xa + Xe).

In the curable resin composition of the present invention, the Michael reaction is further promoted under water or alkaline conditions. The reaction is accelerated by mixing with the wet concrete surface, inside the gap, or with the cement slurry, and has the excellent feature that it hardens in a short time.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The curable resin composition of the present invention comprises
a) a main agent containing a polyfunctional (meth) acrylate compound and b) an organopolysiloxane having a (meth) acryloyl group or an epoxy group, and c) a curing agent containing a polyfunctional amine compound, or a) a polyfunctional (meth) acrylate It is used as a two-pack type curable resin composition in which a base material containing a compound and a curing agent containing an amino group-containing organopolysiloxane and c) a polyfunctional amine compound are mixed when used. 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 1
Desirably, it is 100 to 1000 cps (25 ° C.).

[0010] The liquid mentioned here includes not only a liquid in which two or more kinds of compounds are completely compatible with each other, but also a heterogeneous system in which a powdery compound is dispersed in a liquid compound. 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. Therefore, it is desirable to select a substance having a flash point of 70 to 300 ° C. (hazardous substances, Class 4, Petroleums 4, and Petroleums 4) with low odor.

A) As the polyfunctional (meth) acrylate compound, a polyfunctional (meth) acrylate compound having a hydroxyl group and a polyfunctional (meth) acrylate compound having no hydroxyl group can be used. The curing time of the curable resin composition can be controlled by adjusting the mixing ratio between the polyfunctional (meth) acrylate compound having a hydroxyl group and the polyfunctional (meth) acrylate compound having no hydroxyl group. . This utilizes the effect that the (meth) acryloyl group of the (meth) acrylate compound is activated by the active hydrogen of the hydroxyl group, and the nucleophilic reaction by the amine compound of the curing agent, that is, the Michael reaction is promoted.

As the polyfunctional (meth) acrylate compound having a hydroxyl group, a polyhydric alcohol having a valence of 3 or more, desirably 6 or less can be prepared by using acrylic acid or methacrylic acid (so that at least one hydroxyl group remains). A compound esterified with (meth) acrylic acid) and an epoxy acrylate obtained by adding (meth) acrylic acid to an epoxy resin having two or more epoxy groups are used. Specific examples of the compound obtained by esterifying a polyhydric alcohol with (meth) acrylic acid include pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, 3- (meth) acryloyloxyglycerin mono (meth) acrylate, Examples thereof include dipentaerythritol tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate, but are not necessarily limited thereto. Since the resin composition of the present invention utilizes a Michael addition reaction between a (meth) acryloyl group and an amine having active hydrogen as a first-stage crosslinking reaction, an acrylate compound having high reactivity is preferably used.

Polyfunctional (meth) having no hydroxyl group
As the acrylate compound, a compound in which all the hydroxyl groups of a polyhydric alcohol, preferably a dihydric to hexahydric alcohol are esterified with (meth) acrylic acid is used. Specifically, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate Acrylate,
Ethylene oxide-modified bisphenol A di (meth) acrylate, propylene oxide-modified bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified trimethylol propane tri Polyfunctional (meth) acrylates such as (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and polyvalent metal salts of (meth) acrylic acid or These include mixtures, but are not necessarily limited thereto. Since the resin composition of the present invention utilizes a Michael addition reaction between a (meth) acryloyl group and an amine having active hydrogen as a first-stage crosslinking reaction, an acrylate compound having high reactivity is preferably used.

B) The organopolysiloxane having a (meth) acryloyl group, an epoxy group or an amino group generally has a number average molecular weight (hereinafter, referred to as Mn) of 500.
Functional groups having a double-end functional type, a single-terminal functional type, or a side-chain functional type represented by the following structural formula of about 50,000 can be used.

[0015]

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In the organopolysiloxane having a functional group at both ends, an alkyl chain having l = 1 to 10 and n = 1 to 10 is introduced at both ends of a linear polysiloxane chain having m = 5 to 200,
It has a (meth) acryloyl group, an epoxy group, or an amino group X at both ends. In addition, a part of the methylene portion of the alkyl chain may be substituted with an ether skeleton. In general, a methyl group is introduced into R.

Examples of the siloxane having both ends functional groups having a (meth) acryloyl group include Silaplane FM-7711 manufactured by Chisso Corporation (1 = n = 3, m = 8.2 in the above structural formula).
9, R = methyl group, X = methacryloyl group, Mn1000),
Thyraplane FM-7721 (In the above structural formula, l = n
= 3, m = 62.28, R = methyl group, X = methacryloyl group,
Mn5000), Silaplane FM-7725 (in the above structural formula, l = n = 3, m = 129.77, R = methyl group, X = methacryloyl group, Mn10000).

Examples of the both-end functional siloxane having an epoxy group include Silaplane FM-5511 manufactured by Chisso Corporation.
(In the above structural formula, l = n = 5 (including some ether skeletons), m = 8.61, R = methyl group, X = epoxy group, Mn1000), Thyraplane FM-5521 (in the above structural formula, = n = 5 (including some ether skeletons), m
= 62.60, R = methyl group, X = epoxy group, Mn5000), Silaplane FM-5525 (in the above structural formula, l = n = 5
(Including some ether skeletons), m = 130.10, R = methyl group, X = epoxy group, Mn10000).

Examples of the amino-functional siloxane having both functional groups at both ends include Silaplane FM-3311 manufactured by Chisso Corporation.
(In the above structural formula, l = n = 3, m = 10.15, R = methyl group, X = amino group, Mn1000), Silaplane FM-332
1 (In the above structural formula, l = n = 3, m = 64.14, R = methyl group, X = amino group, Mn5000), Thyraplane FM-3
325 (In the above structural formula, l = n = 3, m = 131.63, R
= Methyl group, X = amino group, Mn10000).

In the organopolysiloxane having a functional group at one end, an alkyl chain having n = 1 to 10 is introduced into one end of a linear polysiloxane chain having n = 5 to 200, and (meth) ) Those having the above structural formula having an acryloyl group, an epoxy group, or an amino group X. In addition, a part of the methylene portion of the alkyl chain may be substituted with an ether skeleton. In general, a methyl group is introduced into R. Further, the terminal siloxane skeleton may be branched.

As a siloxane having a (meth) acryloyl group and having a single-terminal functional group, Silaplane FM-0711 manufactured by Chisso Corporation (m に お い て 8, n = 3, R
= Methyl group, X = methacryloyl group, Mn1000), Silaplane FM-0721 (where m ≒ 62, n =
3, R = methyl group, X = methacryloyl group, Mn5000),
Thyraplane FM-0725 (In the above structural formula, m ≒ 13
0, n = 3, R = methyl group, X = methacryloyl group, Mn10
000), Silaplane TM-0701, Silaplane TM-0
701T (in the above structural formula, n = 3, R = methyl group, X =
A methacryloyl group, and a molecular weight of 423).

Examples of the one-terminal functional siloxane having an epoxy group include Silaplane FM-0511 manufactured by Chisso Corporation.
(In the above structural formula, m ≒ 9, n = 5 (including some ether skeletons), R = methyl group, X = epoxy group, Mn10
00), Silaplane FM-0521 (in the above structural formula,
m ≒ 63, n = 5 (including some ether skeleton), R = methyl group, X = epoxy group, Mn5000), Silaplane FM
-0525 (in the above structural formula, mｎ130, n = 5 (including some ether skeletons), R = methyl group, X = epoxy group, Mn10000).

The side chain functional type organopolysiloxane is
n = about 5 to about 200 The above-mentioned structural formula in which an alkyl group X having a (meth) acryloyl group, an epoxy group or an amino group at a terminal is bonded to a part of silicon atoms of a linear polysiloxane chain. In general, R is a methyl group.
Examples of side-chain functional siloxane having an epoxy group include L-9300, FZ-3720, FZ-3736, and FZ manufactured by Nippon Unicar Co., Ltd.
-3745, Y-7499 (in the above formula, R = methyl group,
X = alkyl group having an epoxy group at the terminal). Examples of the side-chain functional siloxane having an amino group include FZ-3705, FZ-3707, and FZ-3 manufactured by Nippon Unicar Co., Ltd.
710, FZ-3750, FZ-3760 (In the above structural formula, R =
Methyl group, X = alkyl group having an amino group at the terminal) and the like.

B) Among organopolysiloxanes having a (meth) acryloyl group, an epoxy group or an amino group, those having a (meth) acryloyl group or an epoxy group are compounded in a main component, and those having an amino group are mixed in a curing agent. It is appropriate to do. b) The organopolysiloxane having a (meth) acryloyl group, an epoxy group, or an amino group is used in an amount of 0.01 to 0.01% based on the total weight of the curable resin composition.
It is desirable to contain about 10% by weight. When the content is less than 0.01% by weight, the effect of improving the antifouling property and the water / oil repellency is low, and when it exceeds 10% by weight, a) polyfunctional (meth) acrylate compound or c) polyfunctional amine compound is phase-separated. And it is difficult to obtain a uniform curable resin composition.

C) The polyfunctional amine compound is a compound having two or more primary or secondary amino groups, and a liquid compound 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 1000 cps (25
℃), the flash point is 70 considering the working environment and safety.
It is desirable to use those having a low odor of up to 300 ° C. (hazardous substances, Class 4 petroleums, fourth petroleums). Specifically, isophorone diamine (IPDA), bis (4-amino-3-methylcyclohexyl) methane, 4,4′-bis (p-aminocyclohexyl) methane, or Jeffamine D-230 manufactured by Jefferson Chemical Co., Jeffamine D-400
And polyoxyalkyleneamines such as Jeffamine D-2000 and Jeffamine T-403, but are not necessarily limited thereto.

The curable resin composition of the present invention may be mixed with a liquid or solid epoxy resin having two or more epoxy groups at room temperature in order to improve the hardness of the coating film. The epoxy resin is blended with the base material containing the above a).
As the epoxy resin that is liquid at room temperature, a liquid bisphenol-type epoxy resin, a polyglycidyl ether-type epoxy resin, a mixture thereof, or the like can be used, but is not necessarily limited thereto.

Examples of the liquid bisphenol type epoxy resin include Epicoat 801, Epicoat 807, Epicoat 808, Epicoat 815, Epicoat 816, Epicoat 819, Epicoat 876, Epicoat 828, Epicoat 834, and Ciba Geigy, manufactured by Yuka Shell Epoxy Co., Ltd. ) Made of Araldite GY-257, Araldite GY-252, Araldite
GY-250, Araldite GY-260, Araldide GY-280, DER324, DER331, D.C.
ER331C, DER332, DER334, DER335, DE
R.336, DER337, DER353J, DER732, DER
736 and the like.

Examples of polyglycidyl ether type epoxy resins include Denacol EX-211 (neopentyl glycol diglycidyl ether), Denacol EX-212 (1,6-hexanediol diglycidyl ether), and Denacol EX manufactured by Nagase Kasei Kogyo Co., Ltd. -221 (dibromoneopentyl glycol diglycidyl ether), Denacol EX-313,
Denacol EX-314 (glycerol polyglycidyl ether), denacol EX-321 (trimethylolpropane polyglycidyl ether), denacol EX-421 (diglycerol polyglycidyl ether), denacol EX-512, denacol EX-521 (polyglycerol polyglycidyl) Ether), Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-614B, Denacol EX-622
(Sorbitol polyglycidyl ether), denacol
EX-810 (ethylene glycol diglycidyl ether),
Denacol EX-811, Denacol EX-850, Denacol EX-8
51, Denacol EX-821, Denacol EX-830, Denacol
EX-832 (polyethylene glycol diglycidyl ether), denacol EX-911 (propylene glycol diglycidyl ether), denacol EX-941, denacol EX-9
20, Denacol EX-921, Denacol EX-931 (polypropylene glycol diglycidyl ether), Denacol EX
-2000 and Denacol EX-992.

Examples of the epoxy resin which is solid at room temperature include Epicoat 864, manufactured by Yuka Shell Epoxy Co., Ltd.
1001, Epicoat 1004, Epicoat 1007, Epicoat 10
09, Epicort 1310, Araldite GY-6040, Araldite GY-6060, Araldite GY manufactured by Ciba Geigy Corporation
-6071, Araldite 6075, Araldite GY-6084, Araldite GY-6097, Araldite GY-6099, DER661, DER664, DER66 manufactured by Dow Chemical Japan KK
For example, a bisphenol-type epoxy resin such as 7 or a mixture thereof can be used, but is not necessarily limited thereto.

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. In addition,
It is appropriate that the epoxy resin having an epoxy group is blended with the main agent and the amino group having an amino group is blended with a curing agent. Examples of the silane compound having an epoxy group include β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropylmethyl. Epoxy silanes such as dimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and the like, 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 with respect 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, As the wettability deteriorates, the siloxane bond becomes dense, and the film becomes brittle, so that it is difficult to obtain a coating film having high hardness.

Further, the curable resin composition of the present invention includes:
Formulated with a monofunctional (meth) acrylate compound with a fluoroalkyl group, a monofunctional epoxy compound with a fluoroalkyl group, or a monofunctional amine compound with a fluoroalkyl group to improve antifouling properties and water / oil repellency can do. It is suitable that the monofunctional (meth) acrylate compound and the monofunctional epoxy compound are blended in the main component, and the monofunctional amine compound is blended in the curing agent.

The monofunctional (meth) acrylate compound having a fluoroalkyl group, the monofunctional epoxy compound having a fluoroalkyl group and the monofunctional amine compound having a fluoroalkyl group are present in an amount of 0.01 to 0.01% based on the total weight of the curable resin composition. It is desirable to mix in the range of about 3% by weight. If it is less than 0.01% by weight, the antifouling property and water repellency
The effect of improving oil repellency is low, and even if the content exceeds 3%, no further effect of improving water repellency, oil repellency and stain resistance cannot be expected.

The monofunctional (meth) acrylate compound having a fluoroalkyl group includes a (meth) acryloyl group at one end and a partial or total hydrogen atom at the other end represented by the following structural formula. Having an alkyl group substituted with a fluorine atom (m = 1 to about 15) can be used. The main chain is generally a methylene chain (n = 1 to about 5), but a part of hydrogen of the methylene chain may be substituted by a hydroxyl group, or an ether bond may be included in the middle. When R is a hydrogen atom, it corresponds to an acrylate compound, and when R is a methyl group, it corresponds to a methacrylate compound.

[0035]

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Specific examples of the monofunctional (meth) acrylate compound having a fluoroalkyl group include Biscoat 3F (manufactured by Osaka Organic Chemical Industry Co., Ltd. (where m = 1, n = 1, X = F, R = H), biscoat 4F (in the above structural formula, m = 2, n = 1, X = H, R = H), biscoat 8F (in the above structural formula, m = 4, n = 1, X = H, R = H
), Viscote 17F (m = 8, n
= 2, X = F, R = H), biscoat 3FM (in the above structural formula, m = 1, n = 1, X = F, R = methyl group), and biscoat 4FM (in the above structural formula, m = 2, n = 1, X = H, R = methyl group), biscoat 8FM (in the above structural formula, m =
4, n = 1, X = H, R = methyl group), Biscoat 17FM
(In the above structural formula, m = 8, n = 2, X = F, R = methyl group), R-Made by Daikin Fine Chemical Laboratory Co., Ltd.
1210 (in the above structural formula, m = 2, n = 1, X = F, R = H
), R-1420 (in the above structural formula, m = 4, n = 2
, X = F, R = H), R-1433 (in the above structural formula,
m = 4, n = 3 (including those in which one hydrogen atom of a methylene chain is substituted with a hydroxyl group), X = F, R = H), R-
1620 (wherein m = 6, n = 2, X = F, R =
H), R-1633 (in the above structural formula, m = 6, n = 3
(Including one in which one hydrogen atom of the methylene chain is substituted with a hydroxyl group), X = F, R = H), R-1820
(In the above structural formula, m = 8, n = 2, X = F, R = H), R
-1833 (in the above structural formula, m = 8, n = 3 (including one in which one hydrogen atom of the methylene chain is substituted with a hydroxyl group), X = F, R = H), R-2020 (the above structural formula) Where m = 10, n = 2, X = F, R = H), R-3420
(In the above structural formula, m = 2, n = 2, X = CF (CF3) 2, R = H
), R-3433 (in FIG. 2, m = 2, n = 3 (including one in which one hydrogen atom of the methylene chain is substituted with a hydroxyl group), X = CF (CF3) 2, R = H), R-3620
(In the above structural formula, m = 4, n = 2, X = CF (CF ₃ ) ₂ , R = H
), R-3820 (in the above structural formula, m = 6, n = 2
, X = CF (CF ₃ ) ₂ , R = H), R-4020 (in the above structural formula, m = 8, n = 2, X = CF (CF ₃ ) ₂ , R = H), R-521
0 (in the above structural formula, m = 2, n = 1, X = H, R = H),
R-5410 (in the above structural formula, m = 4, n = 1, X = H
, R = H), R-5610 (in the above formula, m = 6
, N = 1, X = H, R = H), R-5810 (m = 8, n = 1, X = H, R = H in the above structural formula), R-6010 (m in the above structural formula, = 10, n = 1, X = H, R = H), but are not necessarily limited to these.

As the monofunctional epoxy compound having a fluoroalkyl group, a monofunctional epoxy compound represented by the following structural formula, having an epoxy group at one terminal and partially or entirely hydrogen atoms at the other terminal substituted by fluorine atoms. A compound having an alkyl group (m = 1 to about 15) can be used. The main chain is generally a methylene chain (n = 1 to about 5), but a part of hydrogen of the methylene chain may be substituted by a hydroxyl group, or an ether bond may be included in the middle.

[0038]

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Specific examples of the monofunctional epoxy compound having a fluoroalkyl group include E-1430 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.)
m = 4, n = 1, X = F), E-1630 (m = 6, n = 1, X = F in the above structural formula), E-1830 (m = 8, n = 1, X = F), E-2030 (in the above structural formula, m = 10, n = 1, X = F), E-3430 (in the above structural formula, m = 2, n = 1, X = CF ( CF ₃ ) ₂ ), E-3630
(In the above structural formula, m = 4, n = 1, X = CF (CF ₃ ) ₂ ), E
−3830 (in the above structural formula, m = 6, n = 1, X = CF
(CF ₃ ) ₂ ), E-4030 (in the above structural formula, m = 8
, N = 1, X = CF (CF ₃ ) ₂ ), E-5244 (in the above structural formula, m = 2, n = 3 (including one in which one of the methylene moieties is substituted with an ether skeleton), X = H), E-544
4 (in the above structural formula, m = 4, n = 3 (including those in which one of the methylene moieties is substituted with an ether skeleton), X =
H), E-5644 (in the above structural formula, m = 6, n = 3
(Including those in which one of the methylene moieties is substituted with an ether skeleton), X = H), E-5844 (in the above structural formula, m = 8, n = 3 (where one of the methylene moieties is substituted with an ether skeleton) , X = H) and the like, but are not necessarily limited to these.

As the monofunctional amine compound having a fluoroalkyl group, a monofunctional amine compound represented by the following structural formula, having an amino group at one terminal and partially or entirely hydrogen atoms at the other terminal substituted by fluorine atoms, is used. Alkyl group (m = 1-15)
Can be used. The main chain is a methylene chain (n = 1
To about 5), but a part of the hydrogen of the methylene chain may be replaced by a hydroxyl group, or an ether bond may be included in the middle.

[0041]

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Specific examples of the monofunctional amine compound having a fluoroalkyl group include U-1310 (manufactured by Daikin Fine Chemical Laboratory, where m = 3 and n =
1, X = F), U-1710 (in the above structural formula, m = 7
, N = 1, X = F), but are not necessarily limited to these.

Each component constituting the curable resin composition of the present invention has a number of (meth) acryloyl groups contained in the curable resin composition as Xa, a number of epoxy groups as Xe, and an active hydrogen of amino group. If the number is Y, Xa ≦ Y ≦ (Xa + Xe)
It is desirable to mix them so that When Y <Xa, the (meth) acryloyl group remains and curing is incomplete, and when Y> (Xa + Xe), unreacted amine remains and water resistance deteriorates. In order to balance the curing speed and the durability of the cured product, (Xa + Xe) = Y, and further, Xa = Xe = Y
It is desirable to make x1 / 2. Xa = Xe = Y × 1 /
By blending so as to be 2, it is possible to obtain a coating film in which the pot life and the adhesion to the inorganic substrate and the durability are well balanced.

In the curable resin composition of the present invention, various additives can be added 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.

The viscosity of the main agent and the curing agent is 100 to 1000 cp.
s (25 ° C) is desirable. If the viscosity is lower than 100 cps, it is difficult to adhere to the base material, and if the viscosity is higher than 1000 cps, the workability of mixing the main agent and the curing agent, and applying and pouring to the base material is deteriorated. The viscosity is
It can be adjusted by selecting the material. When a solid epoxy resin is used at room temperature in the main component, or when the viscosity is reduced in order to facilitate the coating operation, it is preferable to use an organic solvent. Examples of the organic solvent include isopropyl alcohol, methyl ethyl ketone, toluene, xylene, and ethyl acetate.

[0046]

The present invention will be described in more detail with reference to the following examples. Abbreviations and test methods used in the examples are shown below. a) Polyfunctional (meth) acrylate compound M305 = pentaerythritol triacrylate (“Aronix M-305” manufactured by Toa Gosei Chemical Industry Co., Ltd., acryloyl equivalent 99.3 g / eqiv.) M309 = trimethylolpropane triacrylate (Toa Gosei Chemical) "Aronix M-309" manufactured by Kogyo Co., Ltd., acryloyl equivalent 98.7 g / eqiv.) Epoxy resin EX313 = glycerol polyglycidyl ether ("Denacol EX-313" manufactured by Nagase Kasei Kogyo, epoxy equivalent 14
1 g / eqiv.) Silane compound having an epoxy group or an amino group KBM403 = γ-glycidoxypropyltrimethoxysilane (“KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd., epoxy equivalent: 23)
6.3 g / eqiv.) KBE603 = N-β- (aminoethyl) -γ-aminopropyltriethoxysilane (“KBE-60” manufactured by Shin-Etsu Chemical Co., Ltd.)
3 '', active hydrogen equivalent 88.3 g / eqiv.)

B) Organopolysiloxane having a (meth) acryloyl group, an epoxy group or an amino group FM0721 = methacryloxyorganopolysiloxane (“Silaprene FM-0721” manufactured by Chisso Corp., methacryloyl equivalent 5000 g / eqiv.) TM0701T = Methacryloxyorganopolysiloxane ("Silaprene TM-0701T" manufactured by Chisso Corporation, methacryloyl equivalent 423 g / eqiv.) FM5525 = Diglycidyl organopolysiloxane ("Silaprene FM-5525" manufactured by Chisso Corporation, epoxy) Equivalent 50
00g / eqiv.) FM3311 = Diaminoorganopolysiloxane (“Sylaplane FM-3311” manufactured by Chisso Corporation, active hydrogen equivalent 25
0g / eqiv.) FM3325 = diaminoorganopolysiloxane ("Silaplane FM-3325" manufactured by Chisso Corporation, active hydrogen equivalent 25
(00g / eqiv.)

C) Polyfunctional amine compound IPDA = isophoronediamine (Vestamine IPD manufactured by Huls Japan K.K., active hydrogen equivalent: 42.5 g / eqiv.) D2000 = polyoxypropylenediamine (Jeffa manufactured by San Techno Chemical Co., Ltd.) -Min D-2000 '', active hydrogen equivalent
520g / eqiv.) Monofunctional (meth) acrylate compound having a fluoroalkyl group VIS-17F = Perfluoroalkyl acrylate ("Biscoat 17F" manufactured by Osaka Organic Chemical Industry Co., Ltd., acryloyl equivalent 518.2) Epoxy compound having a fluoroalkyl group E-5644 = 3- (1H, 1H, 7H-dodecafluoroheptyloxy) 1,2
-Epoxy propane (Equivalent to 388.14 epoxy, manufactured by Daikin Fine Chemical Laboratory)

[Test for removing graffiti after application of mortar] The curable resin composition was applied to a commercially available mortar plate (7 cm × 7 cm × 2 cm), and a curing time of one week was given at room temperature.
The surface of the coating film was graffitied with an oily magic, and the non-adhesiveness was evaluated (（: hardly adhered, Δ: slightly hardly adhered, ×: adhered). After 24 hours had elapsed, the substrate was rubbed with a dry cloth and the removability was evaluated (○: easily removable,
Δ: can be removed by rubbing strongly, ×: cannot be removed). [Contact angle measurement] A curable resin composition was placed on a metal plate (20 cm ×
10 cm) with an applicator to give a one week cure time at room temperature. Using this sample, the contact angle with respect to water and methylene iodide was measured. For measurement, use a contact angle meter CA-DT-A type manufactured by Kyowa Interface Science Co., Ltd.
The contact angle was determined based on the average value of the three points.

[Examples 1 to 8 and Comparative Examples 1 to 3] For Examples 1 and 2, the formulations in Table 1 were used. For Examples 3 to 5, the formulations in Table 2 were used. After preparing the main agent and the curing agent according to the formulation in Table 4 for Comparative Examples 1 to 3 according to the formulation in Table 3, the two were mixed to obtain a curable resin composition. The main agent and the curing agent were placed in separate containers and sealed, and then sealed at 25 ° C.
For a long time without increasing the viscosity or gelling.

[0051]

[Table 1]

The curable resin compositions obtained in Examples and Comparative Examples were applied to a mortar plate and a metal plate, and a graffiti removal test and a contact angle measurement were performed using the cured coating film. Table 5 shows the results.

[0053]

[Table 2]

[0054]

The curable resin composition of the present invention cures on an inorganic substrate such as concrete or mortar, has high stain resistance, water and oil repellency, and has excellent adhesion to the substrate. It is extremely useful as an antifouling paint in the fields of construction and civil engineering because it forms a coated film.

Claims (6)

[Claims] 1. A) a polyfunctional (meth) acrylate compound,
A curable resin composition comprising b) an organopolysiloxane having a (meth) acryloyl group, an epoxy group, or an amino group, and c) a polyfunctional amine compound. 2. The curable resin composition according to claim 1, comprising an epoxy resin. 3. The curable resin composition according to claim 1, comprising a silane compound having an epoxy group or an amino group. 4. The curable resin composition according to claim 1, further comprising a monofunctional (meth) acrylate compound having a fluoroalkyl group. 5. The curable resin composition according to claim 1, comprising a monofunctional epoxy compound having a fluoroalkyl group. 6. Assuming that the number of (meth) acryloyl groups contained in the curable resin composition is Xa, the number of epoxy groups is Xe, and the number of active hydrogens of amino groups is Y, Xa ≦ Y ≦ (Xa +
The curable resin composition according to any one of claims 1 to 5, which is Xe).