JP6036111B2 - Aqueous surface treatment agent and article using the same - Google Patents

Description

  The present invention relates to an aqueous surface treating agent capable of imparting various design properties to the surface of various articles and a molded 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. Therefore, the surface treatment agent is being made water-based (see, for example, Patent Documents 1 and 2).

  However, the aqueous surface treatment agent is inferior in chemical resistance, particularly solvent resistance, compared to the solvent-based surface treatment agent, and the surface of the aqueous surface treatment agent is wiped with a cleaning agent containing a solvent such as alcohol. There was a problem that the wiped-out traces were noticeable.

  Therefore, there has been a demand for an aqueous surface treatment agent that does not show noticeable marks even when the surface of the coating film comes into contact with a solvent.

JP 2003-342549 A JP 2006-176615 A

  The problem to be solved by the present invention is to impart various design properties to the surfaces of various articles, and even when the surface of the coating film comes into contact with a solvent, the marks (hereinafter abbreviated as “solvent marks”) are conspicuous. It is to provide a non-aqueous surface treatment agent and an article using the same.

  As a result of intensive studies to solve the above problems, the present inventors have found that an aqueous polyurethane having a carboxyl group and / or a hydroxyl group, a polyolefin wax having a specific melting range, and an aqueous surface treating agent containing a crosslinking agent are: The present invention was completed by finding that various design properties can be imparted to the surface of an article, and that solvent marks are not noticeable even when the coating film surface is in contact with a solvent.

That is, the present invention is an aqueous surface treatment agent containing an aqueous polyurethane (A) having a carboxyl group and / or a hydroxyl group, a polyolefin wax (B) having a melting range of 140 to 180 ° C., and a crosslinking agent (C). The polyolefin wax (B) is a polypropylene wax, and relates to an aqueous surface treatment agent and an article using the same.

  The aqueous surface treating agent of the present invention can be used as a surface treating agent for various articles because it can impart various design properties to the surface of the article, and even if the surface of the coating film is in contact with a solvent, solvent traces are not noticeable. . 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 contains an aqueous polyurethane (A) having a carboxyl group and / or a hydroxyl group, a polypropylene wax (B) and a crosslinking agent (C).

  The aqueous polyurethane (A) is a polyurethane having a carboxyl group and / or a hydroxyl group, and can be dispersed in an aqueous medium. 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.

Polypropylene wax is used as the polyolefin wax (B) . Further, the melting range is the 140 to 180 ° C., more preferably 145-175 ° C., more preferably 150-170 ° C.. Such polyolefin wax (B ) can be used alone or in combination of two or more. In the present invention, when two or more kinds of polyolefin waxes (B) 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.

As the polyolefin wax (B), the use of polypropylene wax, preferred since it can reduce the solvent traces. Moreover, as the usage-amount of the said polyolefin wax (B), since the reduction effect of a solvent trace and the coating-film intensity | strength can be improved, it is 0.1-0.1 with respect to 100 mass parts of resin parts of the said water-based polyurethane (A). The range of 20 parts by mass is preferable, and the range of 3 to 15 parts by mass is more preferable.

  Examples of the crosslinking agent (C) 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 is preferable from the viewpoint of crosslinking performance and safety. Moreover, these crosslinking agents (C) can be used alone or in combination of two or more. As a usage-amount of the said crosslinking agent (C), the range of 0.5-30 mass parts is preferable with respect to 100 mass parts of resin parts of the said water-based polyurethane (A) from a viewpoint of coating-film strength, 2-25 The range of parts by mass is more preferable.

  When the article containing the above components (A) to (C) among the aqueous surface treating agent of the present invention is applied to an article, a so-called clear paint is formed, and glossiness can be imparted to the surface of the article. In addition to the above components (A) to (C), the matting agent (D) is added to the aqueous surface treating agent of the present invention when it is desired to impart a matte design to the surface of the article. It is preferable to blend in.

  Examples of the matting agent (D) 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 preferable because it has a high scattering effect and a wide adjustment range of gloss value, and a high effect of reducing solvent marks. 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 usage-amount of the said silica particle, since the gloss value from which the desired mat-like design is obtained can be achieved, it is the range of 0.1-40 mass parts with respect to 100 mass parts of resin parts of the said water-based polyurethane (A). Is preferable, and the range of 10 to 30 parts by mass is more preferable.

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

  The matting agent (D) can be used alone or in combination of two or more.

  In addition to the above components (A) to (D), the aqueous surface treatment agent of the present invention includes various surfactants, antifoaming agents, leveling agents, viscoelasticity adjusting agents, antifoaming agents, wetting agents, dispersing agents, Preservatives, film formers, plasticizers, penetrants, fragrances, bactericides, acaricides, fungicides, UV absorbers, antioxidants, antistatic agents, flame retardants, dyes, pigments (eg, titanium white, Bengala, 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
Aqueous polyurethane (“Hydran WLS-210” manufactured by DIC Corporation, polycarbonate-based aqueous polyurethane, non-volatile content 35% by mass) 47.1 parts by mass (16.5 parts by mass as aqueous polyurethane), polypropylene wax (“MICROMATETE” manufactured by Micro Powders) 1213 UVW "; melting range 150 to 156 ° C.) 1.1 parts by mass, crosslinking agent (Nisshinbo Chemical Co., Ltd.“ Carbodilite E-04 ”, carbodiimide type crosslinking agent) 3.5 parts by mass, nonionic surfactant (first "Neugen EA-157" manufactured by Kogyo Seiyaku Co., Ltd.) 0.1 parts by mass, 0.1 parts by mass of a fluorosurfactant ("Megafac F-444" manufactured by DIC Corporation), viscoelasticity modifier (San Nopco Co., Ltd.) "SN thickener 612NC") 0.9 parts by mass and ion-exchanged water 4 4.2 parts by mass were uniformly mixed to obtain an aqueous surface treating agent (1).

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

[Evaluation of solvent resistance]
After 0.05 ml of ethanol was dropped on the surface of the coating film for evaluation obtained above and left as it was for 3 hours, the diameter of the ethanol drop mark was measured. From the measured values obtained, the solvent resistance was evaluated according to the following criteria.
A: The diameter of the dropping mark is less than 25 mm.
X: The diameter of a drop mark is 25 mm or more.

(Examples 2 to 11)
Aqueous surface treatment agents (2) to (11) were obtained in the same manner as in Example 1 according to the formulation composition shown in Table 1 below. In addition, as in Example 1, the obtained aqueous surface treating agent was evaluated for solvent resistance.

(Comparative Examples 1-9)
According to the composition of Table 2 below, aqueous surface treating agents (R1) to (R9) were obtained in the same manner as in Example 1. In addition, as in Example 1, the obtained aqueous surface treating agent was evaluated for solvent resistance.

  Table 1 shows the composition of the aqueous surface treatment agents (1) to (11) of the above Examples 1 to 11 and the evaluation results of the solvent resistance, and the aqueous surface treatment agents (R1) to (R9) of Comparative Examples 1 to 9. Table 2 shows the evaluation results of the composition and solvent resistance.

The detail of each compounding component described in the said Table 1 and 2 is as follows.
"Hydran WLS-210": Polycarbonate water-based polyurethane manufactured by DIC Corporation (non-volatile content 35% by mass)
“ACEMATT TS-100”: silica particles “ACEMATT 3300” manufactured by a dry method manufactured by Evonik Degussa: silica particles “NIPGEL AZ-200” manufactured by a dry method manufactured by Evonik Degussa and subjected to organic treatment on the surface. : Silica particles “ACEMATT EXP-3600” manufactured by a wet method manufactured by Tosoh Silica Co., Ltd .: Silica particles “Art Pearl G-800” manufactured by a wet method manufactured by Evonik Degussa and treated with an organic surface. Cross-linked polymer fine particles “Toughtic ASF-7” manufactured by Negami Kogyo Co., Ltd .: Matting agent “MICROMATETE 1213UVW” based on polyacrylonitrile manufactured by Toyobo Co., Ltd .: Polypropylene wax manufactured by Micro Powders (melting range: 150 to 156) ℃)
“MICROPRO 440W”: Polypropylene wax manufactured by Micro Powders (melting range: 150 to 156 ° C.)
“MPP-620XF”: polyethylene powder manufactured by Micro Powders (melting range: 114 to 116 ° C.)
“CERAFLOUR 998”: PTPF (polytetrafluoroethylene) -modified polyethylene wax (melting range: 113 to 116 ° C.) manufactured by BYK Japan
“Carbodilite E-04”: Carbodiimide type crosslinking agent “Neugen EA-157” manufactured by Nisshinbo Chemical Co., Ltd .: Nonionic surfactant “Megafac F-444” manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: manufactured by DIC Corporation Fluorosurfactant “SN Thickener 612NC”: Viscoelasticity modifier manufactured by San Nopco

  From the results shown in Table 1, the aqueous surface treatment agents (1) to (11) of Examples 1 to 11 which are the aqueous surface treatment agents of the present invention have a diameter of ethanol dropping marks of 9 to 16 mm, which is not so large. Since only a small drop mark remains, it was found that the film has high solvent resistance.

  On the other hand, Comparative Example 1 is an example in which the polyolefin wax (B) having a melting range of 140 to 180 ° C. used in the present invention was not used and no matting agent was used. In Comparative Examples 1 to 4, it was found that the diameter of ethanol drop marks was relatively large at 34 mm, and the solvent resistance was not sufficient.

  On the other hand, Comparative Examples 2 to 5 are examples using silica particles as a matting agent without using the polyolefin wax (B) having a melting range of 140 to 180 ° C. used in the present invention. In Comparative Examples 2 to 5, it was found that the diameter of ethanol dropping marks was as large as 40 to 48 mm, and the solvent resistance was not sufficient.

  Comparative Examples 6 and 7 are examples in which organic beads were used as the matting agent without using the polyolefin wax (B) having a melting range of 140 to 180 ° C. used in the present invention. In Comparative Examples 6 and 7, it was found that the diameter of ethanol drop marks was as large as 46 to 57 mm, and the solvent resistance was not sufficient.

  Comparative Example 8 is an example in which polyethylene wax having a melting range of 114 to 116 ° C. was used instead of the polyolefin wax (B) having a melting range of 140 to 180 ° C. used in the present invention. In Comparative Example 8, it was found that the diameter of the ethanol drop mark was as large as 46 mm, and the solvent resistance was not sufficient.

  Comparative Example 9 is an example in which PTFE-modified polyethylene wax having a melting range of 113 to 116 ° C. was used instead of the polyolefin wax (B) having a melting range of 140 to 180 ° C. used in the present invention. The thing of this comparative example 9 turned out that the diameter of the drop mark of ethanol was as large as 45 mm, and solvent resistance was not enough.

Claims (5)

An aqueous surface treatment agent containing an aqueous polyurethane (A) having a carboxyl group and / or a hydroxyl group, a polyolefin wax (B) having a melting range of 140 to 180 ° C., and a crosslinking agent (C) , wherein the polyolefin wax (B ) Is a polypropylene wax .   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 crosslinking agent (C) is carbodiimide. Furthermore, the aqueous surface treating agent of any one of Claims 1-3 containing a mat agent (D). An article having the coating film of the aqueous surface treating agent according to any one of claims 1 to 4 .