JP2014214199A - Aqueous surface treatment agent and article using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous surface treatment agent which can impart a matte tone to surfaces of various articles, providing a higher-class feeling thereto, has high adhesiveness to a hardly adhesive substrate such as polyolefin, and provides a coating film by one coating, which does not develop cracks and little change in a matte feeling even when fabrication such as drawing is performed, and to provide an article using the same.SOLUTION: Provided is an aqueous surface treatment agent comprising an aqueous polyurethane (A), an acid-modified non-chlorinated polyolefin (B), a matte agent (C), and a crosslinking agent (D). A mass ratio, [(A)/(B)], of the aqueous polyurethane (A) and the acid-modified non-chlorinated polyolefin (B) is in a range of 55/45 to 98/2.

Description

  The present invention relates to an aqueous surface treatment agent capable of giving a matte (matte) surface to various articles and imparting a more luxurious design, and an article using the same.

  Various articles are often coated with a paint on the surface for the purpose of improving design properties and imparting a high-class feeling. For example, the surface of plastic molded products such as housings for home appliances, housings for electronic devices such as personal computers, mobile phones, and smartphones, and interior and exterior materials for automobiles should be given a high-class design. In addition, a surface treatment agent is used. Conventionally, many of these surface treatment agents are solvent-based. However, since a volatile organic compound (hereinafter abbreviated as “VOC”) is generated and the environmental load is large, the amount of VOC emissions can be reduced. Accordingly, the surface treatment agent is being made water-based.

  However, the aqueous surface treatment agent obtained by making the surface treatment agent water-soluble has a problem that adhesion to a plastic molded product is low, and particularly when the plastic molded product is made of polyolefin, this low adhesion is significant.

  Even if the base material is a plastic molded article made of polyolefin, as a method for improving the adhesion, first, as a primer, an aqueous polyurethane resin having a carboxyl group and / or a hydroxyl group in the molecule, and a carboxyl group in the molecule After applying a primary coating agent obtained by blending a non-chlorine water-based polyolefin resin and a matting agent with a crosslinking agent capable of reacting with a functional group in the resin onto a polyolefin substrate. As a finish, a secondary coating obtained by blending an aqueous polyurethane resin having a carboxyl group and / or a hydroxyl group in the molecule and a matting agent with a crosslinking agent capable of reacting with the functional group in the resin. There has been proposed a method of applying an agent on the coating film of the primary coating agent (see, for example, Patent Document 1). However, this method has a problem that the primer and the finishing agent need to be applied twice. Further, the coating film formed by this method on a film or sheet-like polyolefin substrate has a problem that the coating film surface is cracked when a molding process such as stretching is performed.

  Therefore, a coating film that has high adhesion to difficult-to-adhere substrates such as polyolefin, and that does not cause cracking and has little change in matte feeling even when subjected to molding processing such as stretching is applied once. There has been a demand for an aqueous surface treating agent obtained in the above.

JP 2006-176615 A

  The problem to be solved by the present invention is that the surface of various articles has a matte tone, can give a higher-class design, and has high adhesion to difficult-to-adhere substrates such as polyolefins. By providing a water-based surface treatment agent that can be obtained by a single coating, and an article using the coating film, in which a coating film that does not cause cracking and has little change in matte feeling even when subjected to a molding process such as stretching is provided. is there.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that an aqueous surface treatment agent that uses an aqueous polyurethane and an acid-modified non-chlorinated polyolefin in combination at a specific ratio makes the surface of various articles matte. In addition to being able to impart a more luxurious design, it also has high adhesion to difficult-to-adhere substrates such as polyolefins, and does not crack even when subjected to molding processing such as stretching The present inventors have found that a coating film with little change in mat feeling can be obtained by one coating.

  That is, the present invention is an aqueous surface treating agent containing an aqueous polyurethane (A), an acid-modified non-chlorinated polyolefin (B), a matting agent (C) and a crosslinking agent (D), the aqueous polyurethane (A) Aqueous surface treatment agent characterized in that the mass ratio [(A) / (B)] of the non-chlorinated polyolefin (B) to the acid-modified non-chlorinated polyolefin (B) is in the range of 55/45 to 98/2, and the same It relates to goods.

  The aqueous surface treating agent of the present invention has a matte tone on the surface of various articles, can give a higher-grade design, and has high adhesion to difficult-to-adhere substrates such as polyolefins. However, even if a molding process such as stretching is performed, a coating film that does not cause cracking and has little change in mat feeling can be obtained by a single coating, so that it can be used as a treating agent on the surface of various articles. In particular, it can be suitably used for plastic molded products, and among plastic molded products, it is suitably used for TPO leather and TPO sheets which are molded products of thermoplastic olefin (hereinafter abbreviated as “TPO”). be able to.

  The aqueous surface treating agent of the present invention is an aqueous surface treating agent containing an aqueous polyurethane (A), an acid-modified non-chlorinated polyolefin (B), a matting agent (C) and a crosslinking agent (D), and the aqueous polyurethane The mass ratio [(A) / (B)] of (A) and acid-modified non-chlorinated polyolefin (B) is in the range of 55/45 to 98/2.

  The aqueous polyurethane (A) may be any polyurethane that can be dissolved or dispersed in an aqueous medium, and among them, a polyurethane having a carboxyl group and / or a hydroxyl group is preferable. Among these aqueous polyurethanes (A), examples of the method for producing a polyurethane having a hydroxyl group include a method of reacting an excess amount of polyol and / or glycol with polyisocyanate to obtain a polyurethane having a hydroxyl group at the terminal, an isocyanate group terminal And a method of obtaining a polyurethane having a hydroxyl group by reacting 2-urethane prepolymer with amino alcohol such as 2-aminoethanol, 2-aminoethylethanolamine and diethanolamine, aminophenol and the like. On the other hand, examples of the method for producing a polyurethane having a carboxyl group include a method of using a compound having a carboxyl group as a raw material in the urethanization reaction.

  Examples of the polyol used as a raw material for the aqueous polyurethane (A) include polyester polyols, polyether polyols, polycarbonate polyols, polyacetal polyols, polyacrylate polyols, polyester amide polyols, polythioether polyols, and polybutadiene polyols such as polybutadiene. It is done. Among these, polycarbonate polyol is preferable because of its excellent durability. Moreover, as a compound which has a carboxyl group used as a raw material of the polyurethane which has a carboxyl group, 2,2'- dimethylol propionic acid, 2,2'- dimethylol butanoic acid, 2,2'- dimethylol butyric acid, 2 2,2'-dimethylol valeric acid and the like. Among these, 2,2'-dimethylolpropionic acid is preferable.

  Among the water-based polyurethanes (A) obtained by the above production method, a polycarbonate-based water-based polyurethane using a polycarbonate polyol as a raw material is preferable because of high coating film strength. Moreover, the said water-based polyurethane (A) can be used individually or can be used together 2 or more types.

  The acid-modified non-chlorinated polyolefin (B) is obtained by acid-modifying polyolefin without chlorination. The polyolefin is obtained by polymerizing an olefin compound. Examples of the olefin compound include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 1-nonene. Things can be used. These olefin compounds may be used alone or in combination of two or more. The polyolefin (B) may be a homopolymer or a copolymer.

  Examples of the polyolefin used as a raw material for the polyolefin (B) include polyethylene, polypropylene, polybutadiene, ethylene-propylene copolymer, natural rubber, synthetic isopropylene rubber, and ethylene-vinyl acetate copolymer. When the polyolefin (B) is a copolymer, it may be a random copolymer or a block copolymer.

  The polyolefin (B) is obtained by acid-modifying the polyolefin exemplified above, and the acid modification is preferably a method of reacting with polyolefin using an unsaturated carboxylic acid or an anhydride thereof. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, aconitic acid, crotonic acid and the like, and anhydrides thereof. . Moreover, the half ester, half amide, etc. of unsaturated carboxylic acid are mentioned. Among these unsaturated carboxylic acids, it is preferable to use acrylic acid, methacrylic acid, maleic acid or maleic anhydride.

  The acid modification of the polyolefin can be performed, for example, by mixing a polyolefin dissolved in an organic solvent and an unsaturated carboxylic acid and reacting by heating at a temperature equal to or higher than the softening temperature or melting point of the polyolefin.

  The mass ratio [(A) / (B)] of the aqueous polyurethane (A) and the acid-modified non-chlorinated polyolefin (B) is in the range of 55/45 to 98/2. Within this range, it is possible to achieve both molding processability that does not decrease the mat feeling and high adhesion to the base material, but when the ratio of the aqueous polyurethane (A) is less than 55% by mass, molding process such as stretching can be performed. There exists a problem which produces a crack in the coating-film surface, and when the ratio of aqueous polyurethane (A) exceeds 98 mass%, there exists a problem that adhesiveness with difficult-to-adhere base materials, such as polyolefin, becomes inadequate. Furthermore, in order to improve moldability and adhesion at a higher level, the mass ratio [(A) / (B)] is preferably in the range of 60/40 to 98/2, and 70/30 to 97 / A range of 3 is more preferred.

  Examples of the matting agent (C) include silica particles, organic beads, calcium carbonate, magnesium carbonate, barium carbonate, talc, aluminum hydroxide, calcium sulfate, kaolin, mica, asbestos, mica, calcium silicate, alumina silicate, and the like. Is mentioned.

  Examples of the silica particles include dry silica and wet silica. Among these, dry silica is preferred because of its high scattering effect and wide gloss value adjustment range. Moreover, since it becomes easy to disperse | distribute in a composition, the dry-type silica surface-modified with the organic compound is more preferable. The average particle diameter of these silica particles is preferably in the range of 2 to 14 μm, more preferably in the range of 3 to 12 μm.

  As the amount of the silica particles used, since a gloss value that provides a desired matte design can be achieved, the total resin content of the aqueous polyurethane (A) and the acid-modified non-chlorinated polyolefin (B) is 100 parts by mass. And the range of 0.1-40 mass parts is preferable, and the range of 3-30 mass parts is more preferable.

  Examples of the organic beads include acrylic beads, urethane beads, silicon beads, and olefin beads.

  Said mat agent (C) can be used individually or can be used together 2 or more types.

  Examples of the crosslinking agent (D) include urea resin-based crosslinking agents such as oxazoline, carbodiimide, polyisocyanate, blocked isocyanate, epoxy, polysiloxane, aziridine, and alkylated melamine, and hydrazide-based crosslinking agents. Among these, carbodiimide and polyisocyanate are preferable from the viewpoint of crosslinking performance and safety. Moreover, these crosslinking agents (D) can be used alone or in combination of two or more. As the usage-amount of the said crosslinking agent (D), from a viewpoint of coating-film strength, it is 0.5 ~ with respect to 100 mass parts of total resin content of the said water-based polyurethane (A) and acid-modified non-chlorinated polyolefin (B). The range of 30 parts by mass is preferable, and the range of 1 to 25 parts by mass is more preferable.

  In addition to the aqueous polyurethane (A), acid-modified non-chlorinated polyolefin (B), matting agent (C) and crosslinking agent (D), the aqueous wax surface treatment agent of the present invention is blended with a polyolefin wax (E). be able to.

  Among the polyolefin waxes (E), even when a solvent such as alcohol comes into contact with the coating film, the trace (solvent trace) is hardly left and the solvent resistance is improved, so the melting range is 140 to 180 ° C. A thing of 145-175 degreeC is more preferable, and what is 150-170 degreeC is further more preferable. Examples of such polyolefin wax (E) include polyethylene wax and polypropylene wax. These polyolefin waxes (E) can be used alone or in combination of two or more. In the present invention, when two or more kinds of polyolefin waxes (E) are used in combination, the melting range is the melting range in the mixture. The melting range is measured in accordance with JIS test method K0064-1992.

  Among the above-mentioned polyolefin waxes (E), those having polypropylene wax as a main component are preferable because solvent traces can be reduced. Further, the amount of the polyolefin wax (E) used is that the effect of reducing solvent marks and the strength of the coating film can be increased, so the total resin content of the aqueous polyurethane (A) and the acid-modified non-chlorinated polyolefin (B). The range of 0.1-20 mass parts is preferable with respect to 100 mass parts, and the range of 3-15 mass parts is more preferable.

  In addition to the above components (A) to (E), the aqueous surface treating agent of the present invention includes various surfactants, antifoaming agents, leveling agents, viscoelasticity adjusting agents, wetting agents, dispersing agents, preservatives, and membranes. Forming agents, plasticizers, penetrants, fragrances, fungicides, acaricides, fungicides, UV absorbers, antioxidants, antistatic agents, flame retardants, dyes, pigments (eg titanium white, bengara, phthalocyanine, Carbon black, permanent yellow, etc.) may be added.

  The article of the present invention has a coating film of the aqueous surface treating agent of the present invention. In addition, examples of articles include housings for home appliances (refrigerators, washing machines, air conditioners, televisions, etc.), housings for electronic devices (computers, mobile phones, smartphones, etc.), musical instruments (pianos, electric tones, electronic musical instruments, etc.) Materials: Interior materials for automobiles or railway vehicles (instrument panels, door trims, headlinings, tonneau covers, etc.), building materials or furniture materials (wallpaper, decorative sheets for plywood, decorative sheets for steel plates, leather for chairs, etc.), Examples include plastic molded products such as packaging materials (such as wrapping films); wood materials (plywood, laminated materials, single-layer laminated materials, etc.); and ceramic materials (interior tiles, bricks, etc.). Sport (ski, archery, golf, tennis, etc.) equipment materials; footwear materials (shoe upper, bottom, core material, heel, top lift, insole, etc.); metal materials (iron, copper, zinc, aluminum, etc.), etc. Is mentioned. Among these articles, the aqueous surface treating agent of the present invention can be suitably used for plastic molded products, and among these plastic molded products, it is preferable to use them for TPO leather and TPO sheets.

  Hereinafter, the present invention will be described specifically by way of examples.

Example 1
37 parts by mass (12.95 parts by mass as a resin of the aqueous polyurethane), acid-modified non-chlorinated polyolefin (Starlight), water-based polyurethane (“Hydran WLS-210” manufactured by DIC Corporation, polycarbonate-based aqueous polyurethane, nonvolatile content: 35% by mass) "VE-1217" manufactured by PMC Corporation, nonvolatile content: 31.4 mass%) 10.3 parts by mass (3.23 parts by mass as a resin of acid-modified non-chlorinated polyolefin), cross-linking agent (manufactured by Nisshinbo Chemical Co., Ltd. Carbodilite E-04 ", carbodiimide-based crosslinking agent) 2.6 parts by mass, matting agent (" ACEMATT 3300 "manufactured by Evonik Degussa), silica particles produced by a dry process and organically treated on the surface, average particle size: 9.5 m ) 2.2 parts by mass, polypropylene wax (“MICROMAT” manufactured by Micro Powders) E 1213UVW "; melting range 150 to 156 ° C) 1 part by mass, nonionic surfactant (Daiichi Kogyo Seiyaku" Neugen EA-157 ") 0.1 part by mass, fluorosurfactant (DIC Corporation) "Megafac F-444") 0.1 parts by mass, viscoelasticity modifier ("SN thickener 612NC" manufactured by San Nopco Co., Ltd.) 0.7 parts by mass and 46 parts by mass of ion-exchanged water are uniformly mixed to form an aqueous solution. A surface treating agent (1) was obtained.

[Preparation of sample for evaluation]
The aqueous surface treating agent (1) obtained above was converted into a bar coater No. 14 was applied onto a TPO sheet (thickness 0.4 mm) and then dried at 120 ° C. for 1 minute to obtain an evaluation sample.

[Production of vacuum formed products]
Using the vacuum forming machine (“Vacuum Forming Machine Forming 300X” manufactured by Seiko Sangyo Co., Ltd.), the evaluation sample obtained above is vacuum-formed so that the area ratio is 150% and 250%. I got a product.

[Measure gloss value]
About the coating film surface of the aqueous surface treating agent of the sample for evaluation obtained above, the 60 ° gloss value of the vacuum molded product of 250% before vacuum molding and area ratio was measured with a gloss meter (manufactured by Konica Minolta Optics, Inc. GM-268Plus "). Moreover, the change rate of the 60 degree gloss value of the coating film surface of the aqueous surface treating agent before and after vacuum forming was calculated by the following formula (1).

[Evaluation of moldability]
The surface of the aqueous surface treatment agent coating film of the vacuum molded product having the area ratio obtained above of 250% was visually observed, and the molding processability was evaluated according to the following criteria.
○: No crack on the coating film surface.
X: There is a crack on the coating film surface.

[Measurement of peel strength]
A hot-melt tape ("Polyco Tape No.6000" manufactured by Okuda Sangyo Co., Ltd.) is applied to the surface of the water-based surface treatment agent coating film of a vacuum molded product having a surface ratio of 150% obtained as described above. Using a dedicated press machine, thermocompression bonding was performed at 180 ° C. and 16 kPa for 1 minute to obtain a test piece having a width of 15 mm. Peel strength of hot melt tape and TPO sheet is measured at a tensile rate of 100 mm / min using an A & D Co., Ltd. “Tensilon Universal Testing Machine RTC Series” at an ambient humidity of 50% and an ambient temperature of 23 ° C. It was measured.

[Evaluation of adhesion]
From the measured value of the peel strength measured above, the adhesion was evaluated according to the following criteria.
○: Peel strength is 10 N / 15 mm or more.
X: Peel strength is less than 10 N / 15 mm.

(Example 2)
The acid-modified non-chlorinated polyolefin used in Example 1 was converted to acid-modified non-chlorinated polyolefin (Nippon Paper Co., Ltd. “Aurolen AE-301”, nonvolatile content: 30 mass%) 10.8 parts by mass (acid-modified non-chlorinated polyolefin). The aqueous surface treating agent (2) was obtained in the same manner as in Example 1 except that the amount of ion-exchanged water was changed to 45.5 parts by mass to 3.24 parts by mass as a chlorinated polyolefin resin.

Example 3
15.9 parts by weight of the acid-modified non-chlorinated polyolefin used in Example 1 (acid-modified non-chlorinated polyolefin ("Arrobase SD-1010" manufactured by Unitika Ltd., nonvolatile content: 20.5% by mass)) A water-based surface treating agent (3) was obtained in the same manner as in Example 1 except that the amount of non-chlorinated polyolefin resin was changed to 3.26 parts by mass) and the amount of ion-exchanged water was changed to 40.4 parts by mass. .

Example 4
15.9 parts by weight of the acid-modified non-chlorinated polyolefin used in Example 1 (acid-modified non-chlorinated polyolefin (“Arrobase SE-1200” manufactured by Unitika Ltd., nonvolatile content: 20.2% by mass)) A water-based surface treating agent (4) was obtained in the same manner as in Example 1 except that the amount of ion-exchanged water was changed to 40.4 parts by mass to 3.21 parts by mass as a non-chlorinated polyolefin resin. .

(Example 5)
A cross-linking agent obtained by previously mixing and emulsifying the cross-linking agent used in Example 4 in 1.0 part by mass of ion-exchanged water (“LCC WL FIXER UX-10” manufactured by DIC Corporation, water-emulsifiable polyisocyanate-based cross-linking agent) Except having changed to 6 mass parts and having changed the compounding quantity of ion-exchange water into 41.4 mass parts, it carried out similarly to Example 1 and obtained the aqueous surface treating agent (5).

(Example 6)
The amount of the aqueous polyurethane used in Example 1 was changed to 43.9 parts by mass (15.37 parts by mass as an aqueous polyurethane resin), and the acid-modified non-chlorinated polyolefin was changed to acid-modified non-chlorinated polyolefin (Unitika Co., Ltd.). “Arrow Base SE-1200” (non-volatile content: 20.2% by mass) manufactured by the company was changed to 4 parts by mass (0.81 parts by mass as a resin of acid-modified non-chlorinated polyolefin), and the amount of ion-exchanged water was 45 Except having changed to 4 parts by mass, the same procedure as in Example 1 was carried out to obtain an aqueous surface treating agent (6).

(Example 7)
The amount of the aqueous polyurethane used in Example 1 was changed to 27.7 parts by mass (9.7 parts by mass as a resin of the aqueous polyurethane), and the acid-modified non-chlorinated polyolefin was changed to acid-modified non-chlorinated polyolefin (Unitika Co., Ltd.). Company “Arrow Base SE-1200”, nonvolatile content: 20.2 mass%) changed to 32 parts by mass (6.46 parts by mass as acid-modified non-chlorinated polyolefin resin), and the amount of ion-exchanged water was 33 Except having changed to .6 mass parts, it carried out similarly to Example 1 and obtained the aqueous surface treating agent (7).

(Comparative Example 1)
Aqueous polyurethane (“Hydran WLS-210” manufactured by DIC Corporation, polycarbonate-based aqueous polyurethane, nonvolatile content: 35% by mass) 46.1 parts by mass (21.3 parts by mass as aqueous polyurethane), cross-linking agent (manufactured by Nisshinbo Chemical Co., Ltd.) 2.6 parts by mass of “carbodilite E-04”, carbodiimide-based crosslinking agent), matting agent (“ACEMATT 3300” manufactured by Evonik Degussa), silica particles produced by a dry method and subjected to organic treatment on the surface, average particle size: 9. 5 parts by weight, polypropylene wax (“MICROMATETE 1213UVW” manufactured by Micro Powders, 1 150 parts by melting range), nonionic surfactant (“Neugen EA-157” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) ) 0.1 parts by mass, fluorosurfactant (DIC stock) Co., Ltd. “MegaFuck F-444”) 0.1 part by mass, viscoelasticity modifier (“SN thickener 612NC” by San Nopco Co., Ltd.) 0.7 part by mass and ion-exchanged water 47.2 parts by mass were mixed uniformly. Thus, an aqueous surface treating agent (R1) was obtained.

(Comparative Example 2)
The amount of the aqueous polyurethane used in Example 7 was changed to 18.5 parts by mass (6.48 parts by mass as a resin of the aqueous polyurethane), and the amount of the acid-modified non-chlorinated polyolefin was changed to 48.1 parts by mass (acid The modified non-chlorinated polyolefin resin was changed to 9.71 parts by mass), and the same procedure as in Example 7 was carried out except that the amount of ion-exchanged water was changed to 26.7 parts by mass. Got.

  About the aqueous surface treating agents (2) to (7) and (R1) to (R2) obtained in Examples 2 to 7 and Comparative Examples 1 and 2, the 60 ° gloss value was measured in the same manner as in Example 1. The moldability was evaluated, the peel strength was measured, and the adhesion was evaluated.

  Compositions of aqueous surface treatment agents (1) to (7) and (R1) to (R2) obtained in Examples 1 to 7 and Comparative Examples 1 to 2, 60 ° gloss value, moldability, peeling Table 1 shows the measurement results and evaluation results of strength and adhesion.

  From the results shown in Table 1, the aqueous surface treatment agents (1) to (7) of Examples 1 to 7 which are the aqueous surface treatment agents of the present invention have a change rate of 60 ° gloss value of 62% or less in absolute value. It was found that there was little change in gloss value. Further, it was found that even if stretch molding was performed, the surface of the coating film was not cracked and the moldability was good. Furthermore, it was found that the peel strength is as high as 13.4 N / 15 mm or more and has sufficiently high adhesion to the TPO sheet.

  On the other hand, Comparative Example 1 is an example in which the acid-modified non-chlorinated polyolefin (B) was not blended. In Comparative Example 1, it was found that there was a problem that the change rate of the 60 ° gloss value before and after vacuum molding was 116% and the change was large. It was also found that the peel strength was 1.6 N / 15 mm and the adhesion to the TPO sheet was very low.

  In Comparative Example 2, the mass ratio [(A) / (B)] of the aqueous polyurethane (A) and the acid-modified non-chlorinated polyolefin (B) is outside the range of 55/45 to 98/2 (A). / (B) = 40/60. In Comparative Example 2, it was found that there was a problem that the change rate of the 60 ° gloss value before and after vacuum forming was as large as -72%. Moreover, although the adhesiveness with respect to a TPO sheet | seat was favorable, it also turned out that there exists a problem which produces a crack on the coating-film surface by an extending | stretching molding process.

Claims (6)

  An aqueous surface treating agent comprising an aqueous polyurethane (A), an acid-modified non-chlorinated polyolefin (B), a matting agent (C) and a crosslinking agent (D), the aqueous polyurethane (A) and acid-modified non-chlorinated An aqueous surface treating agent, wherein the mass ratio [(A) / (B)] to the polyolefin (B) is in the range of 55/45 to 98/2.   The aqueous surface treating agent according to claim 1, wherein the aqueous polyurethane (A) is a polycarbonate-based aqueous polyurethane.   The aqueous surface treating agent according to claim 1 or 2, wherein the acid-modified non-chlorinated polyolefin (B) is a non-chlorinated polyolefin modified with an unsaturated carboxylic acid or an anhydride thereof.   The aqueous surface treating agent according to any one of claims 1 to 3, wherein the crosslinking agent (D) is carbodiimide or polyisocyanate.   Furthermore, the aqueous surface treating agent of any one of Claims 1-4 containing polyolefin wax (E).   An article having a coating film of the aqueous surface treating agent according to any one of claims 1 to 5.