JP2019065101A - Resin material for plating, plated resin component, method for producing resin material for plating, and method for producing plated resin component - Google Patents

Abstract

To provide a resin material for plating with a PPS resin (polyphenylene sulfide resin), and a plated resin component with the resin material.SOLUTION: A resin material for plating 1 contains a polyphenylene sulfide resin 3 and an inorganic filler 5. A surface to be plated has anchor holes 7. The area ratio of the anchor holes 7 in the surface is 7-25%, provided the area of the surface is 100%. When the resin material for plating 1 is used, a plate layer 11 provides good adhesion.SELECTED DRAWING: Figure 1

Description

  The present disclosure relates to a plating resin material, a plating resin member, a method of manufacturing the plating resin material, and a method of manufacturing the plating resin member.

Materials for the plating resin include ABS resin, ABS / PC resin, PP resin and the like. However, these materials have limitations in heat resistance and strength. On the other hand, polyamide (nylon) is also used, but it is difficult to use in a water environment because of dimensional stability and physical properties.
The SPS resin which is an engineering plastic has a grade suitable for plating. This resin is higher in heat resistance than ABS resin and PP resin. However, impact strength is not sufficient, and it is difficult to use for a member that requires strength.
Therefore, it is considered to use super engineering plastic (hereinafter referred to as "super engineering plastic") (see, for example, Patent Document 1). Super engineering plastic is high in both heat resistance and strength. And in order to expand the use application of super engineering plastic, plating to super engineering plastic is desired.

JP 10-195302 A

However, in the case of super engineering plastic, the adhesion of the plating layer is not always sufficient. Then, the resin material for plating of super engineering plastic with high adhesiveness of a plating layer was desired.
In particular, a resin material for plating using a PPS resin (polyphenylene sulfide resin) which is low in cost, good in moldability and high in versatility is expected.
This invention is made in view of the said situation, and it aims at providing the resin material for plating using PPS resin, and the plating resin member using the same. The present invention can be realized as the following modes.

[1]
It is a resin material for plating containing polyphenylene sulfide resin and an inorganic filler,
The surface to be plated has anchor holes and
The resin material for plating whose area ratio of the said anchor hole in the said surface is 7 to 25% when the said surface is made into 100%.

[2]
The plating resin member by which the plating layer was formed in the said surface of the resin material for plating as described in [1].

[3]
The manufacturing method of the resin material for plating which forms an anchor hole by removing the said inorganic filler from the surface of the resin material containing polyphenylene sulfide resin and an inorganic filler.

[4]
A method for producing a resin material for plating, wherein anchor holes are formed by removing the inorganic filler present on the exposed surface after shaving a surface portion of a resin material containing a polyphenylene sulfide resin and an inorganic filler.

[5]
A step of forming a resin material for plating, wherein anchor holes are formed by removing the inorganic filler from the surface of a resin material containing a polyphenylene sulfide resin and an inorganic filler;
And a plating step of forming a plating layer on the resin material for plating.

[6]
After shaving a surface portion of a resin material containing a polyphenylene sulfide resin and an inorganic filler, an anchor hole is formed by removing the inorganic filler present on the exposed surface to form a resin material for plating as a resin material for plating Process,
And a plating step of forming a plating layer on the resin material for plating.

When the resin material for plating of [1] is used, the adhesion of the plating layer becomes good.
In the plated resin member of [2], the adhesion of the plated layer is high.
According to the method for producing a resin material for plating of [3], it is possible to produce a resin material for plating in which the adhesion of the plating layer is good.
According to the method for producing a resin material for plating of [4], since the inorganic filler present on the exposed surface is removed after the surface portion of the resin material is scraped, anchor holes can be easily formed. It is possible to manufacture a plating resin material with very good adhesion.
According to the method for producing a plated resin member of [5], it is possible to produce a plated resin member with high adhesion of the plated layer.
According to the method for producing a plated resin member of [6], after scraping the surface portion of the resin material, the inorganic filler present on the exposed surface is removed, so that anchor holes can be easily formed, and adhesion of the plating layer It is possible to manufacture a plated resin member having extremely high properties.

The invention will be further described in the following detailed description referring to the non-limiting examples of typical embodiments according to the invention and with reference to the mentioned figures.
It is sectional drawing which shows an example of the resin material for plating typically. It is sectional drawing which shows an example of a plating resin member typically. It is sectional drawing which shows an example of a manufacturing method. Upper view: Mapping image by SEM (scanning electron microscope). Bottom: The image after binarization.

  Hereinafter, embodiments of the present invention will be described in detail. In the present specification, in the description using “to” for the numerical value range, the lower limit value and the upper limit value are included unless otherwise noted. For example, in the description of "10 to 20", both of the lower limit "10" and the upper limit "20" are included. That is, "10 to 20" has the same meaning as "10 to 20".

1. Resin Material for Plating The resin material 1 for plating of the present invention contains a polyphenylene sulfide resin 3 and an inorganic filler 5 as shown in FIG. And, the surface to be plated has anchor holes 7. The area ratio of the anchor holes 7 in the surface to be plated is 7 to 25% when the entire surface to be plated is 100%.

(1) Polyphenylene Sulfide Resin The polyphenylene sulfide resin 3 used in the present invention is a polymer having a repeating unit represented by the following structural formula (I). The polyphenylene sulfide resin 3 preferably contains 70 mol% or more, more preferably 90 mol% or more of the repeating unit represented by the structural formula (I) from the viewpoint of heat resistance. The polyphenylene sulfide resin 3 may be a homopolymer or a copolymer.
The polyphenylene sulfide resin 3 can be obtained, for example, by the method disclosed in Japanese Patent Publication No. 45-3368 and Japanese Patent Publication No. 63-33775. The melt viscosity and weight average molecular weight of the polyphenylene sulfide resin used in the present invention are not particularly limited. Polyphenylene sulfide resin 3 having a weight average molecular weight of 40,000 to 150,000 is suitably used.

  Although it does not specifically limit as another repeating unit in the case of a copolymer, The repeating unit which has a structure which S atom couple | bonded with the substituted or unsubstituted benzene ring is preferable. For example, the repeating unit shown by following Structural formula described in Unexamined-Japanese-Patent No. 2014-065841 is illustrated.

(2) Inorganic filler (inorganic filler)
The inorganic filler 5 is not particularly limited. As the inorganic filler 5, a substance which is soluble in a liquid such as an acid solution is preferable. The inorganic filler is preferably, for example, one or more selected from the group consisting of calcium carbonate, magnesium carbonate and magnesium hydroxide. Calcium carbonate is particularly preferred in terms of cost advantages and solubility in liquid.
Further, the content of the inorganic filler 5 in the plating resin material 1 is not particularly limited. The content of the inorganic filler 5 is preferably 1 to 60 parts by mass, more preferably 5 to 60 parts by mass, particularly preferably 10 to 10 parts by mass, based on 100 parts by mass of the entire resin material 1 for plating. 60 parts by mass. Within this range, the flowability is good and injection molding is easy.
In addition, the shape of the inorganic filler 5 is not specifically limited, Any form of an indeterminate form, scaly shape, and spherical shape may be sufficient.

(3) Other Components The resin material 1 for plating of the present invention may contain a resin other than the polyphenylene sulfide resin 3. Other resins are not particularly limited, and examples thereof include polyamides such as nylon 6 (PA 6), nylon 66 (PA 66), nylon 610 (PA 610), nylon 11 (PA 11), nylon 12 (PA 12) and aromatic nylon. Polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polycyclohexyl dimethylene terephthalate, polynaphthalene terephthalate, polyethylene, polypropylene, polytetrafluoroethylene, carboxyl group, carboxylic ester group, acid anhydride group, epoxy group, etc. Containing olefin copolymers, polyolefin elastomers, polyether ester elastomers, polyether amide elastomers, polyamide imides, polyacetals, polyimides, polyesters Terimide, polyether sulfone, modified polyphenylene ether resin, polysulfone resin, polyaryl sulfone resin, polyketone resin, polyarylate resin, liquid crystal polymer, polyether ketone resin, polythioether ketone resin, polyether ether ketone resin, polyamide imide resin, Examples thereof include polyethylene tetrafluoride resins and epoxy group-containing polyolefin copolymers.

  Components other than resin and the inorganic filler 5 can be added to the resin material 1 for plating of this invention. The other components are not particularly limited. For example, antioxidants, heat-resistant stabilizers (hindered phenols, hydroquinones, phosphites, and their substitutes), weathering agents (resorcinol, salicylates, benzotriazoles, benzophenones, hindered amines, etc.), Additives and lubricants (Montanic acid and its metal salts, their esters, their half esters, stearyl alcohol, stearamide, various bisamides, bisureas, polyethylene waxes, etc.), pigments (cadmium sulfide, phthalocyanines, carbon blacks for coloring, etc.), dyes (Nigrosin etc.), crystal nucleating agent (talc, silica, kaolin, clay etc.), plasticizers (octyl p-oxybenzoate, N-butylbenzenesulfonamide etc.), antistatic agent (alkyl sulfate type anionic antistatic agent) , Quaternary ammonium salts Cationic antistatic agent, nonionic antistatic agent such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agent, etc., flame retardant (eg, red phosphorus, phosphoric ester, melamine cyanurate, magnesium hydroxide) , Hydroxides such as aluminum hydroxide, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resin, or combinations of these brominated flame retardants with antimony trioxide, etc.), heat stable Conventional additives such as agents, lubricants such as aluminum stearate, lithium stearate, UV inhibitors, colorants, flame retardants and blowing agents can be added.

  The amount of components other than the polyphenylene sulfide resin 3 and the inorganic filler 5 contained in the resin material 1 for plating of the present invention is usually 10 parts by mass or less, based on 100 parts by mass of the entire resin material 1 for plating Preferably it is 5 mass parts or less, More preferably, it is 3 mass parts or less. Within this range, physical properties such as strength of the plating resin material 1 can be sufficiently secured.

(4) Anchor Hole The surface of the plating resin material 1 to be plated has an anchor hole 7. The planar shape of the anchor hole 7 is not particularly limited. The area ratio of the anchor holes 7 in the surface to be plated is 7 to 25%, preferably 9 to 25%, more preferably 11 to 25%, based on 100% of the entire surface to be plated. is there. Within this range, after securing physical properties such as the strength and the like of the plating resin material 1, the anchor effect can be sufficiently exhibited.
Here, a method of calculating the area ratio of the anchor hole 7 will be described.
<1> A resin material 1 for plating is prepared.
<2> An image is taken with a SEM (secondary electron image, 500 ×) (see the upper diagram in FIG. 4).
The <3> image is binarized using the following software (see the lower diagram in FIG. 4). By this processing, the anchor holes 7 become black, and the places where the anchor holes 7 are not formed become white. And the area ratio of the anchor hole 7 is calculated | required by the following formula. In the following formula, the resin area means the area of the place where the anchor hole 7 is not formed.

Anchor hole area ratio (%)
= {Anchor hole area (black) / (Anchor hole area (black) + resin area (white))} × 100

・ Binarization processing software: azpt136 → _Azpainter. Use exe (application).
Area quantification software: i2a100 → I2A. Use exe (application).

  The depth of the anchor holes 7 is not particularly limited. The depth of the anchor hole 7 is preferably 5 to 100 μm, more preferably 10 to 50 μm, and still more preferably 10 to 45 μm from the surface of the resin material 1 for plating at the deepest anchor hole 7. preferable. Within this range, after securing physical properties such as the strength and the like of the plating resin material 1, the anchor effect can be sufficiently exhibited. The depth of the anchor holes can be measured by observing the cross section of the plating resin material 1 with a microscope (optical microscope, electron microscope).

2. Plating Resin Member In the plating resin member 10, as shown in FIG. 2, the plating layer 11 is formed on the surface of the resin member 1 for plating. The plating layer 11 may be formed of a single metal film, or may be formed of a multilayer film formed of a plurality of metal films. Examples of the metal film include a copper plating film, a nickel plating film, and a chromium plating film. It is preferable to form it by the multilayer film which makes an uppermost layer a chromium plating film from a viewpoint of decoration property, intensity | strength, a lifetime, etc. As a plating layer of such a multilayer film, what formed in order a copper plating film, a nickel plating film, and a chromium plating film can be illustrated suitably, for example.
Further, the thickness of the plating layer 11 is not particularly limited. The thickness is preferably 5 to 100 μm, more preferably 10 to 60 μm, and still more preferably 10 to 30 μm from the viewpoint of strength, life and the like.

3. Method of Manufacturing Resin Material for Plating (1) Method of Manufacturing First Resin Material for Plating A method of manufacturing the first resin material for plating 1 will be described with reference to FIGS. 3 (1) and 3 (2).
In the manufacturing method of the first resin material 1 for plating, the anchor holes 7 are formed by removing the inorganic filler 5 from the surface of the resin material 20 containing the polyphenylene sulfide resin 3 and the inorganic filler 5. That is, the surface is roughened by removing the inorganic filler 5 from the surface of the resin material 3. The means for forming the anchor holes 7 by removing the inorganic filler 5 is not particularly limited. As a means, either physical treatment or chemical treatment can be adopted. In addition, conditions in physical treatment and chemical treatment are not particularly limited.
In this manufacturing method, it is preferable to degrease and wash the surface of the resin material 20 in the process of FIG. 3 (1). Usually, a surfactant is suitably used for degreasing.
The method of manufacturing the first plating resin material 1 includes the steps schematically illustrated in FIG. 3. The means for forming the anchor holes 7 is preferably a chemical treatment, and it is preferable that an etchant capable of dissolving the inorganic filler 5 be used. As an etching agent, an inorganic acid, trichloroethane, trichloroethylene, xylene etc. are used suitably, for example. As the inorganic acid, it is preferable to use one or more selected from the group consisting of nitric acid, sulfuric acid, hydrochloric acid, dichromic acid, a mixed solution of dichromic acid / sulfuric acid, chromic acid, and a mixed solution of chromic acid / sulfuric acid.

(2) Second Method of Manufacturing Resin Material for Plating In the second method of manufacturing resin material 1 for plating, the surface portion (skin layer) of resin material 20 containing polyphenylene sulfide resin 3 and inorganic filler 5 was scraped. Later, the anchor holes 7 are formed by removing the inorganic filler 5 present on the exposed surface.
The second method for manufacturing the plating resin material 1 is characterized in that the surface portion of the resin material 20 containing the polyphenylene sulfide resin 3 and the inorganic filler 5 is scraped. After the surface portion is scraped, the same steps as the method of manufacturing the first resin material for plating 1 are included. The description of this same process is the same as that described in 3. above. The description of (1) can be applied as it is.
Here, the process of shaving the surface portion of the resin material 20 will be described. The surface portion of the resin material containing the polyphenylene sulfide resin 3 and the inorganic filler 5 has high chemical resistance. That is, in the surface portion of the resin material, the ratio of the polyphenylene sulfide resin 3 is higher than that of the inner side. Therefore, even if physical treatment or chemical treatment is applied as it is to the resin material 20 (molded article) molded by injection molding or the like, the inorganic filler 5 may be removed to reduce the number of anchor holes 7 formed. In the second method for manufacturing the plating resin material 1, after the surface portion having high chemical resistance is scraped, the above-mentioned physical treatment and chemical treatment are applied. Since the above-mentioned physical treatment and chemical treatment are applied with the inorganic filler 5 sufficiently exposed, the anchor holes 7 with an anchor function are sufficiently formed.

The method of shaving the surface portion is not particularly limited. As a method of scraping the surface portion, known methods such as polishing (grinding), dry blast, liquid honing, wet blasting and the like can be adopted. Moreover, you may combine these methods as a method of shaving a surface part. Wet blasting is preferable from the viewpoint of controlling the adhesion strength. According to wet blasting, it can be shaved mildly. In addition, the abrasives used for wet blasting are not specifically limited, Preferably an alumina, a zirconia, glass etc. can be used. Moreover, the pressure in the case of wet blasting is not specifically limited, either, Preferably it can be 0.1-0.4 Mpa. The treatment time in wet blasting is not particularly limited, and can be preferably 20 to 80 seconds.
The thickness to be cut in the step of cutting the surface portion is not particularly limited. The thickness to be removed is preferably 0.5 to 30.0 μm, more preferably 0.5 to 20.0 μm, and still more preferably 0.5 to 15.0 μm. Within this range, a portion having a high content of polyphenylene sulfide resin 3 can be sufficiently removed, and the strength reduction of resin material 1 for plating due to excessive shaving is also small.

  In addition, in the manufacturing method of the above-mentioned 1st and 2nd resin material for plating, about polyphenylene sulfide resin 3 and the inorganic filler 5, above-mentioned 1.. (1) The description of (2) can be applied as it is.

4. Method of Manufacturing Plating Resin Member (1) Method of Manufacturing First Plating Resin Member 10 In the method of manufacturing the first plating resin member 10, the surface of the resin material 20 containing the polyphenylene sulfide resin 3 and the inorganic filler 5 is inorganic By removing the filler 5, the step of forming the anchor holes 7 to form the plating resin material 1 as the plating resin material 1 and the plating step of forming the plating layer 11 on the plating resin material 1 are provided.
(1.1) Resin material formation process for plating The resin material formation process for plating can employ | adopt the same method as above-mentioned "3. (1) manufacturing method of the 1st resin material for plating". That is, in the plating resin material forming step, the above-mentioned 3. The contents described in (1) can be applied as they are, so detailed description will be omitted here.

(1.2) Plating process Here, the plating process which forms the plating layer 11 in the surface of the resin material 1 for plating is demonstrated. The plating process can adopt the same process as general chemical plating and general electroplating on a resin material. An example thereof will be described with reference to FIGS. 3 (3) (4) (5).
In this example, the plating process includes a chemical plating catalyst application process (FIG. 3 (3)), a chemical plating process (FIG. 3 (4)), and an electroplating process (FIG. 3 (5)).

(1.2.1) Polarization process (optional process)
Prior to the chemical plating catalyst application step of FIG. 3 (3), the surface to be plated with the plating resin material 1 may be treated with a polar compound in order to apply an electric charge. This step is optional and is also referred to as a polarization application step.
Examples of the treating agent in this treatment include primary aliphatic amines such as methylamine, ethylamine, propylamine, isopropylamine and butylamine, and secondary aliphatic amines such as dimethylamine, diethylamine and dipropylamine. Aliphatic tertiary amines represented by trimethylamine, triethylamine and tripropylamine, aliphatic unsaturated amines represented by allylamine and diallylamine, cyclopropylamine, cyclobutylamine and cycloaliphatic amines represented by cyclopentylamine, and aniline Representative aromatic amines, alkyl sulfonic acids, α-olefin sulfonic acids, alkyl benzene sulfonic acids, alkyl naphthalene sulfonic acids, alkyl ether sulfonic acids, alkyl phenyl ether sulfonic acids, alkyl Phenyl ether sulfonic acid, sulfosuccinic acid, dialkyl sulfosuccinic acid, methyl tauric acid, β-naphthalene sulfonic acid, formalin condensate, or polyacrylic acid, polyvinyl sulfonic acid, polymethacrylic acid, polystyrene sulfonic acid, polyhydroxyethyl methacrylate, polyvinyl alcohol , Polyvinyl alcohol copolymer, partially saponified polyvinyl acetate, partially saponified vinyl acetate copolymer, ethyleneimine, polyethyleneimine, polyethylene oxide, polypropylene oxide, polyethylene oxide-polypropylene oxide copolymer, polyvinyl methyl ether, Polyvinyl methyl ether copolymer, pyrrolidone, poly (N-vinyl pyrrolidone), polyvinyl oxazoline, polyacrylamide, poly (acrylamide) Aqueous solutions or salts such as co-critical condition is preferably exemplified. Among these, those having substituted ammonium salts such as aliphatic primary amines and salts of polyethyleneimine are particularly preferable. These aqueous solutions may be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular about processing conditions, It is preferable to process at the temperature of 10-60 degreeC for 1 to 10 minutes. By performing this polarity application step, the chemical plating catalyst 21 is easily attached, the metal film (chemical plating film) 23 is easily formed, and the desired plating resin member 10 is obtained.

(1.2.2) Chemical plating catalyst application process (FIG. 3 (3))
The chemical plating catalyst application step is a step for advancing chemical plating in the next step. The method for applying the chemical plating catalyst 21 is not particularly limited. In this step, methods conventionally used conventionally in plating of resin molded articles can be used.
For example, colloids of stannous chloride and palladium chloride having a negative charge are used as catalyst particles. First, a colloidal substance of tin and palladium is deposited on the surface of the plating resin material 1 to which polarity is imparted in the polarization step by catalyzing, and then tin is released by acceleration, leaving only palladium. A method of applying the chemical plating catalyst 21 can be adopted.
Also, the following method can be adopted. First, as the sensitising (sensitivity imparting treatment), for example, the plating resin material 1 to which polarity is imparted in the polarity imparting step is immersed in a stannous chloride solution to reduce the reduction power on the surface of the plating resin material 1. Treatment to adsorb some ionic tin. Thereafter, as the activation (activation treatment), the chemical plating catalyst 21 can be applied by, for example, immersing the plating resin material 1 in a palladium chloride solution and depositing palladium by the action of the tin.

(1.2.3) Chemical plating process (Figure 3 (4))
The chemical plating step is a step of reducing and precipitating metal ions on the surface of the resin material for plating 1 having passed the chemical plating catalyst application step to form the metal film 23. It does not specifically limit about this chemical plating process, The method conventionally used in the plating process of the resin molding can be used conventionally. For example, by immersing the resin material 1 for plating, which has undergone the catalyst application step for chemical plating, in a copper salt or nickel salt aqueous solution containing a reducing agent at about 10 to 50 ° C. for about 2 to 20 minutes, a copper plating film is formed on the surface. Alternatively, a nickel plating film can be formed.

(1.2.4) Electroplating process (Fig. 3 (5))
In the electroplating process, the metal film (chemical plating film) 23 formed in the chemical plating process is thin and its strength and the like are small. Therefore, in the process of applying electroplating on this to strengthen the plating film (plating layer 11) is there. The electroplating film 25 may be a single metal film or may be a multilayer film consisting of a plurality of metal films. From the viewpoint of decorativeness, strength, life and the like on the design, a multilayer coating having a chromium plating film as the uppermost layer is preferable. As such a multilayer film, the form which provided sequentially a copper plating film, a nickel plating film, and a chromium plating film by electroplating, for example can be mentioned preferably. There is no particular limitation on the method of electroplating, and methods conventionally used in the plating treatment of resin moldings can be used.
A layer obtained by combining both the metal film 23 and the electroplating film 25 corresponds to the plating layer 11.

(2) Method of Manufacturing Second Plating Resin Member In the method of manufacturing the second plating resin member 10, after the surface portion (skin layer) of the resin member 20 containing the polyphenylene sulfide resin 3 and the inorganic filler 5 is scraped, Resin material forming step for forming the anchor holes 7 by removing the inorganic filler 5 present on the exposed surface to make the resin material 1 for plating, and plating step for forming the plating layer 11 on the resin material 1 for plating And.
(2.1) Resin material formation process for plating The resin material formation process for plating can employ | adopt the same method as above-mentioned "3. (2) manufacturing method of the resin material for 2nd plating"". That is, since the contents of description of 3 (2) of the above-mentioned can be applied as it is to the resin material formation process for plating, detailed explanation is omitted here.
(2.2) Plating process The plating process can employ the same method as the above-mentioned "4. (1) First method of manufacturing a plated resin member". That is, since the description content of the above-mentioned "(1.2) plating process" can be applied as it is to a plating process, detailed description is abbreviate | omitted here.

  In addition, in the manufacturing method of the 1st and 2nd plating resin member 10, about polyphenylene sulfide resin 3 and the inorganic filler 5, above-mentioned 1. above-mentioned. (1) The description of (2) can be applied as it is.

  Hereinafter, the present invention will be more specifically described by way of examples. Experimental Examples 1 and 2 correspond to Comparative Examples, and Experimental Examples 3 to 8 correspond to Examples.

1. Preparation of plating resin member (experimental example 1)
Injection molding was performed using as a raw material the compound mixed in the ratio of 80 mass parts of polyphenylene sulfide resin and 20 mass parts of calcium carbonate, and the molded object was obtained. As calcium carbonate, one having an average particle diameter of 19 μm was used.
The surface portion of this molded body was scraped by a grinder. Then, the anchor holes were formed by etching using nitric acid. Thereafter, palladium was attached to the surface and subjected to copper sulfate plating used for general decorative plating.
The area ratio of the anchor holes was 4.5%.

(Experimental example 2)
Injection molding was performed using as a raw material the compound mixed in the ratio of 80 mass parts of polyphenylene sulfide resin and 20 mass parts of calcium carbonate, and the molded object was obtained. As calcium carbonate, one having an average particle diameter of 26 μm was used.
The surface portion of this molded body was scraped by a grinder. Then, the anchor holes were formed by etching using nitric acid. Thereafter, palladium was attached to the surface and subjected to copper sulfate plating used for general decorative plating.
The area ratio of the anchor holes was 6.6%.

(Experimental example 3)
Injection molding was performed using as a raw material the compound mixed in the ratio of 80 mass parts of polyphenylene sulfide resin and 20 mass parts of calcium carbonate, and the molded object was obtained. As calcium carbonate, one having an average particle diameter of 45 μm was used.
The surface portion of this molded body was scraped by a grinder. Then, the anchor holes were formed by etching using nitric acid. Thereafter, palladium was attached to the surface and subjected to copper sulfate plating used for general decorative plating.
The area ratio of the anchor holes was 7.1%.

(Experimental example 4)
Injection molding was performed using as a raw material the compound mixed in the ratio of 40 mass parts of polyphenylene sulfide resin, and 60 mass parts of calcium carbonate, and the molded object was obtained. As calcium carbonate, one having an average particle diameter of 15 μm was used.
The surface portion of this molded body was scraped by wet blasting (abrasive: alumina # 2000, 0.3 MPa, 40 s). Then, the anchor holes were formed by etching using nitric acid. Thereafter, palladium was attached to the surface and subjected to copper sulfate plating used for general decorative plating.
The area ratio of the anchor holes was 9.3%.

(Experimental example 5)
Injection molding was performed using as a raw material the compound mixed in the ratio of 40 mass parts of polyphenylene sulfide resin, and 60 mass parts of calcium carbonate, and the molded object was obtained. As calcium carbonate, one having an average particle diameter of 15 μm was used.
The surface portion of this molded body was scraped by wet blasting (abrasive: alumina # 2000, 0.35 MPa, 40 s). Then, the anchor holes were formed by etching using nitric acid. Thereafter, palladium was attached to the surface and subjected to copper sulfate plating used for general decorative plating.
The area ratio of the anchor holes was 11.4%.

(Experimental example 6)
Injection molding was performed using as a raw material the compound mixed in the ratio of 40 mass parts of polyphenylene sulfide resin, and 60 mass parts of calcium carbonate, and the molded object was obtained. As calcium carbonate, one having an average particle diameter of 26 μm was used.
The surface portion of this molded body was scraped by a grinder. Then, the anchor holes were formed by etching using nitric acid. Thereafter, palladium was attached to the surface and subjected to copper sulfate plating used for general decorative plating.
The area ratio of the anchor holes was 15.5%.

(Experimental example 7)
Injection molding was performed using as a raw material the compound mixed in the ratio of 40 mass parts of polyphenylene sulfide resin, and 60 mass parts of calcium carbonate, and the molded object was obtained. As calcium carbonate, one having an average particle diameter of 35 μm was used.
The surface portion of this molded body was scraped by a grinder. Then, the anchor holes were formed by etching using nitric acid. Thereafter, palladium was attached to the surface and subjected to copper sulfate plating used for general decorative plating.
The area ratio of the anchor holes was 19.3%.

(Experimental example 8)
Injection molding was performed using as a raw material the compound mixed in the ratio of 40 mass parts of polyphenylene sulfide resin, and 60 mass parts of calcium carbonate, and the molded object was obtained. As calcium carbonate, one having an average particle diameter of 45 μm was used.
The surface portion of this molded body was scraped by a grinder. Then, the anchor holes were formed by etching using nitric acid. Thereafter, palladium was attached to the surface and subjected to copper sulfate plating used for general decorative plating.
The area ratio of the anchor holes was 20.7%.

In addition, in the above-mentioned experiment example, plating after forming an anchor hole was specifically performed as follows.
The plating was performed according to the CUP process (see http://www.okuno.co.jp/index.html) of Okuno Pharmaceutical Industries, Ltd.
After the anchor holes were formed, a polarization applying step was performed using a CRP conditioner 551 (trade name, manufactured by Okuno Pharmaceutical Co., Ltd.). Next, pre-dip was performed using dilute hydrochloric acid. And the catalyst provision process for chemical plating was performed using the CRP catalyst 85 (brand name, Okuno Pharmaceutical Industries Co., Ltd. product made). Then, it was accelerated using sulfuric acid (80 mL / L, 40 ° C.).
Next, a chemical plating process was performed. In the chemical plating step, an aqueous solution of the following composition was used.
Chemical Nickel A (trade name, manufactured by Okuno Pharmaceutical Co., Ltd.): 160 mL / L
Chemical Nickel B (trade name, manufactured by Okuno Pharmaceutical Co., Ltd.): 160 mL / L

Next, an electroplating step was performed. In the electroplating step, an aqueous solution of the following composition was used.
Copper sulfate: 200 g / L
Sulfuric acid: 50 g / L
Chloride ion: 70 mg / L
Top Lucina MU (trade name, manufactured by Okuno Pharmaceutical Co., Ltd.): 5 mL / L
Top Lucina A (trade name, manufactured by Okuno Pharmaceutical Co., Ltd.): 0.5 mL / L

2. Evaluation Method of Plating Resin Member A cut of 10 mm in width was made in the plating layer of each plating resin member, and the load when peeled at a speed of 25 mm / min was measured. Thus, the peel strength of each plating resin member was measured.

3. Evaluation results of the plated resin member The results are shown in Table 1. From this Table 1, it was confirmed that the peel strength is high when the area ratio of the anchor holes is 7 to 25%.

4. Effect of Example As described above, it was confirmed that the adhesion of the plating layer is increased when the area ratio of the anchor holes is 7 to 25%. The plated resin member has a metallic luster and therefore has a good appearance. In addition, since the molded product used for the plating resin member is made of resin, it can be molded by various molding methods. Therefore, the plating resin member has a high degree of freedom in shape and is advantageous in cost. In addition, in order to make the area ratio of an anchor hole larger than 25%, it is necessary to increase the ratio of a calcium carbonate, However, In this case, fluidity | liquidity was bad and it was difficult to carry out injection molding.

  The invention is not limited to the embodiments detailed above, but various modifications or alterations are possible within the scope of the claims of the invention.

  The invention can be applied to a wide variety of applications. In particular, it can be suitably used for resin members around water where heat resistance, strength, and impact resistance are required. As a resin member around water, for example, a water passing member through which water and / or warm water passes can be mentioned.

DESCRIPTION OF SYMBOLS 1 ... Resin material for plating 3 ... Polyphenylene sulfide resin 5 ... Inorganic filler 7 ... Anchor hole 10 ... Plating resin member 11 ... Plating layer 20 ... Resin material 21 ... Catalyst for chemical plating 23 ... Metal film (chemical plating film)
25 ... Electroplated film

Claims (6)

It is a resin material for plating containing polyphenylene sulfide resin and an inorganic filler,
The surface to be plated has anchor holes and
The resin material for plating whose area ratio of the said anchor hole in the said surface is 7 to 25% when the said surface is made into 100%.   The plating resin member by which the plating layer was formed in the said surface of the resin material for plating of Claim 1.   The manufacturing method of the resin material for plating which forms an anchor hole by removing the said inorganic filler from the surface of the resin material containing polyphenylene sulfide resin and an inorganic filler.   A method for producing a resin material for plating, wherein anchor holes are formed by removing the inorganic filler present on the exposed surface after shaving a surface portion of a resin material containing a polyphenylene sulfide resin and an inorganic filler. A step of forming a resin material for plating, wherein anchor holes are formed by removing the inorganic filler from the surface of a resin material containing a polyphenylene sulfide resin and an inorganic filler;
And a plating step of forming a plating layer on the resin material for plating. After shaving a surface portion of a resin material containing a polyphenylene sulfide resin and an inorganic filler, an anchor hole is formed by removing the inorganic filler present on the exposed surface to form a resin material for plating as a resin material for plating Process,
And a plating step of forming a plating layer on the resin material for plating.