JP4030754B2 - Plating resin molding - Google Patents

Description

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【表２】

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【表３】

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【表５】

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表１〜表６より明らかなとおり、樹脂成形体中に水溶性物質を配合することで、メッキ層の密着強度が飛躍的に向上された。
【００５０】
【発明の効果】
本発明のメッキ樹脂成形体は、クロム酸等の重金属を含む酸によるエッチング処理を経ていないが、高い密着強度のメッキ層を有している。また、クロム酸等の重金属を含む酸によるエッチング処理をしないので、廃水処理が容易であり、重金属による環境汚染がない。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a plated resin molded body having high plating strength and a method for producing a plated resin molded body that does not require an etching process.
[0002]
[Prior art and problems to be solved by the invention]
For the purpose of reducing the weight of automobiles, resin molded bodies such as ABS resin and polyamide resin are used as automobile parts. To give this resin molded body a high-class feeling and aesthetics, copper, nickel, etc. are plated. ing.
[0003]
Conventionally, when plating a molded body such as an ABS resin, an etching process for roughening the resin molded body after the degreasing process is essential in order to increase the adhesion strength between the resin molded body and the plating layer. For example, when plating an ABS resin molded body or a polypropylene molded body, it is necessary to perform an etching treatment at 65 to 70 ° C. for 10 to 15 minutes using a chromic acid bath (mixed solution of chromium trioxide and sulfuric acid) after the degreasing treatment. Yes, wastewater contains toxic hexavalent chromate ions. For this reason, the process of neutralizing and precipitating the hexavalent chromate ions after reducing them to trivalent ions is essential, and there is a problem during wastewater treatment.
[0004]
In this way, in consideration of safety during work at the site and the environmental impact of wastewater, it is desirable not to perform etching using a chromium bath, but in that case, to a molded body obtained from ABS resin, etc. There is a problem that the adhesion strength of the plating layer cannot be increased.
[0005]
The present invention provides a plated resin molded body having a high adhesion strength between the resin molded body and the plating layer and having a beautiful appearance, and a method for producing the plated resin molded body that can eliminate the etching treatment with chromic acid or the like. This is the issue.
[0006]
[Means for Solving the Problems]
The inventor of the present invention blends a water-soluble substance and, if necessary, a surfactant into a thermoplastic resin into a resin molded body, so that even without an etching treatment with an acid containing a heavy metal such as chromic acid. It has been found that the adhesion strength between the resin molded body and the plating layer can be dramatically increased, and the present invention has been completed.
[0007]
The present invention is a plating resin molded body having a metal plating layer on the surface of a resin molded body containing a thermoplastic resin and a water-soluble substance, as a means for solving the above-mentioned problems, and the resin molded body is etched with an acid containing a heavy metal. Provided is a plated resin molded article that has not been damaged.
[0008]
Moreover, this invention has the process of degreasing the resin molding containing a thermoplastic resin and a water-soluble substance, and the electroless-plating process as another solution means of the said subject, and is based on the acid containing a heavy metal. Provided is a method for producing a plated resin molded body that does not include an etching step.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The plated resin molded article of the present invention is a plated resin molded article having a metal plating layer on the surface of a resin molded article containing a thermoplastic resin and a water-soluble substance, and the resin molded article is an acid containing a heavy metal such as chromic acid. Etching process is not performed.
[0010]
The thermoplastic resin can be appropriately selected from known ones according to the use, but in the present invention, a polyamide resin, a styrene resin, an olefin resin, a polyphenylene ether resin (PPE), a polyphenylene sulfone resin (PPS). Polysulfone resin is preferable.
[0011]
The polyamide-based resin is a polyamide resin formed from diamine and dicarboxylic acid and a copolymer thereof. For example, nylon 66, polyhexamethylene sebacamide (nylon 6 · 10), polyhexamethylene dodecanamide (nylon 6 · 12), polydodecamethylene dodecanamide (nylon 1212), polymetaxylylene adipamide (nylon) MXD6), polytetramethylene adipamide (nylon 46) and mixtures and copolymers thereof; nylon 6/66, nylon 66 / 6T in which 6T component is 50 mol% or less (6T: polyhexamethylene terephthalamide) , Copolymers such as nylon 66 / 6I (6I: polyhexamethylene isophthalamide), nylon 6T / 6I / 66, nylon 6T / 6I / 610, etc., wherein the 6I component is 50 mol% or less; polyhexamethylene terephthalamide ( Nylon 6T), polyhexamethylene isophthalamide (nylon 6) ), Poly (2-methylpentamethylene) terephthalamide (nylon M5T), poly (2-methylpentamethylene) isophthalamide (nylon M5I), nylon 6T / 6I, nylon 6T / M5T, and the like. In addition, copolymer nylon such as amorphous nylon may be used, and examples of amorphous nylon include polycondensates of terephthalic acid and trimethylhexamethylenediamine.
[0012]
Further, a ring-opening polymer of cyclic lactam, a polycondensate of aminocarboxylic acid, and a copolymer comprising these components, specifically, nylon 6, poly-ω-undecanamide (nylon 11), poly-ω-dodecanamide. (Nylon 12) and other aliphatic polyamide resins and copolymers thereof, and copolymers with polyamides comprising diamines and dicarboxylic acids, specifically nylon 6T / 6, nylon 6T / 11, nylon 6T / 12, Mention may be made of nylon 6T / 6I / 12, nylon 6T / 6I / 610/12, and mixtures thereof.
[0013]
Among the polyamide-based resins, PA (nylon) 6, PA (nylon) 66, and PA (nylon) 6/66 are preferable among the above.
[0014]
Examples of the styrenic resin include polymers of styrene and styrene derivatives such as α-substituted and nucleus-substituted styrene. Also included are copolymers composed mainly of these monomers and monomers of vinyl compounds such as acrylonitrile, acrylic acid and methacrylic acid and / or conjugated diene compounds such as butadiene and isoprene. For example, polystyrene, high impact polystyrene (HIPS) resin, acrylonitrile-butadiene-styrene copolymer (ABS) resin, acrylonitrile-styrene copolymer (AS resin), styrene-methacrylate copolymer (MS resin), styrene-butadiene A copolymer (SBS resin) etc. can be mentioned.
[0015]
Further, the polystyrene resin may include a styrene copolymer in which a carboxyl group-containing unsaturated compound for increasing compatibility with the polyamide resin is copolymerized. The styrene-based copolymer in which the carboxyl group-containing unsaturated compound is copolymerized in the presence of the rubber-like polymer, the carboxyl group-containing unsaturated compound and, if necessary, other monomers copolymerizable therewith Is a copolymer obtained by polymerizing Specific examples of ingredients include
1) In the presence of a rubbery polymer copolymerized with a carboxyl group-containing unsaturated compound, a monomer containing an aromatic vinyl monomer as an essential component or an aromatic vinyl and a carboxyl group-containing unsaturated compound as an essential component A graft polymer obtained by polymerizing monomers,
2) A graft copolymer obtained by copolymerizing a monomer having an aromatic vinyl and a carboxyl group-containing unsaturated compound as essential components in the presence of a rubbery polymer,
3) a mixture of a rubber-reinforced styrenic resin that is not copolymerized with a carboxyl group-containing unsaturated compound, and a copolymer of monomers that have a carboxyl group-containing unsaturated compound and an aromatic vinyl as essential components;
4) A mixture of the above 1), 2), a copolymer containing an unsaturated compound containing a carboxyl group and an aromatic vinyl,
5) There is a mixture of the above 1), 2), 3), 4) and a copolymer containing aromatic vinyl as an essential component.
[0016]
In the above 1) to 5), styrene is preferable as the aromatic vinyl, and acrylonitrile is preferable as the monomer copolymerized with the aromatic vinyl. The carboxyl group-containing unsaturated compound is preferably 0.1 to 8% by mass, more preferably 0.2 to 7% by mass in the styrene resin.
[0017]
The olefin-based resin is a polymer having a C 2-8 monoolefin as a main monomer component, such as low density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene random copolymer, One or more kinds selected from ethylene-propylene block copolymer, polymethylpentene, polybutene-1, modified products thereof and the like can be exemplified, and among these, polypropylene and acid-modified polypropylene are preferable.
[0018]
Water-soluble substances are polysaccharides such as starch, dextrin, pullulan, hyaluronic acid, carboxymethylcellulose, methylcellulose, ethylcellulose or salts thereof; propylene glycol, ethylene glycol, diethylene glycol, neopentyl glycol, butanediol, pentanediol, polyoxyethylene Polyhydric alcohols such as glycol, polyoxypropylene glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, glycerin; polyvinyl alcohol, polyacrylic acid, polymaleic acid, polyacrylamide, polyvinylpyrrolidone, polyethylene oxide, acrylic acid-maleic anhydride Copolymer, maleic anhydride-diisobutylene copolymer, maleic anhydride-vinyl acetate copolymer , Naphthalene sulfonate formalin condensates and their salts.
[0019]
The content ratio of the thermoplastic resin and the water-soluble substance in the resin molded body is preferably 0.01 to 50 parts by mass, and 0.01 to 30 parts by mass with respect to 100 parts by mass of the thermoplastic resin. More preferably, 0.01-15 mass parts is still more preferable.
[0020]
In order that the plating resin molding of this invention may improve the adhesive strength of a plating layer, what contains surfactant and / or a coagulant in a resin molding is preferable. These surfactants and / or coagulants may be those in which the surfactant (emulsifier) used when emulsion polymerization is applied during the production of the thermoplastic resin remains in the resin, or an emulsifier such as bulk polymerization. When a production method that does not use is applied, it may be separately added to a thermoplastic resin.
[0021]
The surfactant and / or the coagulant may be other than those used in emulsion polymerization in addition to those used in the emulsion polymerization of resins. The surfactant may be an anionic surfactant, a cationic surfactant, or a nonion. An ionic surfactant and an amphoteric surfactant are preferred.
[0022]
These surfactants include fatty acid salts, rosinates, alkyl sulfates, alkyl benzene sulfonates, alkyl diphenyl ether sulfonates, polyoxyethylene alkyl ether sulfates, sulfosuccinic acid diester salts, α-olefin sulfate salts, Anionic surfactants such as α-olefin sulfonates; Cationic surfactants such as mono- or dialkylamines or polyoxyethylene adducts thereof, mono- or di-long alkyl quaternary ammonium salts; alkyl glucosides, polyoxyethylene alkyls Ether, polyoxyethylene alkyl phenyl ether, sucrose fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene propylene butyl ether Nonionic surfactants such as lock copolymers, fatty acid monoglycerides, amine oxides; amphoteric surfactants such as carbobetaine, sulfobetaine, and hydroxysulfobetaine.
[0023]
The content ratio of the surfactant and / or the coagulant in the resin molded body is preferably 0.01 to 10 parts by mass of the surfactant and / or the coagulant with respect to 100 parts by mass of the thermoplastic resin. -5 mass parts is more preferable, and 0.01-2 mass parts is still more preferable.
[0024]
In the plated resin molded body of the present invention, the adhesive strength between the resin molded body and the metal plating layer (JIS H8630) is preferably a maximum value of 10 kPa or more, more preferably a maximum value of 50 kPa or more, and even more preferably a maximum value of 100 kPa. As described above, the maximum value is particularly preferably 150 kPa or more.
[0025]
The shape of the plated resin molded body of the present invention, the type and thickness of the plated layer can be appropriately selected depending on the application, and can be applied to various applications. In particular, bumpers, emblems, wheel caps, interior parts Suitable for automotive parts such as exterior parts.
[0026]
Next, the manufacturing method of the plating resin molding of this invention is demonstrated for every process. The production method of the present invention includes a degreasing process and an electroless plating process, and preferably includes a process of treating with at least a catalyst-imparting solution between the two processes. Ordinary processing steps performed by a trader can be added as appropriate.
[0027]
First, a resin molded body containing a thermoplastic resin, a water-soluble substance, and a surfactant as necessary is degreased. The resin molded body is obtained by molding into a desired shape suitable for the application by a known method such as injection molding.
[0028]
The degreasing treatment is performed with an aqueous surfactant solution containing an alkali such as sodium hydroxide or sodium carbonate or an acid such as sulfuric acid or carbonic acid. In the present invention, after this degreasing treatment, it is possible to shift to an electroless plating step or another step, and etching etching with an acid containing a heavy metal such as chromic acid, which becomes a roughening treatment for increasing the adhesion strength of the plating layer No process is required.
[0029]
After the degreasing treatment, for example, a water washing step, a step of treating with a catalyst application liquid, a water washing step, a step of treating with an activation liquid (activation step) and a water washing step can be performed. In addition, the process with a catalyst provision liquid and the process with an activation liquid can be performed simultaneously.
[0030]
The treatment with the catalyst-imparting solution is, for example, immersed in a 35% hydrochloric acid solution (10-20 mgl ⁻¹ ) of tin chloride (20-40 gl ⁻¹ ) at room temperature for about 1 to 5 minutes. In the treatment with the activation liquid, immersion is carried out in a 35% hydrochloric acid solution (3 to 5 ml ⁻¹ ) of palladium chloride (0.1 to 0.3 gl ⁻¹ ) at room temperature for 1 to 2 minutes.
[0031]
Thereafter, one or more electroless plating steps are performed. As the plating bath, one containing nickel, copper, cobalt, nickel-cobalt alloy, gold and the like and a reducing agent such as formalin and hypophosphite can be used. The pH and temperature of the plating bath are selected according to the type of plating bath used.
[0032]
In the case of further plating after electroless plating, an electroplating step using copper or the like can be added after the activation treatment with acid or alkali.
[0033]
【Example】
Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, the adhesiveness test of the plating layer performed in the Example and the comparative example, and the detail of the used component are as follows.
[0034]
(1) Adhesion test of plating layer Using the plating resin moldings obtained in Examples and Comparative Examples, the adhesion strength between the resin molding and the metal plating layer was determined by the adhesion test method described in JIS H8630 Annex 6. (Maximum value) was measured.
[0035]
(2) Component used [(A) thermoplastic resin]
(A-1): Polyamide 6 (Ube nylon 1013B, manufactured by Ube Industries)
(A-2): Polyamide 66 (Ubenylon 2020B, manufactured by Ube Industries)
(A-3): AS resin (styrene content 75% by mass, acrylonitrile 25% by mass)
(A-4): ABS resin (styrene content 45% by mass, acrylonitrile 15% by mass, rubber content 40% by mass)
(A-5): Acid-modified ABS resin (styrene content 42% by mass, acrylonitrile 16% by mass, rubber content 40% by mass, methacrylic acid 2% by mass)
(A-6): Acid-modified ABS resin (styrene content 40% by mass, acrylonitrile 14% by mass, rubber content 40% by mass, methacrylic acid 6% by mass)
(A-7): Polypropylene resin (J713M, manufactured by Grand Polymer)
(A-8): Acid-modified polypropylene resin (E109H, manufactured by Grand Polymer)
[(B) Water-soluble substance]
(B-1): Dipentaerythritol (Guangei Chemical Industry Co., Ltd.)
(B-2): Pentaerythritol (manufactured by Guangei Chemical Industry Co., Ltd.)
[(C) Surfactant]
(C-1): α-olefin sulfonate: Lipolane PB800 (manufactured by Lion)
(C-2): Potassium rosinate (C-3): Potassium oleate (C-4): Potassium laurate Examples 1 to 88, Comparative Examples 1 to 9
A composition of the combinations and ratios shown in Table 1 (thermoplastic resin is expressed in mass%, other components are expressed in mass parts relative to 100 parts by mass of thermoplastic resin), mixed with a V-type tumbler, and then a twin-screw extruder (Nippon Steel) Manufactured, TEX30, cylinder temperature 230 ° C.) to obtain a pellet. Next, a molded body of 100 × 50 × 3 mm was obtained by an injection molding machine (cylinder temperature 240 ° C., mold temperature 60 ° C.), and electroless plating was performed in the following process sequence using this molded body as a test piece. A resin molded body was obtained. The test results are shown in Table 1.
[0036]
(Manufacturing method of plated resin molding)
{Circle around (1)} Degreasing step: The test piece was immersed in an aceclin A-220 (Okuno Pharmaceutical Co., Ltd.) 50 g / L aqueous solution (liquid temperature 40 ° C.) for 20 minutes.
[0037]
(2) Catalyst application step: The test piece was placed in a mixed aqueous solution (liquid temperature: 25 ° C.) of 35 mass% hydrochloric acid 150 ml / L and catalyst C (Okuno Pharmaceutical Co., Ltd.) 40 ml / L aqueous solution for 3 minutes. Soaked.
[0038]
(3) First activation step: The test piece was immersed in a 98% by mass sulfuric acid 100 ml / L aqueous solution (liquid temperature 40 ° C.) for 3 minutes.
[0039]
(4) Second activation step: The test piece was immersed in a 15 g / L aqueous solution of sodium hydroxide (liquid temperature 40 ° C.) for 2 minutes.
[0040]
(5) Electroless plating process of nickel: The test pieces were chemical nickel HR-TA (Okuno Pharmaceutical Co., Ltd.) 150 ml / L and chemical nickel HR-TB (Okuno Pharmaceutical Co., Ltd.) 150 ml / L Was immersed in a mixed aqueous solution (liquid temperature: 40 ° C.) for 5 minutes.
[0041]
(6) Acid activation step: The test piece was immersed in 100 g / L aqueous solution (liquid temperature 25 ° C.) of Topsun (Okuno Pharmaceutical Co., Ltd.) for 1 minute.
[0042]
(7) Copper electroplating step: The test piece was immersed in a plating bath (liquid temperature: 25 ° C.) having the following composition and electroplated for 120 minutes.
(Composition of plating bath)
Copper sulfate (CuSO ₄ .5H ₂ O) 200 g / L
Sulfuric acid (98%) 50g / L
Chloride ion (Cl ⁻ ) 5 ml / L,
Top Lucina 2000MU (Okuno Pharmaceutical Co., Ltd.) 5ml / L
Top Lucina 2000A (Okuno Pharmaceutical Co., Ltd.) 0.5ml / L
[0043]
[Table 1]

[0044]
[Table 2]

[0045]
[Table 3]

[0046]
[Table 4]

[0047]
[Table 5]

[0048]
[Table 6]

[0049]
As is clear from Tables 1 to 6, the adhesion strength of the plating layer was dramatically improved by blending a water-soluble substance in the resin molded body.
[0050]
【The invention's effect】
The plated resin molded article of the present invention has not been subjected to etching treatment with an acid containing a heavy metal such as chromic acid, but has a plating layer with high adhesion strength. In addition, since the etching treatment with an acid containing heavy metal such as chromic acid is not performed, waste water treatment is easy and there is no environmental pollution due to heavy metal.

Claims (9)

A plated resin molded body having a metal plating layer on the surface of a resin molded body containing a thermoplastic resin and a water-soluble substance,
The water-soluble substance is selected from propylene glycol, ethylene glycol, diethylene glycol, neopentyl glycol, butanediol, pentanediol, polyoxyethylene glycol, polyoxypropylene glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and glycerin. A monohydric alcohol,
A plated resin molded article in which the resin molded article is not etched with an acid containing heavy metal.   The plated resin molded article according to claim 1, wherein the resin molded article further contains a surfactant and / or a coagulant.   The plated resin molded article according to claim 2, wherein the surfactant contains an emulsifier used for emulsion polymerization.   The plated resin molded article according to any one of claims 1 to 3, wherein a maximum value of adhesion strength (JIS H8630) between the resin molded article and the metal plating layer is 10 kPa or more.   The plated resin molded article according to any one of claims 1 to 4, which is used for automobile parts. It comprises a step of degreasing a resin molded body containing a thermoplastic resin and a water-soluble substance, and an electroless plating step.
The water-soluble substance is selected from propylene glycol, ethylene glycol, diethylene glycol, neopentyl glycol, butanediol, pentanediol, polyoxyethylene glycol, polyoxypropylene glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and glycerin. A monohydric alcohol,
A method for producing a plated resin molded article that does not include an etching step using an acid containing a heavy metal. A step of degreasing the molded body containing a thermoplastic resin and the water-soluble substance, between the electroless plating process, according to claim 6, wherein comprising the step of treating at least the catalyst imparting solution of plated resin molded article Manufacturing method.   The method for producing a plated resin molded article according to claim 6 or 7, wherein the plated resin molded article has a maximum adhesion strength (JIS H8630) between the resin molded article and the metal plating layer of 10 kPa or more.   The method for producing a plated resin molded body according to any one of claims 6 to 8, wherein the plated resin molded body is used for automobile parts.