JP2685600B2 - Aqueous surface treatment agent for polyvinyl chloride - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an aqueous surface treating agent capable of imparting an excellent antifouling property to an article whose surface is formed of polyvinyl chloride.

[Prior Art] Conventionally, polyvinyl chloride leather, sheets, especially a so-called biryl wallpaper having a plasticized polyvinyl chloride layer on its surface is used as a solvent finish of a matte or glossy type using an organic solvent as a surface finish. Surface treatment agents have been widely used because of their excellent finished appearance, touch and anti-blocking ability.

However, in recent years, air pollution, worker health and safety, fire,
Due to price issues and the like, the use of organic solvents is being suppressed as much as possible, and water-based surface treatment agents that use water as a dispersion medium are being rapidly converted.

On the other hand, especially in the field of vinyl wallpaper, there is a demand in the market for a surface treatment agent having a surface treatment agent having an antifouling function against contaminants in addition to the above effects.

However, at present, a method of applying a surface treatment agent for crosslinking a polymer mainly composed of methyl methacrylate with a polyisocyanate compound or a surface treatment agent to which a fluorine-based water / oil repellent is added is carried out, All of them are solvent-based, and they do not have a sufficient antifouling effect, and have drawbacks such as lack of flexibility.

[Problems to be Solved by the Invention] From the above, there has been a demand in the market for a surface treatment agent which is water-based and has an antifouling function. The present invention has been made to solve this problem.

[Means for Solving the Problems] The present invention relates to an aqueous surface treatment agent for polyvinyl chloride, which has solved the above-mentioned problems, and it relates to A. general formula (I). [Wherein R ¹ , R ² and R ³ are one or more groups selected from a monovalent hydrocarbon group having 1 to 20 carbon atoms and a monovalent halogenated hydrocarbon group, Y is one or two selected from organic groups containing radically reactive groups and / or SH groups.
X is a hydrogen atom, a monovalent lower alkyl group and a group represented by the formula R ¹ R ² R ⁴ Si (R ¹ and R ² are the same as described above, R ⁴ is R ¹ or The same group as Y) or the same or different atoms or groups selected from the above, m is a positive integer of 10,000 or less, and n is an integer of 1 or more] Part oil-in-water emulsion and B. a) General formula (II) (Wherein, R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is a C 1-18
Which is an alkyl group or an alkoxy-substituted alkyl group), and one or more monomers selected from the acrylic and / or methacrylic monomers 70 to 99% by weight b) ethylenically unsaturated amide, Alkyrol- or alkoxyalkyl-substituted compounds of ethylenically unsaturated amide, oxirane group, hydroxyl group, carboxyl group, amino group, sulfonic acid group, phosphoric acid group, polyalkyleneoxyo group or quaternary ammonium salt group-containing ethylenically unsaturated monovalent compound Monomer, complete ester of polyhydric alcohol and acrylic acid or methacrylic acid, diallyl ester of dibasic acid, allyl acrylate, allyl methacrylate, and one or more polyfunctional monomer selected from the group of divinylbenzene Body 1 to 20% by weight c) One or more ethylenic dissimilarity other than the above b) and b) Sum monomers 100 to 100% by weight of mixed monomers [a) to c) consisting of 0 to 20% by weight] 9
It is characterized in that it contains a copolymer emulsion obtained by emulsion polymerization of a mixture of 5 to 5 parts by weight in the presence of a radical polymerization initiator.

That is, the inventors of the present invention are capable of imparting an antifouling function equivalent to or higher than that of a solvent type to articles whose surface is formed of polyvinyl chloride, particularly polyvinyl chloride leathers, particularly vinyl wallpaper. As a result of earnest research to obtain a surface treatment agent, a copolymer obtained by emulsion polymerization of a mixture of an emulsion of an organopolysiloxane having a radically active group and a monomer mainly composed of an acrylic and / or methacrylic group. It was found that the purpose could be achieved by using an emulsion, and the present invention was completed by further studying the composition of the organopolysiloxane and the monomer.

The organopolysiloxane of component A used in the aqueous surface treatment agent of the present invention has the general formula (I) as described above. And R ¹ , R ² and R ³ are an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, a phenyl group, a tolyl group,
Selected from monovalent hydrocarbon groups having 1 to 20 carbon atoms exemplified by aryl groups such as xylyl group and naphthyl group, and groups in which some or all of hydrogen atoms bonded to carbon atoms of these groups are substituted with halogen atoms. X is a triorganosilyl group represented by R ¹ R ² R ⁴ Si (R ¹ and R ² are the same as described above, R ⁴ is
R ¹ or Y), a hydrogen atom, a methyl group, an ethyl group,
Propyl group, butyl group and the like are selected from lower alkyl groups having 1 to 5 carbon atoms, Y is a vinyl group, an allyl group,
It is selected from a radical reactive group exemplified by a γ-acryloxypropyl group, a γ-methacryloxypropyl group, a γ-mercaptopropyl group, and an SH group-containing organic group. In addition, m is a positive integer of 10,000 or less, and n is an integer of 1 or more, preferably 500 <m <8,000, 1 <n
It should be in the range of <500.

As a raw material of the organopolysiloxane represented by the general formula (I), (Wherein p = 3,4,5,6) a cyclic organopolysiloxane represented by the formula: (Wherein q is a positive integer) Liquid dimethylpolysiloxane in which both ends of the molecular chain are blocked with hydroxyl groups, formula (Where r is a positive integer) and a liquid dimethylpolysiloxane in which both terminals of the molecular chain are blocked with an alkoxy group, (In the formula, s = 0 or a positive integer) A dimethylpolysiloxane in which both ends of the molecular chain are blocked with a trimethylsilyl group, or as a raw material for introducing a radical reactive group and an SH group, Silanes and their hydrolysis products (Where t = 3, 4, 5, 6).

In addition, if it is a small amount that does not disturb the object of the present invention,
Trifunctional trialkoxysilanes and their hydrolysis products can also be used.

The production of the emulsion of the organopolysiloxane represented by the general formula (I) may be performed according to a known method.
One method is to use a low-molecular-weight cyclic siloxane such as octamethylcyclotetrasiloxane described above and a dialkoxysilane compound containing a radical reactive group or SH group and / or a hydrolyzate thereof as a raw material, and use a strong alkaline catalyst as a raw material. Alternatively, the polymerization is carried out in the presence of a strongly acidic catalyst to obtain a high molecular weight organopolysiloxane, and then emulsified and dispersed in water in the presence of a suitable emulsifier. Another method is to use a low-molecular-weight organopolysiloxane as a raw material and a radical-reactive group or
This is based on emulsion polymerization in water in the presence of a sulfonic acid-based surfactant and / or a sulfate ester-based surfactant using a dialkoxysilane containing an SH group and / or a hydrolyzate thereof. In addition, in the case of this emulsion polymerization, after using the same raw materials and emulsifying and dispersing in water with a cationic surfactant such as alkyltrimethylammonium chloride or alkylbenzylammonium chloride, an appropriate amount of potassium hydroxide, sodium hydroxide or the like is used. Polymerization can also be carried out by adding a strongly alkaline substance.

Among the above-mentioned methods for producing an organopolysiloxane emulsion, potassium hydroxide, sodium hydroxide, cesium hydroxide, tetramethylammonium hydroxide, tetrabutyl Phosphonium hydroxide and the like, and strong acid polymerization catalysts such as sulfuric acid and trifluoromethanesulfonic acid are exemplified. Any of these can be used after neutralization after completion of the polymerization to eliminate the catalytic activity. As a surfactant for emulsifying the obtained high molecular weight organopolysiloxane, various nonionic polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ether,
Polyoxyethylene alkyl ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sucrose fatty acid ester, etc .; anionic sodium lauryl sulfate, polyoxyethylene dodecyl sulfate, etc .; cationic alkyl trimethylammonium chloride, alkyl benzyl Ammonium chloride,
Examples thereof include dialkyldimethylammonium chloride.

Further, when an emulsion of an organopolysiloxane is produced by an emulsion polymerization method, the above-mentioned sulfonic acid-based surfactant and sulfate ester-based surfactant also serve as an emulsifier and a polymerization catalyst. Examples include C ₁₀ H ₂₁ (OC ₂ H ₄ ) ₂ OSO ₃ H, sodium lauryl sulfate, and sodium polyoxyethylene dodecylphenyl sulfate. Of these, the sulfates are converted into the corresponding acids by contacting with a cation exchange resin after the emulsification, and function as a polymerization catalyst. After the completion of the emulsion polymerization, the surfactant in the acid form may be neutralized to eliminate the catalytic activity. Further, as the cationic emulsifier, a quaternary ammonium salt as described above is mainly used, and after the emulsion polymerization, a basic surfactant may be neutralized to eliminate the catalytic activity.

The organopolysiloxane represented by the general formula (I)
If the molecular weight is small, the desired antifouling effect is poor, so the molecular weight is preferably as high as possible. For this reason, when emulsifying and dispersing an organopolysiloxane obtained in advance by polymerization, it is necessary to keep this organopolysiloxane of high molecular weight.In the case of emulsion polymerization, it is necessary to lower the temperature during ripening performed after polymerization. For example, since the molecular weight of the organopolysiloxane becomes large, the aging temperature is preferably set to 30 ° C. or lower, more preferably 15 ° C. or lower.

Next, the component B will be described. This is a mixture of polymerizable monomers for graft-copolymerizing with the above-mentioned organopolysiloxane of the component A, and is composed of the following three components a) to c). is there. A) The component is represented by the general formula (II) (In the formula, R ⁵ is hydrogen or a methyl group, and R ⁶ is an alkyl group or an alkoxy-substituted alkyl group having 1 to 18 carbon atoms) (meth) acrylic monomer [wherein the expression (meth) acrylic is acrylic Both methacrylic and methacrylic are collectively represented, and the same shall apply hereinafter. ], And methyl (meta)
Acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate,
Alkyl (meth) acrylates such as isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate And alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate and butoxyethyl (meth) acrylate, and one or two of these.
Used in combination of more than one species. If the amount of this component is less than 70% by weight in the component B, the properties of the (meth) acrylic, especially the adhesion to vinyl chloride leather are insufficient, so it is necessary to increase the amount.

B) The component is a polyfunctional monomer, and (meth) acrylamide as an ethylenically unsaturated amide, an alkylol of an ethylenically unsaturated amide or an alkoxyalkyl compound,
Diacetone (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth)
Acrylamide, N-methoxymethyl (meth) acrylamide and the like, oxirane group-containing unsaturated monomer glycidyl (meth) acrylate, glycidyl allyl ether and the like, hydroxyl group-containing unsaturated monomer 2-hydroxyethyl (meth) acrylate, 2-Hydroxypropyl (meth) acrylate and the like, carboxyl group-containing ethylenically unsaturated monomer (meth) acrylic acid, maleic anhydride, crotonic acid, methaconic acid and the like, amino group-containing unsaturated monomer N-dimethyl As a sulfone group-containing unsaturated monomer such as aminoethyl (meth) acrylate and N-diethylaminoethyl (meth) acrylate CH ₂ = CHSO ₃ X (In the formula, R ⁷ is an alkyl group having 1 to 18 carbon atoms, R ⁸ is H or a methyl group, and X is H, Na, K or NH ₄ ) As a phosphoric acid group-containing unsaturated monomer (In the formula, R ⁸ is the same as above, v is an integer of 1 or more) As the polyalkylene oxide group-containing unsaturated monomer (Wherein R ⁸ is the same as above, w is an integer of 2 or more) As the quaternary ammonium salt group-containing unsaturated monomer Examples of complete esters of polyhydric alcohol and (meth) acrylic acid include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate, and divinylbenzene. ,
These are used alone or in combination of two or more.

These polyfunctional monomers increase the adhesiveness of the polymer content in the treatment agent to vinyl chloride leather and participate in the cross-linking between the polymers in the treatment agent, thereby improving the durability and solvent resistance of the film. Give. If the amount of this component (b) is increased, the desired properties will be improved, but if it is too large, cracks will occur due to the hardness of the film and the water resistance will decrease. % Is required.

C) the component is another ethylenically unsaturated monomer,
Although the touch, durability, adhesion to vinyl chloride leather, etc., which cannot be exhibited only by the above-mentioned components a) and b), are imparted, if the content exceeds 20% by weight in the component B, the properties of the (meth) acrylic are impaired. , It is necessary to be less than this. Examples of these monomers include styrene, α-methylstyrene, vinyltoluene, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl propionate, and vinyl versatate.

When the amount of the component A is less than 5 parts by weight with respect to the amount of the component B to 95 parts by weight, the water- and oil-repellent effect unique to the organopolysiloxane is poor and the antifouling function cannot be obtained.

Further, when the amount of the component A exceeds 95 parts by weight with respect to the amount of the component B of 5 parts by weight, the adhesion to the base material is poor, and moreover, a sticky feeling occurs.
It is not practical because the dirt prevention effect is poor.

The emulsion copolymerization of the component A and the component B may be carried out by a known emulsion polymerization method using a usual radical initiator.

Examples of the radical initiator used here include persulfates such as potassium persulfate and ammonium persulfate, water-soluble types such as hydrogen peroxide solution, t-butyl hydroperoxide, azobisamidinopropane hydrochloride, and benzoylperoxide. Examples thereof include oil-soluble types such as oxide, cumene hydroperoxide, dibutyl peroxide, diisopropyl peroxydicarbonate, cumyl peroxyneodecanoate, cumyl peroxy octoate, and azobisisobutyronitrile. If necessary, a redox system in which a reducing agent such as acidic sodium sulfite, Rongalite, 1-ascorbic acid, saccharides, amines is used together can be used.

As the emulsifier, the emulsifier contained in the emulsion of the component A does not necessarily have to be newly used, but in order to prevent coagulation during polymerization and improve the stability of the emulsion,
A necessary amount of emulsifier may be added. Examples of the emulsifier used herein include alkyl or alkylallyl sulfate or sulfonate, anionic emulsifier such as dialkyl sulfosuccinate, alkyltrimethylammonium chloride, cationic emulsifier such as alkylbenzylammonium chloride, and polyoxyethylene alkyl. Nonionic emulsifiers such as phenyl ether, polyoxyethylene alkyl ether and polyoxyethylene carboxylate are preferred.

Further, other additives may be added to the aqueous surface treatment agent of the present invention depending on the purpose. For example, in order to obtain a matte coating film, silicic acid anhydride, silicic acid such as hydrous silicic acid, aluminum silicate, magnesium silicate, clay, silicate compounds such as talc, calcium carbonate, barium carbonate, gypsum, talc,
Add a delusterant such as alumina white and synthetic resin powder, then ball mill, colloid mill, homomixer,
Disperse the matting agent with a disperser such as a sand mill or a disper to obtain a paint for forming a matte coating film.

Dyes, pigments and the like may be added to obtain a colored coating film.

Also, when it is necessary to adjust the viscosity of the emulsion,
Polyvinyl alcohol, gelatin, methyl cellulose,
Appropriate amounts of cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, xanthan gum, sodium polyacrylate and polyacrylamide may be added. For uniform coating on the substrate to be treated, anionic, nonionic or cationic surfactants and water-soluble organic solvents such as lower alcohols, acetone and dimethylformamide can be added if necessary.

In addition, a defoaming agent, an antiseptic agent, an antifungal agent and the like can be added as required.

EXAMPLES Next, the present invention will be specifically described based on examples. All parts in the examples are parts by weight. Further, the surface treatment agent was evaluated by the following test methods.

(Test piece) Each surface treatment agent was applied onto the surface of the white vinyl wallpaper before foaming with a bar coater in an amount of 10 g / m ² and then dried at 105 ° C for 1 minute and further heated at 220 ° C for 1 minute to form a vinyl chloride layer. Was foamed to obtain a vinyl wallpaper test piece.

(Appearance) The appearance was visually determined.

(Tactile sensation) Evaluation was performed by touch.

Performance indication: Good ◎ ～ ○ ～ △ ～ × Poor (contamination resistance) After contaminating the surface of the test piece with various contaminants and leaving it for 24 hours,
10% of neutral detergent (trade name: Mama Lemon, manufactured by Lion) when contaminated with oil-based magic ink, crayon, or shoe ink
It was wiped off with an aqueous solution and with water when other contaminants were used, using gauze, and the extent of residual contamination was evaluated.

Performance indication: ◎ ... no pollution, ○ ... almost no pollution, △ ...
Contamination remains, x: Complete contamination (adhesion) After the cellophane tape was attached to the surface of the test piece, it was peeled off at once and judged by the degree of peeling of the surface treatment agent layer.

Performance indication: ◎ ... no peeling, ○ ... almost no peeling, △ ...
Peeling, ×: Peeling completely (blocking resistance) A test piece with the treated surfaces stacked together and a stack of the treated surface and the back side of the paper sheet were subjected to a load of 3 kg per 36 cm ² and a temperature of 83 ° C. After being left in the atmosphere for 24 hours, the peeled state when the both surfaces were peeled off was judged.

Performance indication: ⊚: No abnormality, ∘: Almost no blocking, Δ: Partially blocking, ×: Full blocking Example 1 to 5, Comparative Examples 1 to 2 (Production of organopolysiloxane emulsion) Octamethylcyclotetrasiloxane 1500 Parts, methacryloxypropylmethylsiloxane 3.8 parts and pure water 1500
The resulting mixture was mixed with 15 parts of sodium lauryl sulfate and 10 parts of dodecylbenzenesulfonic acid, and the mixture was stirred with a homomixer to emulsify and then passed through a homogenizer having a pressure of 3000 psi twice to form a stable emulsion. Then it was heated at 70 ℃ for 12 hours, cooled to 25 ℃ and aged for 24 hours.
The pH was adjusted to 7 and nitrogen gas was blown for 4 hours, then steam distillation was carried out to distill off the volatile siloxane, and then pure water was added to adjust the non-volatile content to 45% and the methacrylic group to 0.1%.
An emulsion of organopolysiloxane containing mol% was obtained. (Hereinafter, this is abbreviated as E-1.) Further, as shown in Table 1, the organopolysiloxane emulsion E was prepared in the same manner as in E-1 except that the kind and amount of siloxane and the aging conditions were changed. -2-E-3 were obtained.

(Production of Organopolysiloxane / Acrylic Copolymer Emulsion) 333 parts of the organopolysiloxane emulsion E-1 obtained above in a reaction vessel equipped with a stirrer, condenser, thermometer and nitrogen gas inlet (organopolysiloxane content 150
Part) and 560 parts of pure water, and the inside of the device is kept under a nitrogen gas stream for 30
After adjusting to ℃, t-butyl hydroperoxide 1.
0 part, 0.5 part of 1-ascorbic acid, ferrous sulfate heptahydrate.
002 parts was added, and then while maintaining the temperature inside the vessel at 30 ° C., a mixture of 167 parts of butyl acrylate, 167 parts of ethyl acrylate, 5.5 parts of methacrylic acid and 10.5 parts of acrylic acid was added dropwise over 3 hours, and further 1 Stirring was continued to complete the reaction. The obtained copolymer emulsion (hereinafter abbreviated as P-1) had a solid content concentration of 40%. In the same manner as above, the types of organopolysiloxane emulsions and (meth) acrylic monomers shown in Table 2,
To obtain copolymerized emulsions P-2 to P-5 having a solid content concentration of 39 to 40%.

(Production and Evaluation of Lustered Surface Treatment Agent) A lustered surface treatment agent was produced by the following method with the formulations shown in Table 3.

The viscosity modifier was dissolved in deionized water in advance to form a 10% aqueous solution, and the amount used for dissolving the viscosity modifier was subtracted from the total amount of deionized water. An aqueous surface treatment agent was obtained by adding a copolymer emulsion, an aqueous solution of a viscosity modifier, and an additive in this order and mixing them uniformly. In the case of Example 1, the solid content concentration is 12.8%, the viscosity is 1000 cps (B type viscometer No. 2 rotor, 6
rpm).

As a comparative example, a polyacrylic ester emulsion or a polyvinyl chloride emulsion was used in place of the organopolysiloxane / acrylic copolymer emulsion, and an aqueous surface treating agent was prepared in the same manner as above with the formulation shown in Table 3.

When these surface treatment agents were evaluated by the above-mentioned test methods, the results are as shown in Table 4.

Non-foamed white vinyl wallpaper was also tested by the same method using the same surface treatment agent, and similar results were obtained. From these results, it is clear that the surface treatment agent of the present invention has an excellent antifouling effect and also has excellent touch, adhesion and blocking resistance.

Examples 6 to 8 and Comparative Examples 3 to 4 (Production and Evaluation of Matting Surface Treatment Agent) Matting surface treatment agents were produced by the following methods with the formulations shown in Table 5. Silica fine powder Syloid 244 for matting
(Manufactured by Fuji Devison Co., Ltd.), 200 parts thereof was added to 800 parts of deionized water under stirring, dispersed with a disper, and used as a delusterant dispersion.

The viscosity modifier was dissolved in deionized water in advance to form a 10% aqueous solution, and the amount used for dissolving the viscosity modifier was subtracted from the total amount of deionized water. An aqueous surface treatment agent was obtained by adding the copolymer emulsion, the delusterant dispersion, the aqueous solution of the viscosity modifier, and the additive in that order and mixing them uniformly.

As a comparative example, an aqueous surface treating agent was prepared in the same manner as above except that the formulation shown in Table 5 was changed.

When these surface treatment agents were evaluated by the above-mentioned test methods, the results are as shown in Table 6.

Non-foamed white vinyl wallpaper was also tested by the same method using the same surface treatment agent, and similar results were obtained. From these results, it is clear that the surface treating agent of the present invention has an excellent antifouling effect and also has excellent touch, adhesion and blocking resistance.

EFFECTS OF THE INVENTION The surface treatment agent of the present invention is a novel aqueous surface treatment agent, and is safe for use because it is aqueous, and treatment of an article having a surface formed of polyvinyl chloride with this gives excellent protection. Give a dirty effect. This effect cannot be obtained with conventionally used vinyl chloride resins, (meth) acrylic resins and the like. Moreover, the antifouling effect is excellent even in the case of matte having fine irregularities on the surface. Furthermore, it has excellent appearance, touch, adhesion, blocking resistance, heat resistance, weather resistance and the like. Therefore, the surface treatment agent of the present invention is extremely advantageous in practical use.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location // C08F 283/12 C08F 283/12 C08L 51:00

Claims (1)

(57) [Claims] 1. A. General formula (I) [Wherein R ¹ , R ² and R ³ are one or more groups selected from a monovalent hydrocarbon group having 1 to 20 carbon atoms and a monovalent halogenated hydrocarbon group, Y is one or two selected from organic groups containing radically reactive groups and / or SH groups.
X is a hydrogen atom, a monovalent lower alkyl group and a group represented by the formula R ¹ R ² R ⁴ Si (R ¹ and R ² are the same as described above, R ⁴ is R ¹ or The same group as Y) or the same or different atoms or groups selected from the above, m is a positive integer of 10,000 or less, and n is an integer of 1 or more] Part oil-in-water emulsion and B. a) General formula (II) (Wherein, R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is a C 1-18
Which is an alkyl group or an alkoxy-substituted alkyl group), and one or more monomers selected from the acrylic and / or methacrylic monomers 70 to 99% by weight b) ethylenically unsaturated amide, Alkyrol or alkoxyalkyl substituted compound of ethylenically unsaturated amide, oxirane group, hydroxyl group, carboxyl group, amino group, sulfonic acid group, phosphoric acid group, polyalkylene oxide group or quaternary ammonium salt group-containing ethylenically unsaturated monomer Body, complete ester of polyhydric alcohol and acrylic acid or methacrylic acid, diallyl ester of dibasic acid, allyl acrylate, allyl methacrylate and one or more polyfunctional monomers selected from the group of divinylbenzene 1 to 20% by weight c) One or more ethylenic satiety other than the above b) and b) Sum monomers 100 to 100% by weight of mixed monomers [a) to c) consisting of 0 to 20% by weight] 9
An aqueous surface treatment agent for polyvinyl chloride, comprising a copolymer emulsion obtained by emulsion polymerization of a mixture of 5 to 5 parts by weight in the presence of a radical polymerization initiator.