JP2000144042A - Coating material and surface treatment using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating material excellent in coating performance and curability relative to various substrates such as concrete, glass, aluminum, polyethylene terephthalate and acrylics and capable of forming smooth coated films having a high water-repellent effect, particularly antifouling resistance to scribblings. SOLUTION: Into a coating material is incorporated a copolymer having (a) a polyorganosiloxane portion and (b) a polymer portion having an average SP value of 9.7-12 in the same molecule as the means to lower the surface free energy and to increase solvent resistance. Furthermore, crosslinking reaction is caused on the substrate material to be coated with the coating material to give high antifouling resistance to scribblings.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating agent for water- and oil-repellent treatment of a surface of an object to be coated, and a surface treatment method.

[0002]

2. Description of the Related Art In recent years, methods for lowering the free energy of various substrate surfaces have been developed for imparting various functions. The fields are diverse, and there is a demand for a substrate having a surface such as antifouling, paper sticking prevention, graffiti prevention, snow formation prevention, water repellency, oil repellency, and ink repellency. Polyorganosiloxane-based paints are used as one of these functions, but coating agents with anti-graffiti performance are particularly strict because they require organic solvent resistance, so they exhibit sufficient effects continuously. Many of these have problems, such as those that cannot be used, those that cause phase separation due to low compatibility between various resins and polyorganosiloxane, and those that cause poor transparency and tackiness of the coating film.

[0003] In order to solve this compatibility problem, for example, Japanese Patent Publication No. 03-46026 and Japanese Patent Application Laid-Open No.
No. 511, Japanese Patent Application Laid-Open No. 06-228467 and the like,
It is widely practiced to use graft or block copolymers of other component polymers and polyorganosiloxanes. However, there is no mention of a polymer portion other than the silicone component in the graft or block copolymer except for the cross-linking functional group, cross-link density, glass transition temperature and the like.

[0004]

SUMMARY OF THE INVENTION The present invention is characterized in that it comprises a copolymer in which a polyorganosiloxane part and another polymer part are present in the same molecule. It is an object of the present invention to provide a coating agent capable of effectively exhibiting anti-graffiti performance by limiting the average SP value, and a water- and oil-repellent treatment method using the coating agent.

[0005]

DISCLOSURE OF THE INVENTION The present inventors have found that a polyorganosiloxane having a low surface free energy is present in the same molecule as another polymer, and the SP value of the polymer portion other than the polyorganosiloxane portion is reduced. By limiting, we succeeded in effectively giving stain resistance, especially high graffiti stain resistance,
The present invention has been reached. The stain resistance of the cured coating surface is manifested by the fact that the polyorganosiloxane part of the copolymer having a polyorganosiloxane part and another polymer part in the same molecule is oriented on the surface because of its low free energy. I do. Here, by limiting the SP value, required physical properties, particularly, anti-graffiti performance can be effectively exhibited.

That is, in the first invention, the polyorganosiloxane part (a) and the average SP value are in the same molecule within the range of 9.7 to 9.7.
A coating agent comprising at least a copolymer (P) in which 12 polymer parts (b) are present. In the second invention, the copolymer (P) is a block polymer of a polyorganosiloxane part (a) and a polymer part (b) and / or
Alternatively, the coating agent according to the first invention, wherein the copolymer (P) is a graft polymer having the polymer part (b) as a backbone polymer and one or more polyorganosiloxane parts (a) in a side chain. The third invention has an average SP value of 9.7 to 1
2. The coating agent according to the first or second aspect, comprising the polymer (S).

[0007] A fourth aspect of the present invention is that the polymer (b) and / or the polymer (S) in the copolymer (P) contains one or more α, β-ethylenically unsaturated monomers. The coating agent according to any one of the first to third inventions, characterized in that: According to a fifth aspect of the present invention, in the polymer part (b) of the copolymer (P) and / or the polymer (S)
One or more kinds of α, β-ethylenically unsaturated monomers having a crosslinkable functional group therein are copolymerized, and the crosslinkable functional group is a self-reactive functional group; and And / or a polyfunctional crosslinking agent (C) capable of reacting with the crosslinking functional group
The first invention to the fourth invention, wherein one or more kinds are included.
A coating agent according to any one of the inventions.

In a sixth aspect, a crosslinkable self-reactive functional group present in the polymer part (b) of the copolymer (P) and / or in the polymer (S) is a hydrolyzable silyl group. Group, N
A polymethyl group or an N-alkoxymethyl group and / or a polymer which can react with a crosslinkable functional group present in the polymer part (b) and / or in the polymer (S) of the copolymer (P). The combination of the functional groups of the functional crosslinking agent (C) may be a hydrolyzable silyl group and a hydrolyzable silyl group, an epoxy group and an amino group, an epoxy group and a carboxyl group, a hydroxyl group and an isocyano group, an N-methylol group or an N-methylol group. −
The coating agent according to any one of the first to fifth inventions, wherein one or more kinds are selected from an alkoxymethyl group and an N-methylol group or an N-alkoxymethyl group.

A seventh aspect of the present invention is directed to the fifth or fifth aspect, which further comprises a copolymer (P) and / or a crosslinking catalyst for accelerating a crosslinking reaction between the copolymer (P) and the polymer (S). 6 A coating agent according to the invention. The eighth invention is
At least one of the monomers constituting the polymer part (b) and / or the polymer (S) in the copolymer (P) has 2
1st invention to 7th invention selected from -hydroxy (meth) acrylate and (meth) acrylic acid
A coating agent according to any one of the inventions. A ninth invention provides a surface treatment method comprising applying the coating agent according to any one of the first invention to the eighth invention to civil engineering buildings or other supports to impart surface water repellency and stain resistance. It is.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The coating agent of the present invention contains at least a copolymer having a polyorganosiloxane part and another polymer part in the same molecule. The copolymer may be used alone at the time of coating, or may be used as a one-pack type using a latent reactive cross-linking agent, or a curing agent containing a reactive cross-linking agent or a curing catalyst when used. It is used as a coating agent of a mixed type over liquid. The coating agent of the present invention may be in a liquid state at the time of use, but in order to quickly and uniformly mix and obtain excellent cured physical properties, each of the components to be mixed and used is in a liquid state, and the viscosity after mixing is 1000.
It is desirable that the temperature be less than cps (25 ° C.).

The term "liquid" as used herein means not only a liquid in which two or more 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 coating agent of the present invention, any compound can be used as long as it is liquid at the time of mixing. As a method for producing a polymer used in the present invention in which a polyorganosiloxane portion and another polymer portion are present in the same molecule, a polyorganosiloxane having one or more reactive functional groups in one molecule is industrially used. A method using a polymer-polymer reaction in which siloxane is reacted with another polymer, or using a polyorganosiloxane having polymerization ability, radical generation ability, and chain transfer ability to obtain other α, β-ethylenic property There is a method of reacting with an unsaturated monomer, but the latter is simpler because it can be prepared in one step.

The radically polymerizable polyorganosiloxane has a general formula

[0013]

Embedded image

(Where x is an integer from 10 to 300, Y ₁ , Y
₂ is a linear molecule having a molecular weight of 200 or less, and at least one of R ₁ and R ₂ is an acryloxy group or a methacryloxy group, and the rest is an alkyl group. However, in a solution polymerization system, if the amount of the compound capable of polymerizing at both ends is too large, the whole reaction system is gelled, so it is necessary to use the compound at a gelling amount or less. Examples of the radical-generating polyorganosiloxane include a polyorganosiloxane compound having a group that acts as a polymerization initiator such as an azo group and a peroxy group.

[0015]

Embedded image

(Where x and n are integers, x = 10 to 300;
n = 1 to 20), and α, β- using the polymer azo initiator.
By copolymerizing an ethylenically unsaturated monomer, a silicone-based block copolymer can be produced. As the chain transfer polyorganosiloxane, a general formula

[0017]

Embedded image

(Where x is an integer from 10 to 300, Y ₁ , Y
₂ is a linear molecule having a molecular weight of 200 or less, and at least one of R ₁ and R ₂ is an SH group, and the rest is an alkyl group). By copolymerizing an α, β-ethylenically unsaturated monomer using an agent, a silicone-based block copolymer can be produced. 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 the structure of a bonding portion between a polydimethylsiloxane portion and another polymer portion may be in a solution or Any structure may be used as long as it is stable for a long time in the coating film. The above-mentioned polyorganosiloxane component is indispensable for imparting surface characteristics such as anti-graffiti, water repellency, ink repellency, antifouling properties, slipperiness, and anti-snow properties to the coating film, and the required performance is required. One of these may be used alone, or two or more of them may be used in combination. In order to obtain sufficient surface characteristics, 0.1% by weight of the active ingredient of the coating agent is required.
It is desirable to copolymerize as described above, and to obtain sufficient coating properties such as adhesion to the substrate and toughness, solubility in a solvent, or 20% by weight in the effective component from the viewpoint of cost. The following composition is desirable. More preferably, it is not less than 0.2% by weight and not more than 15% by weight. Regarding the polymer part other than the polyorganosiloxane of the polymer in which the polyorganosiloxane part and the other polymer part are present in the same molecule, any polymer may be used as long as the average SP value is 9.7 to 12. The glass transition temperature may be -3 from the viewpoint of workability and the like.
It is desirable to set the temperature at 0 to 80 ° C, more preferably at 0 to 70 ° C. If it is lower than -30 ° C, sufficient coating film hardness cannot be obtained, and if it exceeds 80 ° C, the impact resistance of the coating film may decrease. The weight average molecular weight is 5,000 to 200,000, preferably 10,000 to 100,000. When it is less than 5,000, the solvent resistance is not sufficient, and when it is applied to a porous substrate, there is a problem that the coating agent is impregnated. When it exceeds 200,000, the viscosity is too high and workability deteriorates. In order to set such SP value, glass transition temperature and molecular weight as required, it is a simple and inexpensive method to copolymerize a wide variety of α, β-ethylenically unsaturated monomers according to required physical properties. It is.

The α, β-ethylenically unsaturated monomer used in the present invention includes, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate,
Alkyl esters of unsaturated monocarboxylic acids such as 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate and lauryl (meth) acrylate; nitriles such as (meth) acrylonitrile; styrene; Styrenes such as methylstyrene, unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol (meth) acrylate Hydroxyl-containing monomers such as (meth)
Acrylamide, N, N-dimethylacrylamide, N
Amide group-containing monomers such as isopropyl acrylamide 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 and N, N-diethylaminoethyl (meth) acrylate; glycidyl (meth) acrylate; glycidyl allyl ether; 3-epoxy-2-methylpropyl (meth) acrylate, (3,
4-epoxycyclohexyl) methyl (meth) acrylate, epoxy group-containing monomers such as 4-vinyl-1-cyclohexene 1,2 epoxide, olefins such as ethylene, propylene and isoprene, dienes such as chloroprene and butadiene, methyl vinyl ether, Examples include vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; and fatty acid vinyls such as vinyl acetate and 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) Acrylamide refers to methacrylamide or acrylamide. The greatest feature of the present invention is that the polymer (b) other than the polyorganosiloxane moiety in the copolymer (P) and the SP of the α, β-ethylenically unsaturated monomer constituting the polymer (S) Set the value to 9.
The point is to adjust to 7 to 12. In particular, when used in anti-graffiti coating agents, it is necessary to consider volatile organic solvents contained in lacquers and magic inks used in graffiti, and organic solvents having an SP value of 10 or less, especially 9.5 or less. May dissolve polyorganosiloxane, and when such an organic solvent is used for lacquer or magic ink, the solubility of the polymer part other than the polyorganosiloxane part in the organic solvent is low or insoluble. There is a need. Therefore, the SP value of the polymer portion other than the polyorganosiloxane portion needs to be 9.7 to 12, preferably 10 to 11. By setting the content in this range, not only the organic solvent resistance can be improved, but also the cohesive force such as hydrogen bonding between the polymers can be appropriately increased, and the polyorganosiloxane portion is more easily oriented on the surface. If it is less than 9.7, the SP value is 9.5.
It has a high affinity with the following organic solvents, and the lacquer, the magic ink and / or the solvent used permeates into the coating film. On the other hand, above 12, the number of hydrophilic groups increases so that the water resistance deteriorates.

Here, the SP value is an abbreviation of a solubility parameter and is an index of the interaction between liquid molecules or between a polymer and a liquid molecule. Regarding the SP value mentioned here, the SP value of a polymer having a clear repeating unit is described in R.C. F. F
edors, Polym. Eng. Sci. , 14
(2) Defined as a value calculated by the calculation method described in 147 (1974), and the unit of the SP value is (cal / c
m ³ ) ^1/2 . When the polymer part (b) other than the polyorganosiloxane part or the polymer (S) of the copolymer (P) constituting the coating agent is a polymer of an α, β-ethylenically unsaturated monomer, Monomers having at least one of the α, β-ethylenically unsaturated monomers constituting a homopolymer having an SP value of 10.7 to 18 (this is referred to as a monomer (m) To adjust the SP value of the polymer portion other than the polyorganosiloxane portion. S of copolymer of α, β-ethylenically unsaturated monomer
The P value cannot be calculated by the above method because copolymerization does not occur regularly. Therefore, the homopolymer SP
Although the usage range of the monomer (m) having a value of 10.7 to 18 cannot be completely limited, the average SP value of the copolymer of α, β-ethylenically unsaturated monomer is as follows. It is preferable that the value calculated using Expression 1 is 9.7 to 12.

[0022] Formula ^{_{1 SP = (SP 1 2 ×}} m1 + SP 2 2 × m 2 + ··· + SP
i ² × mi) ^{1/2 In the} above formula 1, SP ₁ , SP ₂ , and SPi are each the SP value of a homopolymer of each monomer, and m ₁ , m ₂ , and mi are each based on the total amount of each monomer. Indicates the weight fraction. Monomers (m) having a homopolymer having an SP value of 10.7 to 18 include (meth) acrylonitrile and (meth) acryl among the α, β-ethylenically unsaturated monomers shown above. Acid, maleic acid, fumaric acid, itaconic acid, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, diethylene glycol (meth)
Acrylate, triethylene glycol (meth) acrylate, tetraethylene glycol acrylate, (meth) acrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) ) Acrylamide, N,
N-di (methoxymethyl) (meth) acrylamide, N
-Butoxymethyl (meth) acrylamide, etc., but are not necessarily limited thereto, and any homopolymer having an SP value of 10.7 to 18 may be used. Among them, (meth) acrylic acid and 2-hydroxyethyl (meth) acrylate are preferably used from the viewpoint of solubility in a polymerization solvent, cost, and safety. The above monomers (m) can be used alone or in combination of two or more.

The SP value of the homopolymer described above is 1
The functional group of the monomer (m) of 0.7 to 18 may or may not be used in the crosslinking reaction. When used in a cross-linking reaction, it is preferable to use a cross-linking agent whose SP value does not largely change even after cross-linking, or otherwise to set the amount of the cross-linking agent so that a part of the functional group remains. The coating agent of the present invention has, in addition to the copolymer (P) in which a polyorganosiloxane part and a polymer part having an average SP value of 9.7 to 12 in the same molecule, an average SP value of 9.7. ~ 1
The two polymers (S) can be used simultaneously or mixed.

When a radical-generating polyorganosiloxane is used as the polyorganosiloxane component, a polyorganosiloxane compound having a group acting as a polymerization initiator such as an azo group or a peroxy group is used, or a chain-transferring polyorganosiloxane is used. When used, the polymer (S) can be produced simultaneously with the production of the copolymer (P) by using other polymerization initiators or chain transfer agents in combination. In addition, it is possible to mix a polymer (S) obtained by copolymerizing various α, β-ethylenically unsaturated monomers with a copolymer (P) in order to reduce costs and improve physical properties of a coating film. it can.

The α, β-ethylenically unsaturated monomer having a crosslinkable functional group is used for crosslinking after coating to form a hard coating film adhered to the substrate. Crosslinkable functional groups include hydrolyzable silyl groups, carboxyl groups,
Isocyano group, epoxy group, N-methylol group, or
Examples thereof include an N-alkoxymethyl group and a hydroxyl group. Particularly, when a monomer having a hydrolyzable silyl group is used, a hard coating film is obtained. Examples of the monomer having a hydrolyzable silyl group include (meth) such as γ- (meth) acryloxypropyltrimethoxysilane and γ- (meth) acryloxypropylmethyldimethoxysilane.
Acryloxyalkylalkoxysilane, (meth) acryloxyalkylalkoxyalkylsilane, trimethoxyvinylsilane, dimethoxyethylsilane, triethoxyvinylsilane, triethoxyallylsilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinyltris (2-methoxyethoxy) Examples include silane.

Examples of the monomer having one or more carboxyl groups include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid. Examples of the monomer having an isocyano group include (meth) acryloyloxyethyl isocyanate, (meth) acryloyloxypropyl isocyanate, 2-hydroxyethyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Hydroxy (meth) acrylate such as toluene diisocyanate, isophorone diisocyanate, coronate L
And those obtained by reacting with a polyisocyanate.

Examples of monomers having an epoxy group include glycidyl methacrylate, glycidyl cinnamate, glycidyl allyl ether, glycidyl vinyl ether, vinyl cyclohexane monoepoxide,
3-butadiene monoepoxide, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and the like. Examples of the monomer having an N-methylol group or an N-alkoxymethyl group include N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, and N-methylol (meth) acrylamide. (Meth) acrylamide having an N-monoalkoxymethyl group such as propoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethylol (meth) acrylamide, N, N-di (methoxymethyl) ( N, N such as meth) acrylamide, N, N-di (ethoxymethyl) (meth) acrylamide, N, N-di (propoxymethyl) (meth) acrylamide, N, N-di (butoxymethyl) (meth) acrylamide -(Meth) acrylamide having a dialkoxymethyl group is It is below.

Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate,
1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) A) acrylate, hydroxystyrene and the like. One of these is selected according to the required performance.
Species or a mixture of two or more species can be used. Further, the one used in the copolymer (P) and the one used in the polymer (S) are not necessarily required to be the same.

The α, β-ethylenically unsaturated monomer having a crosslinkable functional group is 10 to 80 in the copolymer (P).
% By weight, preferably 20 to 60% by weight. If it is less than 10% by weight, sufficient solvent resistance may not be obtained, and if it is more than 80% by weight, the surface properties and impact resistance of the coating film may be insufficient. In the polymer (S), 10 to 100% by weight, preferably 2 to 100% by weight.
It is used at a copolymerization ratio of 0 to 60% by weight. 10% by weight
If it is smaller, sufficient solvent resistance cannot be obtained. The copolymer (P) and the polymer (S) of the present invention are usually produced by solution polymerization or non-aqueous dispersion polymerization. As the polymerization solvent, methanol, ethanol, isopropanol,
Alcohols such as 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, aromatic hydrocarbons such as toluene and xylene, hexane, Examples thereof include aliphatic hydrocarbons such as heptane, and these can be used alone or in a mixed system. The charged concentration of the monomer at the time of synthesis is 0 to 80.
% By weight is preferred.

Examples of the polymerization initiator include ordinary peroxides or azo compounds such as benzoyl peroxide, azoisobutylvalenonitrile, azobisisobutyronitrile, di-t-butyl peroxide, t-butyl perbenzoate, T-butyl peroctoate, cumene hydroxyperoxide or the like is used, and the polymerization temperature is 50 to 140.
° C, preferably 70 to 120 ° C. When the polymerization is carried out using only a polyorganosiloxane-based polymer azo initiator, the amount of azo groups in the system is relatively small, and the polymerization conversion rate decreases, the molecular weight increases, and the viscosity increases. This causes problems in workability and the like. Therefore, it is necessary to adjust the polymerization conversion, the molecular weight of the polymer, and the viscosity by a method using the above radical polymerization initiator in combination.

In the present invention, various crosslinking agents (C) can be used as needed in order to crosslink the crosslinkable functional group in the composition. Representative crosslinking agents (C) include melamine compounds having an alkylol group or an alkoxy group such as hexamethylolated melamine, hexamethoxymethylated melamine, and hexabutoxymethylated melamine, cyanuric acid, ammelide, melamine, benzoguanamine, Amino resins such as diethanolamine, triethanolamine, diaminopyridine, benzoguanamine resin, methanol-modified melamine resin, urea resin, hydrazine compounds such as hydrazine, adipic dihydrazide, ethylenediamine, propanediamine, butanediamine, pentanediamine, hexanediamine, diamino Octane, diaminodecane, diaminododecane, 2,5-dimethyl-2,5-hexamethylenediamine, polyoxypropylenediamine, diethyleneto Linear diamines such as amines, triethylenetetramine, tetraethylenepentamine, polyethyleneglycol-terminated amine-substituted products, and polypropyleneglycol-terminated amine-substituted products, mensendiamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) ) Methane, diaminodicyclohexylmethane, 3,9
-Bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,4-bis (2-amino-2-methylpropyl) piperazine, m-
Xylenediamine, polycyclohexylpolyamine, bis (aminomethyl) bicyclo [2,2,1] heptane,
Cyclic diamines such as methylenebis (furanmethanamine), 1,6-hexamethylenediamine, polyamines such as triethylenetetramine, tetraethylenepentamine and diethylenetriamine, toluylene diisocyanate, naphthylene-1,5-diisocyanate, o-toluylene diisocyanate , Diphenylmethane diisocyanate, trimethylhexamethylene diisocyanate,
Isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, lysine diisocyanate, hydrogenated 4,4 '
-Diphenylmethane diisocyanate, diisocyanates such as hydrogenated tolylene diisocyanate, or both terminal isocyanate adducts thereof with glycols or diamines, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, polyvalent isocyanates such as coronate L, Dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, hexanedioic acid, citric acid, maleic acid, methylnadic acid, dodecenylsuccinic acid, sebacic acid, pyromellitic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and these Acid anhydrides, glyoxal, dialdehydes such as terephthalaldehyde, amino acids such as glycine and alanine and their lactams, citric acid, 12-hydroxystearic acid, 6- Mud carboxymethyl hydroxycarboxylic acids and lactones such as pentanoic acid, 1,4-butanediol, 2,3-butanediol diol such as,
1,1,1-trimethylolpropane ethylene glycol, diethylene glycol, glycerin, erythritol, arabitol, xylitol, sorbitol, dulcitol, mannitol, catechol, resorcinol, hydroquinone, guaiacol, hexyl resorcinol, pyrogallol, trihydroxybenzene, phloroglucin,
Polyhydric alcohols such as dimethylolphenol, or polyhydric phenolic compounds, or alkoxy-modified products thereof, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, tripropylene glycol Bisepoxy compounds such as diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and diglycidyl phthalate; 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate; bis Polyfunctional alicyclic epoxy compounds such as-(3,4-epoxycyclohexyl) adipate, manufactured by Yuka Shell Epoxy Co., Ltd. Epikote 801,802,80
7,815,827,828,834,815X, 81
5XA1, 828EL, 828XA, 1001, 100
2, 1003, 1055, 1004, 1004AF, 1
007, 1009, 1010, 1003F, 1004
F, 1005F, 1100L, 834X90, 1001
B80,1001X70,1001X75,1001T
75, 5045B80, 5046B80, 5048B7
0,5049B70, 5050T60, 5050,50
51, 152, 154, 180S65, 180H65,
1031S, 1032H60, 604, 157S70,
Nagase Kasei Kogyo Co., Ltd., trade name Denacol EX-6
11, 612, 614, 614B, 622, 651, 6
51A, 512, 521, 411, 421, 301, 3
13, 314, 321, 201, 211, 212, 81
0, 811, 850, 851, 821, 830, 83
2, 841, 861, 911, 941, 920, 92
1,931,2000,4000,922,111,1
21, 141, 145, 146, 171, 192, 70
1,721,203,251,711,731,14
Epoxy compounds such as 7,221,125,1101,1102,1103, phosphorus compounds such as pyrophosphoric acid, ethyl phosphite, bisphenol A-modified polyphosphoric acid, and triphenyl phosphite; and phosphoric acid dichloride compounds. .

When a monomer having a carboxyl group is used among these crosslinking agents (C), a phenol resin,
It is preferable to use amino resins, diamines, polyamines, diisocyanates, bisepoxy compounds, epoxy resins and the like. When a monomer having an isocyano group is used, use of a hydrazine compound, a diamine, a dicarboxylic acid and its anhydride, a diol, a polyhydric alcohol or a polyhydric phenol compound, a bisepoxy compound, an epoxy resin, or the like Is preferred. When a monomer having an epoxy group is used, dicarboxylic acids and anhydrides thereof, polyhydric alcohols or polyphenol compounds, or alkoxy-modified products thereof, amino resins, diisocyanates, polyvalent isocyanates, amino acids and , Its lactams, hydroxycarboxylic acids and their lactones,
The use of diamines, polyamines and the like is preferred.

When a monomer having an N-methylol group or an N-alkoxymethyl group is used, use of a melamine compound or an amino resin compound having a dicarboxylic acid, an alkylol group or an alkoxy group is preferred. preferable. When a monomer having a hydroxyl group is used, it is preferable to use an amino resin, a diamine, a polyamine, a diisocyanate, a dialdehyde, a bisepoxy compound, an epoxy resin, a phosphorus compound, a phosphoric acid dichloride compound, or the like. Two or more of these crosslinking agents (C) may be used, and the total amount used is in the range of 1 to 500% by weight, preferably 10 to 50% by weight, based on 100% by weight of the resin composition. When used in an amount of 50% by weight or more, the SP value of the crosslinking agent (C) is preferably set in the range of 9.7 to 12.

In the present invention, in order to promote a crosslinking reaction of a crosslinkable functional group in a composition or a crosslinking reaction between a crosslinkable functional group and a crosslinking agent, the composition may be selected according to each functional group. Various crosslinking catalysts can be used. Representative crosslinking catalysts include aluminum triacetylacetonate, iron triacetylacetonate, manganese tetraacetylacetonate, nickel tetraacetylacetonate, chromium hexaacetylacetonate, titanium tetraacetylacetonate, cobalt tetraacetylacetonate, and the like. Metal complex compounds, aluminum ethoxide, aluminum propoxide, aluminum butoxide, titanium ethoxide, titanium propoxide, metal alkoxides such as titanium butoxide, sodium acetate,
Tin octylate, lead octylate, cobalt octylate, zinc octylate, calcium octylate, lead naphthenate,
Metal salt compounds such as cobalt naphthenate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltin malate dibutyltin di (2-ethylhexoate), formic acid, acetic acid, propionic acid, p-toluenesulfonic acid, trichloroacetic acid, phosphorus Acid, monoalkyl phosphoric acid, dialkyl phosphoric acid, β-hydroxyethyl (meth) acrylate phosphoric acid ester, monoalkyl phosphorous acid, acidic compound such as dialkyl phosphorous acid, p-toluenesulfonic acid,
Acids such as phthalic anhydride, benzoic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, formic acid, acetic acid, itaconic acid, oxalic acid, maleic acid and their ammonium salts, lower amine salts, polyvalent metal salts, sodium hydroxide, Organometallic compounds such as lithium chloride, diethylzinc, tetra (n-butoxy) titanium, dicyclohexylamine, triethylamine, N, N-dimethylbenzylamine, N, N, N ', N'-tetramethyl-1,3-
Examples thereof include amines such as butanediamine, diethanolamine, triethanolamine, and cyclohexylethylamine. When a monomer having a hydrolyzable silyl group is used among these crosslinking catalysts, it is preferable to use a metal complex compound, a metal alkoxide, a metal salt compound, an acidic compound, or the like. In particular, the use of tin compounds such as dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltin dimaleate, and p-toluenesulfonic acid is preferred.

When a monomer having a carboxyl group is used, it is preferable to use acids and their ammonium salts, lower amine salts and polyvalent metal salts. When a monomer having an isocyano group is used, it is preferable to use amines, metal salt compounds and the like. When a monomer having an epoxy group is used, it is preferable to use an organic metal compound, an amine or the like. When a monomer having an N-methylol group or an N-alkoxymethyl group is used, it is preferable to use acids and their ammonium salts, lower amine salts, polyvalent metal salts, and the like.

When a monomer having a hydroxyl group is used, the use of acidic compounds, acids and their ammonium salts, lower amine salts, polyvalent metal salts and the like is preferred. Two or more of these crosslinking catalysts may be used, and the total amount used is 0.01% to 100% by weight of the resin composition.
The range is from 10 to 10% by weight, preferably from 0.1 to 5% by weight. In the present invention, a silane coupling agent can be further used as needed. Specific examples of silane coupling agents include tetrafunctional silanes such as tetramethoxysilane and tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, γ-
Chloropropyltrimethoxysilane, vinyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl)
Ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane,
trifunctional silanes such as γ-morpholinopropyltrimethoxysilane, and bifunctional silanes in which part of the trifunctional silane is substituted with an alkyl group, a phenyl group, a vinyl group, and the like, for example, dimethyldimethoxysilane, phenylmethyldimethoxysilane, Vinylmethyldimethoxysilane,
γ-chloropropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and the like. In addition, hydrolysates and partial condensates of these compounds can be used. The silane coupling agent is
It is used in an amount of 1 to 40% by weight, preferably 3 to 20% by weight, based on the total of the polymer (P) and the polymer (S).

In the present invention, a filler, a thixotropy-imparting agent, a coloring pigment, an extender pigment, a dye, an antioxidant, an ultraviolet absorber, a light stabilizer, an antioxidant, if necessary, as long as the effects of the present invention are not impaired. Agents, antistatic agents, flame retardants, thermal conductivity improvers, plasticizers, sagging agents, antifouling agents, preservatives,
Various additives such as a bactericide, an antifoaming agent, a leveling agent, and a curing agent may be added. 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 base material 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 coating 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. These can be used alone or in a mixed system, but are not necessarily limited thereto.

The coating agent of the present invention is applied to building materials or other supports such as bricks, tiles, natural stones, ceramics, concrete, cement, mortar, slate, metal and the like. In addition, by applying to a transparent substrate such as a plate or a film such as glass, acrylic, polycarbonate, or polyethylene terephthalate film, surface properties with low surface energy can be imparted. The coating agent is preferably used in an amount of 10 to 500 g per 1 m ^{2 of the} surface to be treated, and applied by a known method such as spraying, dipping, brush, brush or roller.

After the coating, the coating is usually dried naturally or dried at a high temperature in an oven or the like. The coating of the present invention is a windshield for automobiles, a rear glass, a door glass, a fender mirror, a door mirror and a glass for transportation equipment such as a railway and an airplane, a window glass of a high-rise building, a general window glass, a glass bottle for storing enzymes and the like, Ampoule bottle, reagent storage bottle, other commonly used glass bottle,
Glass products such as mirrors, medical-related fields, food, industry,
Water repellency, oil repellency, stain resistance, weather resistance, etc. are required for plastic products, various film products, metal products, concrete, ceramic products, cloth, leather products, etc. used in various industrial fields such as agriculture and general households. Non-adhesive glass bottles such as water-repellent glass, anti-fog mirror, enzymes, reagents, anti-bacterial and anti-mold plastics, inkjet printer heads, snow- and anti-icing coated plates, kitchen garments It can be used for printing plate materials such as dirty aluminum sheet and waterless offset plate, paint for discarded plate used in offset printing, and other printing plate related products.

[0041]

(Synthesis of resin)

Production Example 1 Methyl isobutyl ketone 1 was placed in a 1000 ml flask equipped with a stirrer, thermometer, condenser and nitrogen inlet tube.
The mixture was heated to 90 ° C. and 40 parts of glycidyl methacrylate and methyl methacrylate 40 separately prepared.
Parts, 2-hydroxyethyl methacrylate 10 parts, VP
S-0501 (manufactured by Wako Pure Chemical Industries, Ltd .: polydimethylsiloxane-based polymer azo initiator, molecular weight of polydimethylsiloxane part about 5,000, number average molecular weight about 20,000 to 30,000) 1
0 parts, a mixture of 1.5 parts of azobisisobutyronitrile and 50 parts of methyl isobutyl ketone was added dropwise over 2 hours using a dropping funnel. One hour later, 0.5 part of azobisisobutyronitrile was added. Then, after stirring at the same temperature for 3 hours, the polymerization was terminated. As described above, an epoxy group-containing silicone block copolymer solution was obtained. This is designated as Resin Solution 1.

Production Example 2 Methyl isobutyl ketone 1 was placed in a 1000 ml flask equipped with a stirrer, thermometer, condenser and nitrogen inlet tube.
Then, 00 parts were heated to 90 ° C., and 25 parts of separately prepared γ-methacryloxypropyltrimethoxysilane, 30 parts of methyl methacrylate, and 15 parts of butyl methacrylate were prepared.
Parts, 2-hydroxyethyl methacrylate 20 parts, VP
A mixture of 10 parts of S-0501, 1.5 parts of azobisisobutyronitrile and 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. Was added thereto, followed by stirring at the same temperature for 3 hours, and then the polymerization was terminated. As described above, a hydrolyzable silyl group-containing silicone block copolymer solution was obtained. This is referred to as a resin solution 2.

Production Example 3 Methyl isobutyl ketone 1 was placed in a 1000 ml flask equipped with a stirrer, thermometer, condenser and nitrogen inlet tube.
Charge 00 parts and raise the temperature to 90 ° C.
-Butyl methacrylate 40 parts, isobutyl acrylate 10 parts, glycidyl methacrylate 40 parts, VPS-
0501, 10 parts of azobisisobutyronitrile 1.5
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, an epoxy group-containing silicone block copolymer solution was obtained. This is referred to as a resin solution 3.

Production Example 4 Methyl isobutyl ketone 1 was placed in a 1000 ml flask equipped with a stirrer, thermometer, condenser and nitrogen inlet tube.
The mixture was heated to 90 ° C., and 40 parts of separately prepared isobutyl methacrylate and 10 parts of isobutyl acrylate were prepared.
Parts, 15 parts of methyl methacrylate, 25 parts of γ-methacryloxypropyltrimethoxysilane, VPS-050
A mixture of 10 parts of 1, 1 part of azobisisobutyronitrile and 50 parts of methyl isobutyl ketone was added dropwise over 2 hours using a dropping funnel. After 1 hour, 0.5 part of azobisisobutyronitrile was added. After stirring at the same temperature for 3 hours, the polymerization was terminated. As described above, a hydrolyzable silyl group-containing silicone block copolymer solution was obtained. This is referred to as a resin solution 4.

Production Example 5 Methyl isobutyl ketone 1 was placed in a 1000 ml flask equipped with a stirrer, thermometer, condenser and nitrogen inlet tube.
And then heated to 80 ° C., and separately prepared 40 parts of glycidyl methacrylate and methyl methacrylate 40
Part, 2-hydroxyethyl methacrylate 10 parts, Chisso Corporation Silaplane FM-0721 (one-terminal methacryloxy group-containing polysiloxane compound) 10 parts, azobisisobutyronitrile 1.5 parts, methyl isobutyl ketone 50 parts One hour after the mixture was added dropwise over 2 hours using a dropping funnel, 0.5 part of azobisisobutyronitrile was added, and the mixture was stirred at the same temperature for 3 hours to complete the polymerization. As described above, an epoxy group-containing silicone-based graft copolymer solution was obtained. This is referred to as a resin solution 5.

Production Example 6 Methyl ethyl ketone 100 was placed in a 1000 ml flask equipped with a stirrer, thermometer, condenser and nitrogen inlet tube.
The temperature was raised to 80 ° C and acrylic acid 3 prepared separately
0 parts, 30 parts of methyl methacrylate, 30 parts of butyl methacrylate, 10 parts of FM-0721, 1.5 parts of azobisisobutyronitrile, and 50 parts of methyl ethyl ketone were dropped over 2 hours using a dropping funnel for 1 hour. Thereafter, 0.5 parts of azobisisobutyronitrile was added, and then the mixture was stirred at the same temperature for 3 hours to terminate the polymerization. As described above, a carboxyl group-containing silicone graft copolymer solution was obtained. This is referred to as a resin solution 6.

Production Example 7 Methyl ethyl ketone 100 was placed in a 1000 ml flask equipped with a stirrer, thermometer, condenser and nitrogen inlet tube.
And heated to 80 ° C., and 50 parts of separately prepared methyl methacrylate, 10 parts of butyl methacrylate, N, N
-Di (methoxymethyl) methacrylamide 30 parts, FM
-0721, 10 parts of azobisisobutyronitrile.
A mixture of 5 parts and 50 parts of methyl ethyl 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 the polymerization was terminated. did. A methoxymethyl group-containing silicone graft copolymer solution was obtained as described above. This is referred to as a resin solution 7.

Production Example 8 Methyl isobutyl ketone 1 was placed in a 1000 ml flask equipped with a stirrer, thermometer, condenser and nitrogen inlet tube.
The mixture was heated to 80 ° C., and separately prepared 40 parts of glycidyl methacrylate, 40 parts of tert-butyl methacrylate, 10 parts of isobutyl acrylate, and FM-0.
721, 10 parts of azobisisobutyronitrile 1.5
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, an epoxy group-containing silicone-based graft copolymer solution was obtained. This is referred to as a resin solution 8.

Production Example 9 100 ml of methyl ethyl ketone was placed in a 1000 ml flask equipped with a stirrer, thermometer, condenser and nitrogen inlet tube.
Of tert-butyl methacrylate and 10 parts of butyl methacrylate separately prepared.
Part, N, N-di (methoxymethyl) methacrylamide 3
0 parts, 10 parts of FM-0721, 1.5 parts of azobisisobutyronitrile, and 50 parts of methyl ethyl ketone were added dropwise over 2 hours using a dropping funnel. One hour later, azobisisobutyronitrile 0.5 The polymerization was terminated after stirring for 3 hours at the same temperature. A methoxymethyl group-containing silicone graft copolymer solution was obtained as described above. This is referred to as a resin solution 9.

Production Example 10 Methyl isobutyl ketone 1 was placed in a 1000 ml flask equipped with a stirrer, thermometer, condenser and nitrogen inlet tube.
The mixture was heated to 90 ° C. and 40 parts of glycidyl methacrylate and methyl methacrylate 40 separately prepared.
Part of butyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate, 1.5 parts of azobisisobutyronitrile, and 50 parts of methyl isobutyl ketone were added dropwise over 2 hours using a dropping funnel. 0.5 part of isobutyronitrile was added, and the mixture was stirred at the same temperature for 3 hours, and then the polymerization was terminated. This is resin solution 1
Set to 0.

Production Example 11 Methyl ethyl ketone 100 was placed in a 1000 ml flask equipped with a stirrer, thermometer, condenser and nitrogen inlet tube.
And heated to 80 ° C., and separately prepared 40 parts of methyl methacrylate, 15 parts of butyl methacrylate, 20 parts of 2-hydroxyethyl methacrylate, 25 parts of γ-methacryloxypropyltrimethoxysilane, and azobisisobutyronitrile. A mixture of 5 parts and 50 parts of methyl ethyl 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 the polymerization was terminated. did. This is referred to as a resin solution 11.

Production Example 12 100 ml of methyl ethyl ketone was placed in a 1000 ml flask equipped with a stirrer, thermometer, condenser and nitrogen inlet tube.
The temperature was raised to 80 ° C and acrylic acid 3 prepared separately
0 part, a mixture of 35 parts of methyl methacrylate, 35 parts of butyl methacrylate, 1.5 parts of azobisisobutyronitrile, and 50 parts of methyl ethyl ketone 2
One hour after the dropwise addition over a period of time, 0.5 parts of azobisisobutyronitrile was added, and the mixture was stirred at the same temperature for 3 hours, and then the polymerization was terminated. This is referred to as a resin solution 12.

Production Example 13 Methyl ethyl ketone 100 was placed in a 1000 ml flask equipped with a stirrer, thermometer, condenser and nitrogen inlet tube.
And heated to 80 ° C., and separately prepared 40 parts of methyl methacrylate, 30 parts of butyl methacrylate, N, N
A mixture of 30 parts of di (methoxymethyl) methacrylamide, 1.5 parts of azobisisobutyronitrile, and 50 parts of methyl ethyl ketone was added dropwise over 2 hours using a dropping funnel. One hour later, azobisisobutyronitrile 0.1 part was added. After adding 5 parts, the mixture was stirred at the same temperature for 3 hours, and then the polymerization was terminated. This is referred to as a resin solution 13. [Blending of Coating Agents of Examples 1 to 10 and Comparative Examples 1 to 8] The resin solutions obtained as described above were mixed so as to have the weights shown in Tables 1 to 4 in terms of solid content. The SP value of the polymer part other than the polyorganosiloxane part of the polymer used in each of the examples and comparative examples was 1:10.
2. Resin solution 2: 9.9, Resin solution 3: 9.6, Resin solution 4: 9.1, Resin solution 5: 10.2, Resin solution 6: 1
0.9, resin solution 7: 9.9, resin solution 8: 9.6, resin solution 9: 9.5, resin solution 10: 10.1, resin solution 11: 9.9, resin solution 12:10. 7. Resin solution 1
3: 9.9.

The SP value of the homopolymer of the monomer is determined according to F.
Fedors, Polym. Eng. Sci. , 14
(2) Calculated from the calculation method described in 147 (1974). As SP values of the homopolymer of each monomer used in the above synthesis example, 10.33 for polyglycidyl methacrylate and 9.4 for polymethyl methacrylate.
8, poly (2-hydroxyethyl methacrylate) is 1
1.96, 9.05 for poly (γ-methacryloxypropyltrimethoxysilane), 8.99 for polybutyl methacrylate, 9.0 for polyisobutyl methacrylate
0, polyisobutyl acrylate 9.25, poly (t
ert-butyl methacrylate) used 8.81, polyacrylic acid used 13.61, and poly (N, N-di (methoxymethyl) methacrylamide) used 10.76.

[0055]

[Table 1]

[0056]

[Table 2]

[0057]

[Table 3]

[0058]

[Table 4]

The abbreviations in Tables 1 to 4 are as follows. 1) D-230: Polyoxypropylenediamine manufactured by Sun Techno Chemical Co., Ltd. (trade name: Jeffamine D)
-230) 2) DBTDL: dibutyltin dilaurate 3) EMEM: 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate 4) PTS: p-toluenesulfonic acid [Test for preventing graffiti of coated base material, etc. In each of the examples and comparative examples, a coating agent was obtained by adding methyl ethyl ketone to the mixture ratio shown in Tables 1 to 4 and further adjusting the solid content to 30%. Examples 1 and 6 and Comparative Example 1 were applied to an acrylic plate with a 5 mil applicator, Examples 2, 7 and Comparative Example 2 were applied to a glass plate with a 1 mil applicator. Examples 3, 8 and Comparative Example 3 were slate plates. Nos. 4 and 9 were applied with a brush at 120 g / m ² . 2
No. 0 was applied to a polyethylene terephthalate film with a bar coater. Examples 5 and 10 and Comparative Examples 4 and 8
5 was applied to an aluminum plate using a bar coater.

The drying conditions were the same as in Examples 1, 2, 3, 6, 7, and 8.
And Comparative Examples 1, 2, 3, 5, 6, and 7 were dried at room temperature for 3 days,
Examples 4 and 9 were dried in a 120 ° C. oven for 20 minutes, and Examples 5 and 10 and Comparative Examples 4 and 8 were dried in a 200 ° C. oven for 20 minutes. Various tests were performed on the substrate coated in this manner. The test method is as follows. The results are shown in Table 5. Water repellency: The contact angle of pure water to the coating film surface was measured with a contact angle meter. Solvent resistance: Rubbing was performed 50 times with absorbent cotton containing ethyl acetate, and abnormality of the coating film was visually observed.

：: No abnormality Δ: Partial swelling of the coating film observed ×: Scratches due to rubbing observed Graffiti antifouling property: Graffiti was performed with oil-based magic, and non-adhesion was evaluated. ○: repelling ：: bleeding ：: partial bleeding ×: completely adhered Also, after 24 hours, the removability was evaluated.

○: It can be removed by dry wiping and there is no abnormality in the coating film. ：: It can be removed with an ethanol impregnated paper waste and there is no abnormality in the coating film. 跡: It can be removed but there is a trace, or there is an abnormality in the coating film after removal. × : Cannot be removed

[0063]

[Table 5]

[0064]

From the above results, the coating agent of the present invention shows that the average SP value of the polymer parts other than the polyorganosiloxane part is the same for the polymer in which the polyorganosiloxane part and the other polymer part are present in the same molecule. By using a copolymer in which is set in the range of 9.7 to 12, the anti-graffiti performance can be effectively exhibited. As described above, the coating agent can be widely used and applied as a paint for preventing graffiti, and furthermore, the surface water-repellent / oil-repellent treatment of civil engineering buildings or other supports can be performed by using the coating agent. Further, the support provided with the anti-graffiti property can be widely used and applied as an antifouling substrate.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C08G77 / 442 C08G77 / 442 C09D 133/00 C09D 133/00 201/00 201/00

Claims (9)

[Claims] 1. A copolymer (P) comprising at least a polyorganosiloxane part (a) and a polymer part (b) having an average SP value of 9.7 to 12 in the same molecule. Coating agent. 2. A copolymer (P) comprising a block polymer of a polyorganosiloxane part (a) and a polymer part (b) and / or
The coating agent according to claim 1, wherein the copolymer (P) is a graft polymer having the polymer part (b) as a backbone polymer and having at least one polyorganosiloxane part (a) in a side chain. 3. The coating agent according to claim 1, comprising a polymer (S) having an average SP value of 9.7 to 12. 4. The polymer (b) and / or the polymer (S) in the copolymer (P) contains one or more α, β-
The coating agent according to any one of claims 1 to 3, comprising an ethylenically unsaturated monomer. 5. α, having a crosslinkable functional group in the polymer part (b) and / or in the polymer (S) of the copolymer (P).
β-ethylenically unsaturated monomer is copolymerized by one or more kinds, and the crosslinkable functional group is a self-reactive functional group, and / or reacts with the crosslinkable functional group. The coating agent according to any one of claims 1 to 4, wherein the coating agent comprises at least one polyfunctional crosslinking agent (C). 6. A crosslinkable self-reactive functional group present in the polymer part (b) and / or in the polymer (S) of the copolymer (P) is a hydrolyzable silyl group, Multifunctional capable of reacting with a crosslinkable functional group present from a methylol group or an N-alkoxymethyl group and / or in the polymer part (b) and / or in the polymer (S) of the copolymer (P) The combination of the functional groups of the hydrophilic crosslinking agent (C) includes a hydrolyzable silyl group and a hydrolyzable silyl group, an epoxy group and an amino group,
One or more selected from epoxy groups and carboxyl groups, hydroxyl groups and isocyano groups, N-methylol groups or N-alkoxymethyl groups and N-methylol groups or N-alkoxymethyl groups. 6. The coating agent according to any one of 1 to 5. 7. The method according to claim 1, further comprising a copolymer (P) and / or a crosslinking catalyst for promoting a crosslinking reaction between the copolymer (P) and the polymer (S). Coating agent. 8. At least one of the monomers constituting the polymer part (b) and / or the polymer (S) in the copolymer (P) is 2-hydroxy (meth) acrylate, (meth) 8. The coating agent according to claim 1, wherein the coating agent is selected from acrylic acid. 9. A surface treatment method comprising applying a coating agent according to any one of claims 1 to 8 to civil engineering buildings or other supports to impart surface water repellency and antifouling properties.