JP2000212478A - Stain-proofing coating agent and plastic sheet coated with the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a stain-proofing coating agent which shows excellent cohesiveness on a plasticizer-containing plastic film, excellent stain-proofness, easy removal of dirt and almost no stain of dirt. SOLUTION: This stain-proofing coating agent comprises a polymer (A) comprising (a) 5-70 wt.% of (meth)acrylonitrile, (b) 5-40 wt.% of a monomer having a carbon-carbon unsaturated double bond and a crosslinkable functional group, and (c) 90-0 wt.% of a monomer copolymerizable with (a) or (b) and a polymer (B) comprising (d) 5-60 wt.% of a carbon-carbon unsaturated double bond and a polyorganosiloxane chain, (b) 5-40 wt.% of a monomer having a carbon-carbon unsaturated double bond and a crosslinkable functional group and (c) 90-0 wt.% of a monomer copolymerizable with (a) or (b).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an antifouling coating agent and a plastic sheet coated with the same. In particular, the present invention relates to an antifouling coating agent for preventing adhesion of dirt due to migration of a plasticizer contained in plastic and a plastic sheet coated with the same.

[0002]

2. Description of the Related Art Plastic sheets are used in a wide variety of types. For example, with respect to polyvinyl chloride, as a high-grade application, PVC leather or foamed PVC is used for seats and interiors of vehicles, furniture such as sofas, building materials such as wallpapers, bags for bags and the like. In these PVC films, sheets, and leathers, particularly soft products, there is a problem of stain coloring that is not easily decontaminated by the environment and contact during use. The coloring is caused by the fact that the coloring component is dissolved in the plasticizer contained in a large amount in the soft PVC and penetrates into the inside of the PVC sheet. For this reason, various coating agents have been proposed. However, since the plasticizer in the PVC gradually migrates (migrate) to the resin constituting the coating agent, a problem of stain coloring occurs over time.

[0003]

An object of the present invention is to prevent migration of a plasticizer into a coating agent layer,
An object of the present invention is to provide a plastic sheet having excellent stain removal properties in which a coloring component is not dissolved and fixed in a plasticizer present in a coating agent layer.

[0004]

Means for Solving the Problems The present inventors have found that a coating agent containing an acrylonitrile copolymer prevents migration of a plasticizer, and a polymer containing a polyorganosiloxane chain in the coating agent is coated with the coating agent. They have found that they migrate to the surface during film formation and significantly improve the resistance to dirt, and have succeeded in inventing a plastic sheet having excellent antifouling properties. That is, the present invention
(A) 5 to 70% by weight of (meth) acrylonitrile,
(B) 5 to 40% by weight of a monomer having a carbon-carbon unsaturated double bond and a crosslinkable functional group, and (c) 90 to 0% of a monomer copolymerizable with (a) or (b) (B) a polymer having a carbon-carbon unsaturated double bond and a polyorganosiloxane chain;
5 to 40% by weight of a monomer having a carbon-carbon unsaturated double bond and a crosslinkable functional group, and (c) 90 to 0% of a monomer copolymerizable with (a) or (b). The present invention relates to an antifouling coating agent comprising the union (B).

Further, according to the present invention, the crosslinkable functional group of the monomer (b) having a carbon-carbon unsaturated double bond and a crosslinkable functional group may be a hydrolyzable silyl group, a carboxyl group or an isocyano group. The present invention relates to the above antifouling coating agent, which is at least one functional group selected from the group consisting of an epoxy group, an epoxy group, an N-methylol group, an N-alkoxymethyl group, and a hydroxyl group.

Further, the present invention is characterized in that the monomer (d) is 0.1 to 10% by weight based on the total of the polymer (A) and the polymer (B). It relates to a coating agent. Further, the present invention relates to the above antifouling coating agent, which comprises a compound having a reactive functional group capable of reacting with the crosslinkable functional group of the polymer (A) and the polymer (B) as a crosslinking agent. Further, the present invention relates to the above antifouling coating agent, which comprises a crosslinking catalyst for accelerating a crosslinking reaction between the polymer (A) and the polymer (B).

[0007] The present invention also relates to a plastic sheet obtained by coating a plastic substrate containing a plasticizer with the above antifouling coating agent. The present invention also relates to the above-mentioned plastic sheet, wherein the plastic substrate is a soft polyvinyl chloride.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION A monomer (b) having a carbon-carbon unsaturated double bond and a crosslinkable functional group is crosslinked after coating with a coating agent to form a hard coating film adhered to a substrate. Used to Examples of the crosslinkable functional group include a hydrolyzable silyl group, a carboxyl group, an isocyano group, an epoxy group, an N-methylol group, an N-alkoxymethyl group, and a hydroxy group, and particularly a simple group having a hydrolyzable silyl group. When a monomer is used, a hard coating film of a coating agent is obtained. Further, a monomer having a carboxyl group is also effective.

A monomer (b) having a hydrolyzable silyl group
Examples of (meth) acryloxyalkylalkoxysilanes such as γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, (meth) acryloxyalkylalkoxyalkylsilane, Examples include methoxyvinylsilane, dimethoxyethylsilane, triethoxyvinylsilane, triethoxyallylsilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, and vinyltris (2-methoxyethoxy) silane.

[0010] Examples of the monomer (b) having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and styrenesulfonic acid. Examples of the monomer (b) having an isocyano group include (meth) acryloyloxyethyl isocyanate, (meth) acryloyloxypropyl isocyanate, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl ( Examples thereof include those obtained by reacting a hydroxy (meth) acrylate such as meth) acrylate with a polyisocyanate such as toluene diisocyanate, isophorone diisocyanate, or coronate L. Examples of the monomer (b) having an epoxy group include glycidyl methacrylate, glycidyl cinnamate, glycidyl allyl ether, glycidyl vinyl ether, vinylcyclohexane monoepoxide, and 1,3-butadiene monoepoxide.

Examples of the monomer (b) having an N-methylol group or an N-alkoxymethyl group include N-methylol group and N-alkoxymethyl group.
N-monoalkoxymethyl groups such as methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, and N-butoxymethyl (meth) acrylamide (Meth) acrylamide, N, N-dimethylol (meth) acrylamide, N, N-di (methoxymethyl) (meth)
Acrylamide, N, N-di (ethoxymethyl) (meth) acrylamide, N, N-di (propoxymethyl)
(Meth) acrylamide having an N, N-dialkoxymethyl group such as (meth) acrylamide and N, N-di (butoxymethyl) (meth) acrylamide. Examples of the monomer (b) having a hydroxyl group include 2-hydroxyethyl (meth) acrylate,
-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) Acrylate, hydroxystyrene and the like can be mentioned.

Depending on the required performance, one or more of these can be used in combination. Further, the one used in the polymer (A) and the one used in the polymer (B) are not necessarily required to be the same. The monomer (b) is used at a copolymerization ratio of 5 to 40% by weight in the polymer (A). If it is less than 5% by weight, sufficient hardness may not be obtained, and if it is more than 40% by weight, the surface performance of the coating film may be insufficient. Further, the polymer (B)
Among them, it is used at a copolymerization ratio of 5 to 40% by weight, preferably 10 to 30%. If it is less than 5% by weight, sufficient hardness cannot be obtained.

The monomer (d) having a carbon-carbon unsaturated double bond and a polyorganosiloxane chain in one molecule used in the polymer (B) constituting the present invention is represented by the general formula (a). . (N is a positive integer) R1: CH2 = CH-COO- (CH2) m-, CH2 = C (CH3) -COO
-(CH2) m- CH2 = CH- (CH2) m- or CH2 = C (CH3)-(CH2)
m- (m is an integer of 0 to 10) R2: hydrogen, methyl group, or the same functional group as R1 R3, R4, R5, R6, R7, R8: selected from alkyl group, phenyl group, hydroxyl group, and carboxyl group.

Specifically, for example, Toshiba Silicone Co., Ltd.
One-terminal (meth) acryloxy group-containing polyorganosiloxane compounds, such as TSL9705, manufactured by Chisso Co., Ltd .; and Silanoplane FM-0711, FM-0721, FM-0725, manufactured by Chisso. No. Monomer (d) having a carbon-carbon unsaturated double bond and a polyorganosiloxane chain in one molecule is indispensable for imparting surface properties such as water repellency, antifouling property and slipperiness to the coating film. Depending on the required performance, one of these may be used alone, or two or more of them may be used in combination, and are used at a copolymerization ratio of 5 to 60% by weight. It is desirable that the copolymerization be at least 50% by weight, and that the copolymerization ratio be at most 50% by weight in order to obtain sufficient coating film performance such as adhesion to the substrate and toughness.

The monomer (c) having a carbon-carbon unsaturated double bond other than (a) and (b) used in the present invention is:
It is used for imparting various coating properties such as hardness, toughness, scratch resistance, and gloss improvement. These monomers include (i) (meth) acrylic acid derivatives, (ii) aromatic vinyl monomers, (iii) olefinic hydrocarbon monomers, (iv) vinyl ester monomers, and (v) vinyl halides. Monomer, and (vi) a vinyl ether monomer. (i) Examples of (meth) acrylic acid derivatives include (meth) acrylate, methyl (meth) acrylate, butyl (meth) acrylate, ethylhexyl (meth) acrylate, stearyl (meth) acrylate, and benzyl (meth) acrylate. Is mentioned.

(Ii) Examples of the aromatic vinyl monomer include styrene, methylstyrene, ethylstyrene, chlorostyrene and the like. (iii) Examples of the olefinic hydrocarbon monomer include ethylene, propylene, butadiene, isobutylene, isoprene, and 1,4-pentadiene. (iv) Examples of the vinyl ester monomer include vinyl acetate. (v) Examples of the vinyl halide monomer include vinyl chloride, vinylidene chloride, monofluoroethylene, difluoroethylene, trifluoroethylene and the like. (vi) Examples of the vinyl ether monomer include vinyl methyl ether and the like. Two or more of these may be used.

In the polymer (A), the monomer (c) is
Used at ~ 90% by weight. In the polymer (B),
Used at 0-90% by weight. If it is more than 90% by weight, sufficient adhesion to the substrate cannot be obtained. Further, the compatibility with the polymer (A) is reduced, and a uniform and good coating film of the coating agent cannot be obtained.

The polymer (A) and the polymer (B) can be obtained by a known method, for example, solution polymerization. As the solvent to be used, methanol, ethanol, propanol, butanol, alcohols such as ethylene glycol methyl ether, diethylene glycol methyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, tetrahydrofuran,
Dioxane, ethylene glycol dimethyl ether, ethers such as diethylene glycol dimethyl ether, hexane, heptane, hydrocarbons such as octane,
It is possible to use aromatics such as benzene, toluene, xylene and cumene, and esters such as ethyl acetate and butyl acetate. The solvent may be a mixture of two or more. The charged concentration of the monomer during the synthesis is preferably from 0 to 80% by weight.

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 140 ° C. The preferred average molecular weight of the obtained polymer is 2,000 to 100,000 for both the polymer (A) and the polymer (B).

In the present invention, various crosslinking agents can be used as needed in order to crosslink the crosslinkable functional groups in the coating agent. Representative crosslinking agents include melamine-based compounds having an alkylol group or an alkoxy group such as hexamethylolated melamine, hexamethoxymethylated melamine, and hexabutoxymethylated melamine, cyanuric acid, ammelide, melamine, benzoguanamine, diethanolamine, triethanolamine, and the like. Ethanolamine, diaminopyridine, benzoguanamine resin, methanol-modified melamine resin, amino resin such as urea resin, hydrazine, hydrazine compounds such as ADH, ethylenediamine, propanediamine, butanediamine,
Linear diamines such as pentanediamine, hexanediamine, diaminooctane, diaminodecane, diaminododecane, 2,5-dimethyl-2,5-hexamethylenediamine, polyoxypropylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine , 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-
Cyclic diamines such as amino-2-methylpropyl) piperazine, m-xylenediamine, polycyclohexylpolyamine, bis (aminomethyl) bicyclo [2.2.1] heptane, and methylenebis (furanmethanamine);
6-hexamethylenediamine, triethylenetetramine, tetraethylenepentamine, polyamines such as 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,
Diisocyanates such as lysine diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, or isocyanate adducts of these with glycols or diamines, triphenylmethane triisocyanate, polymethylene polyphenylisocyanate , 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 and tetrahydrophthalic acid And their acid anhydrides glyoxal, dialdehydes such as terephthalaldehyde, amino acids such as glycine and alanine, and lactams, citric acid, 12-hydroxystearic acid, hydroxycarboxylic acids such as 6-hydroxypentanoic acid and lactones thereof,

Diols such as 1,4-butanediol and 2,3-butanediol, 1,1,1-trimethylolpropane ethylene glycol, diethylene glycol, glycerin, erythritol, arabitol, xylitol, sorbitol, dulcitol, mannitol, catechol , Resorcin, 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 diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether , Bisepoxy compounds such as phthalic acid diglycidyl ester, manufactured by Yuka Shell Epoxy,
Product name Epicoat 801, 802, 807, 815, 8
27,828,834,815X, 815XA1,82
8EL, 828XA, 1001, 1002, 1003,
1055, 1004, 1004AF, 1007, 100
9, 1010, 1003F, 1004F, 1005F,
1100L, 834X90, 1001B80, 1001
X70,1001X75,1001T75,5045B
80, 5046B80, 5048B70, 5049B7
0, 5050 T60, 5050, 5051, 152, 1
54, 180S65, 180H65, 1031S, 10
Examples include epoxy resins such as 32H60, 604, and 157S70, phosphorus compounds such as pyrophosphoric acid, ethyl phosphite, bisphenol A-modified polyphosphoric acid, and triphenyl phosphite, and phosphoric acid dichloride compounds.

When a monomer (b) having a carboxyl group is used among these crosslinking agents, a phenol resin,
It is preferable to use amino resins, diamines, polyamines, diisocyanates, bisepoxy compounds, epoxy resins and the like. When the monomer (b) having an isocyano group is used, a hydrazine compound, a diamine, a dicarboxylic acid and its anhydride, a diol, a polyhydric alcohol or a polyphenol compound, a bisepoxy compound, an epoxy resin Use of such as is preferred.

When the monomer (b) having an epoxy group is used, dicarboxylic acids and their anhydrides, polyhydric alcohols or polyphenolic compounds, or alkoxy-modified products thereof, amino resins, diisocyanates,
Polyvalent isocyanates, amino acids and their lactams,
Hydroxycarboxylic acids and their lactones, diamines,
The use of polyamines and the like is preferred. When the monomer (b) having an N-methylol group or an N-alkoxymethyl group is used, use of a dicarboxylic acid, a melamine compound having an alkylol group or an alkoxy group, an amino resin compound, or the like is preferable. preferable. When the monomer (b) 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 may be used, and the total amount used is in the range of 1 to 500% by weight, preferably 10 to 200% by weight, based on 100% by weight of the coating agent.

In the present invention, in order to promote a crosslinking reaction of a crosslinkable functional group in a coating agent or a crosslinking reaction between a crosslinkable functional group and a crosslinking agent, the crosslinking reaction is performed 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, cobalt naphthenate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltin malate dibutyltin di (2-ethyl Metal salt compounds such as soyate), formic acid, acetic acid, propionic acid, p-toluenesulfonic acid, trichloroacetic acid, phosphoric acid, monoalkyl phosphoric acid, dialkyl phosphoric acid, β-hydroxyethyl (meth) acrylate phosphate, mono Acidic compounds such as alkylphosphorous acid and dialkylphosphorous acid,

P-toluenesulfonic acid, phthalic anhydride,
Acids such as 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, lithium chloride, diethyl Organometallic compounds such as zinc, tetra (n-butoxy) titanium, dicyclohexylamine, triethylamine, N, N-dimethylbenzylamine,
Examples thereof include amines such as N, N ', N'-tetramethyl-1,3-butanediamine, diethanolamine, triethanolamine, and cyclohexylethylamine.

When a monomer (b) 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 the monomer (b) having a carboxyl group is used, it is preferable to use acids and their ammonium salts, lower amine salts, polyvalent metal salts, and the like. When the monomer (b) having an isocyano group is used, it is preferable to use amines, metal salt compounds and the like. When the monomer (b) having an epoxy group is used, it is preferable to use an organic metal compound, an amine or the like. Further, an N-methylol group or N
When the monomer (b) having an alkoxymethyl group is used, it is preferable to use acids and their ammonium salts, lower amine salts, polyvalent metal salts, and the like. When the monomer (b) having a hydroxyl group is used, it is preferable to use an acidic compound, an acid and their ammonium salts, lower amine salts, polyvalent metal salts, and the like. Two or more of these crosslinking catalysts may be used, and the total amount used is in the range of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on 100% by weight of the coating agent.

In the present invention, a filler, a thixotropy-imparting agent, a coloring pigment, an extender pigment, a dye, an antioxidant, an antioxidant, an antistatic agent, and a flame retardant may be used as long as the effects of the present invention are not impaired. Various additives such as a thermal conductivity improver, a plasticizer, an anti-sagging agent, an antifouling agent, a preservative, a bactericide, an antifoaming agent, a leveling agent, and a curing agent may be added.

The coating agent of the present invention is obtained by mixing and dissolving the polymer (A), the polymer (B), and, if necessary, a crosslinking agent, a crosslinking catalyst and additives in a solvent. Solvents include alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol methyl ether and diethylene glycol methyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether. Ethers, hexane, heptane, hydrocarbons such as octane, benzene,
Among the aromatics such as toluene, xylene and cumene, and the esters such as ethyl acetate and butyl acetate, appropriate ones are used according to the composition of the resin. Two or more solvents may be used. The mixing method is not particularly limited, but usually, the polymer solution used at the time of polymerization may be mixed as it is and stirred with a stirring blade, a shaking stirrer, a rotary stirrer, or the like. In order to improve coatability and the like, a solvent may be further added or concentrated. The mixing ratio of the polymer (A) and the polymer (B) is such that the monomer (a) is a polymer (A) and a polymer (B).
Is preferably 0.01 to 10% by weight of the total amount of If it is less than 0.01% by weight, sufficient surface properties of the coating film cannot be obtained, and if it is more than 10% by weight, sufficient coating film hardness cannot be obtained and the cost increases.

The coating agent thus obtained is coated on a plastic sheet substrate, and exhibits functions such as water repellency, ink repellency, antifouling property, and easy removal of contamination. The coating method is not particularly limited, but it can be coated by gravure coating, roll coating, dip coating, spray coating, brush coating, or the like. A tough coating film can be obtained by air-drying or heating the coating film at 30 to 300 ° C. for several seconds to several weeks.

The plastic sheet used in the present invention is not particularly limited as long as it is a plastic sheet containing a plasticizer. Specific examples include polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, natural rubber, polybutadiene, polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, acrylic resin, and styrene resin. In particular, it is suitable for antifouling of a plastic sheet containing a large amount of a plasticizer such as soft polyvinyl chloride. Further, the size, thickness, and shape of the sheet are not limited. A plastic sheet having a plate shape, a spherical shape, a rod shape, or the like can also be suitably used.

[0034]

EXAMPLES Next, examples of the present invention will be described more specifically. All parts in the examples are parts by weight. All the synthesis was performed under a nitrogen atmosphere. (Synthesis example A1) 500 equipped with a cooling pipe, a stirrer, and a thermometer
A 60 ml methyl flask was charged with 60 g of methyl ethyl ketone, and heated to 75 ° C. while stirring under a nitrogen stream. In a dropping funnel, 60 g of acrylonitrile, 60 g of 2-hydroxyethyl methacrylate, 34 g of butyl methacrylate, 40 g of methyl methacrylate, 6 g of acrylic acid, 1.6 g of azobisisobutyronitrile, and 20 g of methyl ethyl ketone were weighed and thoroughly stirred. The dropping funnel was set in the flask, and the monomer mixture was added dropwise over one hour. During the addition, the temperature was kept at 80 ° C.
After the completion of the dropwise addition, a polymerization reaction was carried out for 2 hours. Further, 0.4 parts of azobisisobutyronitrile was added to carry out polymerization for 2 hours to obtain a polymer (A1) solution having a weight average molecular weight of about 40,000.

(Synthesis Example A2) 60 g of methyl ethyl ketone was placed in a 500 ml flask equipped with a cooling tube, a stirrer, and a thermometer.
It was charged and heated to 75 ° C. while stirring under a nitrogen stream.
In a dropping funnel, 60 g of acrylonitrile, 60 g of glycidyl methacrylate, 40 g of butyl methacrylate, 40 g of methyl methacrylate, 1.6 g of azobisisobutyronitrile, and 20 g of methyl ethyl ketone were weighed and stirred well. The dropping funnel was set in the flask, and the monomer mixture was added dropwise over one hour. During the addition, the temperature was kept at 80 ° C. After dripping 2
Polymerization was conducted for 2 hours, and 0.4 parts of azobisisobutyronitrile was further added, followed by polymerization for 2 hours to obtain a polymer (A2) solution having a weight average molecular weight of about 43,000.

(Synthesis Example B1) 50 g of Silaplane FM-0721 (a polysiloxane compound having a methacryloxy group at one end) manufactured by Chisso Corporation, 30 g of 2-hydroxyethyl methacrylate, 20 g of butyl methacrylate, and 200 g of methyl ethyl ketone (MEK) were placed in a cooling tube. Stirrer,
The mixture was charged into a four-necked flask equipped with a thermometer, heated to 80 ° C. while stirring under a nitrogen stream, and 1.6 g of azobisisobutyronitrile was added. 0.4 part of lonitrile was added and polymerization was carried out for 2 hours to obtain a polymer having a weight average molecular weight of about 16,000 (B
1) A solution was obtained.

(Synthesis Example B2) A four-necked flask equipped with a cooling tube, a stirrer, and a thermometer was charged with 50 g of Silaplane FM-0721 manufactured by Chisso Corporation, 30 g of glycidyl methacrylate, 20 g of butyl methacrylate, and 200 g of methyl ethyl ketone (MEK). The mixture was heated to 80 ° C. while stirring under a nitrogen stream, and 1.6 g of azobisisobutyronitrile was added to carry out a polymerization reaction for 2 hours. Further, 0.4 part of azobisisobutyronitrile was added. Polymerization was performed for 2 hours to obtain a polymer (B2) solution having a weight average molecular weight of about 15,000. (Synthesis Example C1) 500 m equipped with a cooling pipe, a stirrer, and a thermometer
1 g of flask was charged with 60 g of methyl ethyl ketone, and the temperature was raised to 75 ° C. while stirring under a nitrogen stream. In a dropping funnel, 60 g of 2-hydroxyethyl methacrylate, 94 g of butyl methacrylate, 40 g of methyl methacrylate, acrylic acid 6
g, azobisisobutyronitrile 1.6 g and methyl ethyl ketone 20 g were weighed and stirred well. The dropping funnel was set in the flask, and the monomer mixture was added dropwise over one hour.
During the addition, the temperature was kept at 80 ° C. After the completion of the dropwise addition, a polymerization reaction was carried out for 2 hours. Further, 0.4 parts of azobisisobutyronitrile was added and polymerization was carried out for 2 hours, and the weight average molecular weight was about 44,000.
Was obtained as a polymer (C1) solution.

(Synthesis Example C2) 60 g of methyl ethyl ketone was charged into a 500 ml flask equipped with a cooling tube, a stirrer, and a thermometer, and the temperature was raised to 75 ° C. while stirring under a nitrogen stream. In a dropping funnel, 60 g of glycidyl methacrylate, 100 g of butyl methacrylate, 40 g of methyl methacrylate, 1.6 g of azobisisobutyronitrile, and 20 g of methyl ethyl ketone were weighed and stirred well. Place the dropping funnel on the flask,
The monomer mixture was added dropwise over one hour. During the addition, the temperature was kept at 80 ° C. After the completion of the dropwise addition, a polymerization reaction was carried out for 2 hours. Further, 0.4 parts of azobisisobutyronitrile was added, and polymerization was carried out for 2 hours. A polymer having a weight average molecular weight of about 47,000 (C
2) A solution was obtained.

(Examples 1 and 2, Comparative Examples 1 and 2) Each solution of the polymer (A) and the polymer (B) thus obtained was
Mix in the ratio shown in Table 1 in terms of solid content, and solid content 1
A paint was prepared by diluting with 5% methyl ethyl ketone. These coating liquids are applied to a PVC sol sheet for foamed PVC wallpaper using a 20 μm-thick bar coater, and are applied at 80 ° C.
After drying in an electric oven for 1 minute, the mixture was heated and foamed in an oven at 220 ° C. for 40 seconds.

Table 1 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Example Polymer Polymer Crosslinker, Crosslinking catalyst Addition amount (A) (B)-------------------------------Example 1 A1 94 g B16 g Crosslinking agent; SUMIDURE BL-4265 45 g Example 2 A2 94 g B2 6 g Crosslinking agent; Epicoat 828 60 g Crosslinking catalyst; triethylamine 1 g Comparative Example 1 C1 94 g B16 g Crosslinking agent; SUMIDURE BL-4265 45 g Comparative Example 2 C2 94 g B2 6 g Epicoat 828 60 g Cross-linking catalyst; Triethylamine 1 g ----------------------------------------- SUMIDURE L-75: Sumitomo Bayer Urethane Co., Ltd. isocyanate-based curing agent Epicoat 828: Yuka Shell Epoxy Co., Ltd. epoxy resin

The aluminum sheet thus coated was tested for antifouling properties. The test method is as follows. Oil-repellent Magic (registered trademark) property: Draw a black oil-based magic on the coating film and visually evaluate the degree of adhesion Oil-based magic stainability: Draw a red, blue, black oil-based magic on the coating film, 24 hours After standing at room temperature, it was wiped off with a waste cloth impregnated with ethanol, and the degree of dirt was visually evaluated. Coffee stainability: Coffee was applied on the coating film, allowed to stand at room temperature for 24 hours, wiped off with a watered rag, and visually evaluated for the degree of stain. Table 2 shows the results.

Table 2 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Examples Oil repellent magic Oily stains Coffee Pollution -------------------------------------------------------------------------- 1 Example 1 Almost no writing 4-5 5 Example 2 Hardly write 4-5 5 Comparative Example 1 Hardly write 1 1 Comparative Example 2 Hardly write 11 1 -------- ------------------------------------ −−−−−−−−− 5 point rating: 5 (excellent) to 1 (poor)

[0043]

As described above, according to the present invention, a plasticizer-containing plastic film is coated with a coating agent comprising a polymer (A) comprising (meth) acrylonitrile and a polymer (B) comprising a silicone-containing polymer. As a result, a high-performance sheet having excellent adhesion to the plasticizer-containing plastic film, having surface characteristics that are difficult to be stained, and capable of easily removing the stains was able to be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 27:06 F term (Reference) 4F006 AA04 AA12 AA15 AA16 AA17 AA18 AA22 AA35 AA36 AB24 AB39 BA11 EA05 4J038 CG161 DL032 GA01 GA02 GA03 GA04 GA06 GA07 GA08 GA15 KA03 KA04 MA07 MA09 NA05 PB02 PB05 PB07 PC08 4J100 AA02R AA03R AB02R AB03R AB07Q AB08R AC03R AC04R AC23R AC24R AC25R AE03R AE09Q AE18Q AG04R AJ01Q AJ02Q AJ08Q AJ09Q AK03R AK08R AK13R AL03R AL04R AL05R AL08Q AL08R AL09Q AL10Q AM02P AM21Q AP16Q AQ01Q AS02R AS03R AS11R BA03Q BA04Q BA05Q BA06Q BA08Q BA42Q BA56Q BA77Q BC43R BC54Q CA04 CA05 FA03 JA01

Claims (7)

[Claims] (A) (a) 5 to 7 (meth) acrylonitrile
0% by weight, (b) 5 to 40% by weight of a monomer having a carbon-carbon unsaturated double bond and a crosslinkable functional group, and (c) (a)
Or a polymer (A) consisting of 90 to 0% of a monomer copolymerizable with (b), and (d) a monomer having a carbon-carbon unsaturated double bond and a polyorganosiloxane chain in 5 to 60% by weight. %,
(B) 5 to 40% by weight of a monomer having a carbon-carbon unsaturated double bond and a crosslinkable functional group, and (c) 90 to 0% of a monomer copolymerizable with (a) or (b) Antifouling coating agent comprising a polymer (B) comprising: 2. The crosslinkable functional group of the monomer (b) having a carbon-carbon unsaturated double bond and a crosslinkable functional group is a hydrolyzable silyl group, a carboxyl group, an isocyano group, an epoxy group, At least one selected from the group consisting of an N-methylol group, an N-alkoxymethyl group, and a hydroxyl group
The antifouling coating agent according to claim 1, which is a kind of functional group. 3. The method according to claim 1, wherein the amount of the monomer (d) is 0.1 to 10% by weight based on the total of the polymer (A) and the polymer (B). Antifouling coating agent. 4. The method according to claim 1, further comprising a compound having a reactive functional group capable of reacting with a crosslinkable functional group of the polymer (A) and the polymer (B) as a crosslinking agent. The antifouling coating agent according to the above. 5. The antifouling coating agent according to claim 1, further comprising a crosslinking catalyst for promoting a crosslinking reaction between the polymer (A) and the polymer (B). 6. A plastic sheet obtained by coating a plastic substrate containing a plasticizer with the antifouling coating agent according to claim 1. 7. The plastic sheet according to claim 6, wherein the plastic substrate is a soft polyvinyl chloride.