JP4749500B1 - Aqueous surface treatment composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous surface treatment agent composition which is compatible in blocking resistance and crumpling resistance when being applied to a synthetic resin sheet, leather, tarpaulin, a molding or the like, and can form a coating which is excellent in smoothness, abrasion resistance, transparency, and stainproof by low-temperature drying. <P>SOLUTION: The aqueous surface treatment agent composition includes: (A) (a) methyl methacrylate, (b) a silicone macromonomer which has an acryloyl group at the one terminal, (c) an ethylenically unsaturated monomer which has a hydroxy group, (d) an ethylenically unsaturated monomer which has a carbonyl group originating in a keto group or an aldehyde group, and (e) an aqueous emulsion of a (meth)acrylic based copolymer resin obtained by copolymerizing an ethylenically unsaturated monomer other than methyl methacrylate; and (B) a hydrazine derivative which has at least two hydrazino groups per one molecule. Further, a coated article covered by the same is disclosed. <P>COPYRIGHT: (C)2012,JPO&amp;INPIT

Description

  The present invention is a one-component cross-linking aqueous surface treatment that can protect a surface of a synthetic resin sheet, leather, tarpaulin, and molded product, and can form a film that imparts slipperiness, wear resistance, and antifouling properties at a low temperature. It is related with an agent composition.

Generally, a resin sheet is made of (meth) acrylic resin or urethane to prevent the plasticizer added to give flexibility from bleeding on the surface and causing stickiness and dirt adhesion. Surface treatment is performed with a coating agent made of a resin.
Conventionally, most of the coating agents used in these surface treatments are solvent-based, but in recent years, efforts to make water-based have been promoted due to the increased awareness of regulations on VOC emissions and improvement of the working environment. ing.
However, in the case of an aqueous surface treatment agent, the film-forming property at low temperatures is poor compared to the solvent system, so that drying at high temperatures is required, and there is a problem that heat is deformed in a highly flexible sheet. .

Therefore, it was necessary to add a large amount of high-boiling organic solvent as a film-forming aid, or to use a resin having a low Tg, but this causes blocking of the film and deterioration of lubricity and antifouling properties. It was not a satisfactory treatment method.
In order to solve these problems, many methods utilizing the room temperature crosslinking property of ketone groups and hydrazino groups have been developed, but this alone is not sufficient for solving the problems, and further improvements have been proposed.
For example, room temperature curing containing a diacetone acrylamide-containing polymer emulsion and a hydrazide-based compound obtained by multi-layer polymerization of a resin with increased hardness by blending a silane coupling agent and a resin with low Tg with good film forming properties by multi-stage polymerization Type resin composition (Patent Document 1), hydrolyzable silyl group-containing emulsion, colloidal silica and an aqueous coating material containing an organic hydrazide compound (Patent Document 2).

However, these methods have a problem that a portion having high hardness is generated in the film, and when the substrate is coated on a highly flexible substrate, the bent portion is whitened and the resistance to abrasion is deteriorated.
In order to achieve both resistance to blockage and blocking, it contains an aqueous dispersion of vinyl polymer copolymerized with an acrylic acid-based macromonomer having an unsaturated double bond and a carboxyl group at the end, and an organic hydrazine derivative. An aqueous coating composition (Patent Document 3) has been proposed, but due to the long hydrophobic group of the vinyl polymer, the antifouling property against hydrophobic dirt was insufficient.
In order to improve the antifouling property, a silicon macromonomer and a carbonyl group-containing vinyl polymerizable monomer prepared by ring-opening a cyclic dimethylsiloxane oligomer with a vinyl polymerizable functional group-containing silane coupling agent, and other vinyl polymerizable monomers. There has been proposed a resin composition for coating (Patent Document 4) comprising a graft block copolymer emulsion obtained by graft copolymerization with a monomer and an organic hydrazine compound.

However, this method has good antifouling properties, but has problems with the slipperiness and wear resistance of the film.
In the polyurethane system, a crosslinkable aqueous coating agent has been proposed in which a core / shell type polyol having a specific molecular weight distribution dispersion ratio and a water-dispersed isocyanate are cross-linked by a urethanization reaction catalyst (Patent Document 5).
Although these have been improved in pot life as compared with the conventional ones, they are two-pack type and increase in viscosity within a few hours, so strict management of the work process is required, and problems still remain.

In addition, when sewing surface-treated sheets, there is a problem that the position is difficult to adjust because the slip between the film and the sheet or the film is poor (the smoothness between the treated surfaces), and the final product is a bag, furniture, or table. In the case of applications such as a cloth that touches the hand, improvement in slipperiness such as a light touch (surface slipperiness) is also desired.
As described above, as a surface treatment agent composition, it is excellent in film-forming properties, has both resistance to blockage and blocking, and has a one-component cross-linking type aqueous solution that is excellent in slipping property, abrasion resistance, transparency, and antifouling property. No surface treatment agent composition has been developed so far.

JP 2006-45397 A JP2009-269972A Patent 3421162 Patent 3642846 JP2007-186582

  In order to solve the above-mentioned problems, the present invention has a good film-forming property, achieves both blocking resistance and rub resistance, and is low-temperature dried from a film having excellent lubricity, abrasion resistance, transparency and antifouling properties. An object of the present invention is to provide a one-component cross-linking aqueous surface treating agent composition that can be formed by

As a result of intensive studies to solve the above problems, the present inventors have
(A) (a) methyl methacrylate, (b) a silicone macromonomer having a (meth) acryloyl group at one end, (c) an ethylenically unsaturated monomer having a hydroxyl group, (d) a keto group or an aldehyde group Aqueous (meth) acrylic copolymer resins obtained by copolymerizing specific amounts of ethylenically unsaturated monomers having carbonyl groups derived from (e) ethylenically unsaturated monomers other than methyl methacrylate, respectively Emulsions,
(B) The present inventors have found that an aqueous surface treatment composition comprising a specific amount of a hydrazine derivative having at least two hydrazino groups per molecule can achieve the above object, and has reached the present invention.

The aqueous surface treating agent composition of the present invention is applied to a synthetic resin sheet, leather, tarpaulin used for furniture, interiors, bags, etc. with a gravure coater and dried at 50 ° C. or more for 0.5-2 minutes. Thus, a protective film that is flexible and excellent in blocking resistance can be formed.
Excellent followability to a flexible base material, and whitening does not occur even when the coated sheet is folded, and the resistance to cracking is good. Moreover, although it is a flexible film | membrane, it becomes a tough film | membrane by bridge | crosslinking, can prevent the bleeding of the plasticizer from a base material, and does not raise | block blocking even if a sheet | seat is wound up and accumulated.
Furthermore, since this film is excellent in surface slipperiness, it is easy to adjust the position when sewing the coated sheet, and the touch feeling when the final product touches the hand is also excellent. Since it is a transparent film, it can be applied to a sheet printed with a pattern or a transparent sheet.
Moreover, when the resin product is a molded product, it can be applied by a method such as spray coating or dipping.

Hereinafter, the present invention will be described in detail.
The method for obtaining an aqueous emulsion of the (A) (meth) acrylic copolymer resin to be a base resin is not particularly limited, but the method of neutralizing with an alkali after solution polymerization and dispersing in water is a hydrophilic functional group. It is necessary to introduce a large number of groups, and the film easily absorbs external moisture.
Moreover, the molecular weight of the resin obtained by solution polymerization is relatively small, and the surface migration preventing effect of the plasticizer that bleeds out from the base material is inferior. For this reason, emulsion polymerization is preferred as a method for obtaining an aqueous emulsion of (A) (meth) acrylic copolymer resin.
Emulsion polymerization may be performed by a general method, and the surfactant may be any one of anionic, cationic, and nonionic anionic surfactants having polyethylene oxide, or may be used in combination with a nonionic surfactant. A reactive emulsifier having an ethylenically unsaturated double bond in the molecule can also be used.

(A) Each monomer component of the aqueous emulsion of (meth) acrylic copolymer resin will be described.
(a) Methyl methacrylate is 20 to 80 parts by weight, preferably 30 to 70 parts by weight, more preferably 40 to 60 parts by weight, of the resin solid content of the aqueous emulsion of (A) (meth) acrylic copolymer resin. By containing a part, flexibility and blocking resistance can be balanced.
When the amount is less than 20 parts by weight, the film becomes harder and whitens when bent, and the resistance to padding is poor. Inferior properties, lubricity and antifouling properties.

(b) A silicone macromonomer having a (meth) acryloyl group at one end has a structure as shown in Chemical Formula 1 and is copolymerized with a compound having an ethylenically unsaturated double bond to form a (meth) acrylic copolymer. A silicone polymer can be introduced into the side chain of the coalesced resin.
When the number average molecular weight in terms of polystyrene by gel permeation is 10,000 to 30,000, the film is lubricated, and even if the treated surfaces of the coated sheets or the film and the untreated surface are overlapped, it moves smoothly. This makes it easy to adjust the position during sewing. In addition, wear resistance and tactile sensation when the sheet is touched by hand are also improved.
When the number average molecular weight is less than 10,000, the effect on lubricity is inferior, and when it exceeds 30,000, the reactivity is remarkably lowered and remains as an unreacted product. Such silicone macromonomers are commercially available Silaplane FM-0725 (Mn = 10000, Chisso Corporation), MCR-22 (Mn = 10000, US Gelest), AK-32 (Mn = 20000, Toagosei Co., Ltd.) ), AK-30 (Mn = 30000, Toagosei Co., Ltd.) and the like can be used, but are not limited thereto.
Content is 0.1-5 weight part in the resin solid content of the aqueous emulsion of (A) (meth) acrylic-type copolymer resin, Preferably it is 0.5-3 weight part, More preferably, it is 1-2. If it is less than this, the effect on lubricity is low, and if it is more than this, polymerization stability is inferior and aggregates are generated.

(c) The ethylenically unsaturated monomer having a hydroxyl group improves the blocking resistance of the film. Particularly in the case of a vinyl chloride base material, the effect is remarkable, and the force (dissolution strength) required for the work of drawing out the coated sheet after being wound up and stored can be suppressed.
Specific examples of the component (c) include 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate and the like, and can be selected according to the desired Tg of the film.
Content should just add 1-10 weight part among resin solid content of the aqueous emulsion of (A) (meth) acrylic-type copolymer resin, and if it is less than this, an effect will not be seen in suppression of anti-cracking strength. If it is more than this, the polymerization stability of the resin is lowered.

(d) By copolymerizing an ethylenically unsaturated monomer having a carbonyl group derived from a keto group or an aldehyde group into an aqueous emulsion of (A) (meth) acrylic copolymer resin, Cross-linking with a hydrazine derivative by dehydration reaction. Thereby, the film can achieve both flexibility and blocking resistance.
Specific examples of the component (d) include diacetone (meth) acrylamide, acetoacetoxyethyl (meth) acrylate, acrolein, vinyl methyl ketone, vinyl ethyl ketone, and vinyl isobutyl ketone. In particular, use of diacetone acrylamide is preferable.
Content is 1-10 weight part among resin solid content of the aqueous emulsion of (A) (meth) acrylic-type copolymer resin, Preferably improvement of a film physical property can be aimed at by 3-7 weight part. If it is less than this, the crosslinking effect cannot be obtained, and if it is more than this, the polymerization stability is lowered, and the film becomes excessively hydrophilic, resulting in poor water resistance.

(E) Specific examples of ethylenically unsaturated monomers other than methyl methacrylate include styrene, acrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride, ethyl methacrylate, propyl methacrylate, hexyl methacrylate and other methacrylates other than methyl methacrylate, methyl Examples thereof include acrylates such as acrylate, ethyl acrylate, propyl acrylate, and hexyl acrylate, acrylic acid, methacrylic acid, acrylic amide, and methacrylic amide. Among these, one type may be used or two or more types may be used in combination.
Content should just add 17.9-55.0 weight part among resin solid content of the aqueous emulsion of (A) (meth) acrylic-type copolymer resin, and if it is less than this, the coating resistance of a coating film will be sufficient as it. If it is more than this, the blocking resistance is lowered.
In particular, a monomer containing a carboxyl group such as acrylic acid or methacrylic acid is 1 to 3 in the ethylenically unsaturated monomer (e) in order to improve the polymerization stability and the storage stability of the obtained emulsion. It is preferable to blend by weight.

Moreover, if the Tg of the aqueous emulsion of (A) (meth) acrylic copolymer resin is 20 to 60 ° C., both resistance to abrasion and blocking resistance can be achieved.
The pH of the obtained emulsion is preferably neutralized to pH 7 to 9 with amines such as ammonia, trimethylamine, triethylamine, dimethylethanolamine and the like. When the pH is lower than 7, the storage stability is deteriorated, and the crosslinking between the carbonyl group or aldehyde group and the hydrazino group is given priority in the emulsion particles rather than between the emulsion particles, and the effect of improving the blocking resistance of the film is inferior. If the pH is higher than 9, the viscosity change during storage of the aqueous surface treatment agent becomes large.

(B) Specific examples of hydrazine derivatives having at least two hydrazino groups per molecule include oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, itaconic acid dihydrazide and the like. It is done. The use of adipic acid dihydrazide is particularly preferred.
The blending amount is required to be 0.2 to 2.0 mol of hydrazino group per 1 mol of carbonyl group or aldehyde group in component (d) constituting the emulsion (A). If it is less than this, the anti-blocking property and slipperiness of the film will be inferior.

In addition to the above (A) aqueous emulsion and (B) hydrazine derivative, matting agents, film-forming aids, wetting agents, thickeners, antifoaming agents, etc., depending on the coating method and various functions required for the film Additives can be added.
This aqueous surface treatment agent is applied to a synthetic resin base material by a gravure coater, knife coater, roll coater, dipping or the like and dried to form a protective film. For example, in the case of a gravure coater, a desired film can be obtained by coating with 100 to 200 mesh and drying at 50 to 120 ° C. for 0.5 to 2 minutes. In order to obtain sufficient film strength and transparency, the drying temperature is desirably 50 ° C. or higher.

  A primer can be used when the adhesiveness with the synthetic resin substrate is insufficient. An appropriate primer can be selected depending on the type of the substrate, but a non-yellowing type polyurethane resin or an aliphatic acrylic resin is preferable so as not to impair the weather resistance of the coated material. For example, in a commercially available resin for an aqueous primer, for a vinyl chloride substrate, Bontiter HUX-232, Bontiter HUX-420A (above ADEKA Co., Ltd.), Mobile DM772, Movia DM774 (above Nippon Synthetic Chemical Industry Co., Ltd.), PET For the film, Bontiter HUX-1032 (ADEKA Corporation), Superflex 210 (Daiichi Kogyo Seiyaku Co., Ltd.), and for the polyolefin sheet, Movinyl 7523 (Nippon Synthetic Chemical Industry Co., Ltd.) can be used.

Hereinafter, embodiments of the present invention will be described in detail. Each formulation is in parts by weight.
((Meth) acrylic copolymer resin aqueous emulsion production example A)
It can be obtained by ordinary emulsion polymerization. The monomer is weighed with the formulation shown in Table 1, and mixed and stirred. Monomer Y-100, a pre-emulsion surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 42.9 parts of deionized water mixed and dissolved in a homogenizer and mixed well. 100.0 parts of the body was added and stirred at 5000 rpm for 5 minutes to obtain a pre-emulsion. 5% of the pre-emulsion, 1.7 parts of surfactant Y-100 (Daiichi Kogyo Seiyaku Co., Ltd.) and 7.2 parts of deionized water were weighed into a separable flask, and a stirrer, thermometer, condenser A device equipped with a nitrogen gas introduction tube and a metering pump was attached, and the inside of the reaction vessel was replaced with nitrogen gas. The mixture was heated with stirring at 200 rpm, and when the inside of the reaction vessel reached 70 ° C., 0.5 parts of ammonium persulfate (APS) as an initiator dissolved in 4.5 parts of deionized water was added. From 10 minutes after the initiator was charged, the remaining pre-emulsion was uniformly supplied over a period of 3 hours with a metering pump, and the inside of the reaction vessel was kept at 70 ° C. during that time. After completion of the pre-emulsion supply, the temperature in the reaction vessel was raised to 75 ° C. and further reacted for 90 minutes. After completion of the reaction, the flask was cooled to 30 ° C. or less, and then 0.6 parts of 15% ammonia water was added to neutralize to pH 7.0 to 8.0. Filtration was carried out using nylon 200 mesh to obtain an aqueous emulsion of (A) (meth) acrylic copolymer resin having a solid content of 45%.

((Meth) acrylic copolymer resin aqueous emulsion production examples B to L)
The same reaction as in Production Example A of (meth) acrylic copolymer resin aqueous emulsion was carried out except that the monomer composition was changed to the formulation shown in Table 1.

Example 1
8. 120 parts (meth) acrylic copolymer resin aqueous emulsion obtained in Production Example A, 2.8 parts adipic acid dihydrazide (ADH), urethane thickener (Primal SCT-275: manufactured by Rohm and Haas) 0 parts, 6.0 parts of butyl carbitol, 1.5 parts of silicone wetting agent (FZ-77: manufactured by Toray Dow Corning), 160.7 parts of deionized water, and an aqueous surface with a solid content of 20% A treating agent was obtained.

(Example 2)
Production Example A of Example 1 (Meth) acrylic copolymer resin aqueous emulsion obtained in Production Example B 122.0 parts, ADH 1.9 parts, deionized water 159.5 parts 1 was used to obtain an aqueous treatment agent.

(Example 3)
Production Example A of Example 1 (Meth) acrylic copolymer resin aqueous emulsion obtained in Production Example B 114.0 parts, ADH 5.5 parts, deionized water 164.0 parts 1 was used to obtain an aqueous treatment agent.

Example 4
Production Example A of Example 1 (meth) acrylic copolymer resin aqueous emulsion obtained in Production Example C 114.7 parts, ADH 5.3 parts, deionized water 163.5 parts 1 was used to obtain an aqueous treatment agent.

(Comparative Examples 1-6)
Production Example A of Example 1 (meth) acrylic copolymer resin aqueous emulsion obtained in Production Examples D to G and I to J, 118.0 parts, ADH 3.8 parts, deionized water 161.7 parts An aqueous treatment agent was obtained in the same manner as in Example 1 except for the change. Since Production Example H and Production Example L could not be polymerized normally, they were excluded from the evaluation.

(Comparative Example 7)
Production Example A Example 1 A (meth) acrylic copolymer resin aqueous emulsion obtained in Production Example K 126.7 parts, no ADH, and changed to 156.8 parts deionized water and Example 1 An aqueous treatment agent was obtained in the same manner.

(Comparative Example 8)
Production Example A of Example 1 (Meth) acrylic copolymer resin aqueous emulsion obtained in Production Example B, except for 125.3 parts, ADH 0.4 parts, deionized water 157.8 parts Example 1 was used to obtain an aqueous treatment agent.

(Comparative Example 9)
Production Example A of Example 1 (Meth) acrylic copolymer resin aqueous emulsion obtained in Production Example B, except that 107.3 parts, ADH 8.7 parts, and deionized water 167.5 parts were used. 1 was used to obtain an aqueous treatment agent.

(Application method)
The aqueous treatment agent was applied to a vinyl chloride sheet with a 150 mesh gravure coater and dried at 50 ° C. for 30 seconds to form a film.

(Polymerization stability)
After emulsion polymerization of Production Examples A to L, the mixture was filtered through nylon 200 mesh, and the aggregate was visually confirmed.
○: No agglomerate △: Slightly agglomerate x: A large amount of agglomerate generated

(transparency)
Visually determine the transparency of the film formed on the vinyl chloride sheet.
○: Transparent △: Very slightly cloudy ×: Cloudy

(Surface smoothness)
The surface of the film formed on the vinyl chloride sheet is judged by touch.
○: Gently slipping △: No stickiness but not slipping ×: Sticky

(Lubricity between treated surfaces)
Rub surface treated surfaces of vinyl chloride sheet together.
○: Glide with light force △: Glide with slight force ×: Not glide

(Scratch resistance)
The surface-treated vinyl chloride leather was squeezed 1000 times at a load of 1 kg using a Scott-type rice cracker (Toyo Seiki Seisakusho), and the whitening of the film was confirmed visually.
○: No whitening △: Slightly whitening ×: Fully whitened

(Blocking resistance)
A non-surface-treated vinyl chloride sheet is laminated on the film formed on the vinyl chloride sheet, and the load is 7.5 kg / cm ² and held in a constant temperature bath at 60 ° C. for 30 minutes, and then released at room temperature. Cool and measure 180 ° T-peel strength with a tensile tester (Tensilon Universal Tester RTE-1210: manufactured by Orientec Corp.).
○: Peel strength 0.3 kg / 2.5 cm or less Δ: Peel strength 0.6 to 1.0 kg / 2.5 cm
X: Peel strength 1.0 kg / 2.5 cm or more

(Abrasion resistance)
The film formed on the PET film coated with an aqueous primer was reciprocated with a cotton cloth using a dyeing friction fastness tester (model 428 manufactured by Yasuda Seiki Co., Ltd.) for 200 cycles and checked for the presence or absence of damage or damage to the film. Check visually.
○: No damage or breakage △: The surface of the film is damaged ×: The film reaches the substrate

(Anti-fouling property for food)
About 2 g of curry or tabasco is placed on the film formed on the vinyl chloride sheet, left at room temperature for 8 hours, wiped with a neutral detergent, and visually confirmed for adhesion of dirt.
○: Dirt hardly adheres.
Δ: Dirt adheres thinly.
X: Dirt adheres thickly.

(Anti-fouling property against outdoor dirt)
The surface-treated vinyl chloride tarpaulin is mixed with carbon, machine oil, humus and the like and placed in an artificially prepared dirt compound, kept at 80 ° C. for 1 hour, washed with water and visually checked for dirt adhesion.
The performance evaluation results of Examples 1 to 4 and Production Examples 1 to 9 are shown in Table 2.

As is clear from the results in Tables 1 and 2, the coatings obtained from the aqueous surface treating agents of Examples 1 to 4 were all good.
On the other hand, when the methyl methacrylate content in the (meth) acrylic copolymer aqueous emulsion is high as in Comparative Example 1, film formation at low temperatures is insufficient and a transparent film is not obtained. On the other hand, when the content of ethyl methacrylate is high as in Comparative Example 2, a soft film is formed, and the blocking resistance, slipperiness and antifouling properties are significantly reduced.
Further, as in Comparative Example 3, the number average molecular weight of the silicone macromonomer having a (meth) acryloyl group at one end is less than 10,000, or as in Comparative Example 4, it has a (meth) acryloyl group at one end. When the silicone macromonomer is not used, the slipperiness of the film is inferior, and the tactile feeling is particularly reduced.

When Comparative Example 5 does not contain a hydroxyl group or when Comparative Example 7 does not take a crosslinked structure, the peel strength increases.
As in Production Examples H, J, and L, a silicone macromonomer having a (meth) acryloyl group at one end, a hydroxyl group-containing ethylenically unsaturated monomer, a carbonyl group-containing ethylenic unsaturated group derived from a keto group or an aldehyde group When the amount of the monomer is large, the polymerization stability is inferior, and polymerization cannot be performed or a large amount of aggregates are generated.
As in Comparative Example 8, when the amount of the hydrazine derivative is small, a sufficient crosslinked structure cannot be obtained, and the slipperiness and blocking resistance are lowered. On the contrary, if the amount of the hydrazine derivative is excessive as in Comparative Example 9, the antifouling property, particularly the contamination with curry, is remarkable even if the lubricity is good.

  The present invention is a one-component cross-linking aqueous surface treatment that can protect a surface of a synthetic resin sheet, leather, tarpaulin, and molded product, and can form a film that imparts slipperiness, wear resistance, and antifouling properties at a low temperature. It can be preferably used as an agent composition.

Claims (3)

(A) (a) 20-80 parts by weight of methyl methacrylate,
(b) 0.1 to 5 parts by weight of a silicone macromonomer having a (meth) acryloyl group at one end and having a number average molecular weight of 20,000 to 30,000,
(c) 1 to 10 parts by weight of an ethylenically unsaturated monomer having a hydroxyl group,
(d) 1 to 10 parts by weight of an ethylenically unsaturated monomer having a carbonyl group derived from a keto group or an aldehyde group;
(e) A (meth) acrylic copolymer obtained by copolymerizing 17.9 to 55.0 parts by weight of one or more ethylenically unsaturated monomers selected from acrylic acid, methacrylic acid and ethyl acrylate An aqueous emulsion of a copolymer resin and (B) a hydrazine derivative having at least two hydrazino groups per molecule is 1 per 100 parts by weight of resin solid content of the aqueous emulsion of (A) (meth) acrylic copolymer resin. vinyl chloride resin product for aqueous surface treating agent composition characterized by being 10 parts by weight.   (B) The content of the hydrazine derivative having at least two hydrazino groups per molecule is 0.2 to 2 mol with respect to 1 mol of the carbonyl group derived from the keto group or aldehyde group of the component (d). The aqueous surface treating agent composition according to claim 1, wherein   A resin product, wherein a film is formed on the surface using the aqueous surface treating agent composition according to claim 1 or 2.