WO2006121186A1

WO2006121186A1 - Coating material difficult to plate and method of pretreatment for plating

Info

Publication number: WO2006121186A1
Application number: PCT/JP2006/309767
Authority: WO
Inventors: Toshihiro Tai; Masahiko Itakura
Original assignee: Daicel Polymer Ltd.
Priority date: 2005-05-11
Filing date: 2006-05-10
Publication date: 2006-11-16
Also published as: TW200643214A; JP4663394B2; JP2006316297A

Abstract

A coating material difficult to plate which, even when immersed in an electroless plating bath, can prevent deposition on a desired part. The coating material difficult to plate comprises 100 parts by mass of an olefin resin and 0.1-100 parts by mass of a water-repellent resin and optionally contains 0.1-100 parts by mass of one or more members selected among compounds containing antimony or bismuth. The olefin resin preferably is polyethylene and the water-repellent resin preferably is a fluororesin and/or silicone resin.

Description

Technical Report Technical Field

The present invention relates to a hard-wearing coating agent used when a molded body surface made of metal or resin is attached, and a pretreatment method for plating using the same. Background art

To reduce the weight of an automobile. Purpose: A resin molding such as AB S. Resin is used as an automobile article. Poly: Ami: K resin. Therefore, copper, nickel, nickel, etc. are plated.

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 affixing ABS resin moldings or polypropylene moldings, use a chromic acid bath (a mixture of glommonium trioxide and sulfuric acid) after degreasing and etch at 65-70 ° C for 10 15 minutes. Wastewater contains toxic hexavalent chromate ions. For this reason, it is essential to neutralize and precipitate after reducing hexavalent chromate ions to trivalent ions. .:

In this way, considering the safety at work and the environmental impact of wastewater, it is desirable not to use an etching bath that uses a mouthwater bath. There is a problem that 'the adhesion strength of the plating layer to the formed body cannot be increased'.

The inventions of J PA 2003-82138 and JPA 2003- 1.66067 solve such problems of the prior art, and have a metal adhesive with high adhesion strength even though the etching process using a rom bath is unnecessary. A plated resin molded body having a layer is obtained. Disclosure of the invention

When plating on a resin molded body, immerse it in a non-electrolytic bath while holding the resin molded body with a metal jig. When an etching process using a chromic acid bath is performed, chromic acid remains on the metal jig surface, which acts as a catalyst poison. For this reason, plating does not deposit on the surface of metal jigs when electroless plating is performed, but JP-A 2 0 0 3— 8 2 1 3 8 and JP— A 2 0 0 3 _ 1 6 6 In the invention of 0 6 7, there is a problem that the adhesion is deposited on the surface of the metal jig because there is no etching process using a chromic acid bath.

In the invention of JP—A 1 0-5 3 8 7 8, a resist coating inhibitor for applying to a non-sticking part of a resin molded body, a composition for inhibiting precipitation of plating applied to a resist ink, etc. are disclosed. Yes. However, as described in the examples of the same document, it is used in a method of fitting based on an etching process using a chromic acid bath.

The present invention provides a hard-to-stick coating that can prevent a desired portion from being stuck when the surface of a molded body made of metal or resin is electrolessly attached, and a pretreatment method for plating using the same. .

The present invention relates to 100 parts by mass of the olefin-based resin, 0.1 to 100 parts by mass of the water-repellent resin and optionally 0.1 or more selected from compounds containing antimony and bismuth. Provided is a hard-coating agent containing 100 parts by mass.

The present invention also provides a plating pretreatment method in which the above-mentioned hard-to-stick coating agent is powder-coated on the non-sticking portion of the surface of the molded body.

In addition, the present invention provides a use of a hard coating composition for a hard coating composition containing 100 parts by weight of an olefin resin and 0.1 to 100 parts by weight of a water-repellent resin. The present invention provides a method for applying a hard coating so that a desired portion is not stuck when the surface of a molded body made of a metal or a resin is electrolessly stuck, and then subjecting this to a treatment.

The hard-to-stick coating of the present invention is in a powder form and does not contain a solvent like paints and inks.

In the present invention, “difficult to stick” means that the surface of the molded body is electrolessly attached. This means preventing plating deposition or making it difficult to deposit.

Even when immersed in an electroless plating bath, plating is deposited on the surface of the molded body by coating the surface of the molded body by the powder coating method using the hard-to-stick coating material of the present invention. There is nothing. Therefore, it is possible to prevent the desired portion of the molded body from being plated (that is, to allow the desired portion of the molded body to be plated). Brief Description of Drawings

FIG. 1 is an explanatory view of the plating pretreatment method of the present invention. Detailed Description of the Invention

<Hard-plating coating agent>

The olefin-based resin used in the present invention is a base component for forming a film on the non-sticking portion of the surface of the molded body and making the portion difficult to stick. As long as powder coating is possible, thermoplastic resins other than olefin-based resins can be blended, but 50% by mass or less is preferable in the total amount with olefin-based resins. The olefin resins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 3-methylbutene-1, 1,4-methylpentene-1, etc. Polymers, copolymers of these α-olefins such as random or block, or copolymers of these monomers (preferably 50% by mass or more) and other monomers are copolymerized. A polymer can be mentioned.

Other monomers include butadiene, isoprene, dicyclopentene, 1,4 monohexagen, 4-ethylidene-2-nonolebonenene, dicyclopentagen and other gens, acrylic acid, methacrylic acid, maleic acid, vinyl acetate, Examples thereof include unsaturated acids such as methyl methacrylate and imide maleic acid or derivatives thereof, and aromatic alkenyl compounds such as styrene and α_methylstyrene. These may be used alone or in combination of two or more. it can. The olefin resin may be amorphous or crystalline, but preferably exhibits crystallinity. Among these, polyethylene, polypropylene, poly (1-butene), ethylene-propylene copolymer, poly (3-methylbutene-1), and poly (4-methylpentene-1) are preferable.

(Polyethylene homopolymer and foremost, of ethylene units and 5 Monore ⁰ /. The following other Orefin unit of copolymer, of ethylene units and 1 mole ^_0/0 following other copolymerizable monomer a unit except the Orefin units Copolymers) are preferred.

For polyethylene, if the powder coating method can be applied to form a coating layer that becomes a non-stick part on the surface of the molded body, the average molecular weight, density, molecular structure (straight chain structure or branched structure), etc. There is no particular limitation.

The water-repellent resin used in the present invention is a component for imparting difficulty to the coating agent of the present invention by being dispersed in the base olefin-based resin.

The water-repellent resin, fluorine resin, silicone resin, polyisobutylene and the like can ani ^{gel, Polymer Handbook 3 rd Ed Wiley,} Interscience (1989) and Kakinai Hiroshi "paint resin chemistry", Shokodo, P241 ( (1972) etc., and those having a solubility index (SP value) of 8 or less in the polymer blend system are desirable.

The fluororesin is not particularly limited as long as it has a fluorine-carbon bond. For example, polytetrafluoroethylene, polychlorotrifluoroethylene, polytetrafluoroethylene-hexafluoropropylene Examples thereof include polymers, polyvinylidene fluoride, polyvinyl fluoride, alternating ethylene / fluoroethylene copolymer, and polyfluoride.

As the silicone resin, the type of silicone resin is not particularly limited as long as it has a carbon-oxygen bond. For example, dimethylpolysiloxane, dimethylhydrodienepolysiloxane, and dimethylpolysiloxane are various main skeletons. Examples of the polymer include various polymers having a main skeleton of dimethylhydropolyenepolysiloxane.

The blending amount of the water repellent resin is 0.1 to 100 parts by weight, preferably 0.1 to 50 parts by weight, more preferably 0 to 100 parts by weight of the olefin resin. 1-3 parts by mass.

The compound containing antimony and bismuth used in the present invention is a component that is blended as necessary, and acts as a catalyst poison like chromic acid, thereby enhancing the effect of preventing plating deposition on the surface of the molded body. It is an ingredient to do. A compound containing antimony and bismuth can be used alone as a single compound selected from these forces \ Two or more compounds selected from compounds containing antimony or two compounds selected from compounds containing bismuth A combination of the above can be used. Further, two or more kinds selected from a compound containing antimony and a compound containing bismuth can be used in combination.

Antimony compounds include antimony chloride, antimony trioxide, antimony pentoxide, potassium antimonate, antimony hydroxide, antimony trisulfide, antimony pentasulfide, etc. Examples include organic antimony compounds such as antimony acid sodium and pyrogallol antimony chelate.

Examples of bismuth compounds include bismuth trioxide, bismuth pentoxide, bismuth trisulfide, bismuthyl sulfate, bismuth nitrate oxide (III) hydrate, bismuth carbonate oxide (III) hemihydrate, and bismuth phosphate, Examples thereof include organic bismuth compounds such as bismuth citrate and pyrogallol.bismuth chelate.

The amount of one or more selected from compounds containing antimony and bismuth is 0.1 to 100 masses of one or more selected from compounds containing antimony and bismuth with respect to 100 parts by mass of the olefin resin. Parts, preferably 0.1 to 50 parts by mass, more preferably 0.1:! To 30 parts by mass.

The difficult-to-stick coating according to the present invention has an average particle size in consideration of applying the powder coating method; ˜10, OOO / m is preferred, 1-1, Ο Ο Ο μπι is more preferred, and 1˜100 μμπι is even more preferred. As the grain system is finer, a more uniform coating can be obtained. The insidious coating agent of the present invention can be obtained by mixing olefin-based resin and water-repellent resin, and further antimony and bismuth blended as necessary, and pulverizing, if necessary. Classification (adjustment of particle size) can also be performed. Book The inventive hard coatings do not contain organic solvents.

When the plating pretreatment method of the present invention includes an electroless plating process in the plating process, it is difficult for a part or all of the surface of the molded body at a desired time before reaching the electroless plating process. It imparts sturdiness.

The pre-treatment method of the present invention is a method for holding a resin molded body, which is a target to be tested, particularly in the method of attaching a resin molded body surface described in JP-A 2003-821 38 and JP-A 2 003-166067. It is suitable for the case where the metal jig is provided with difficulty and prevents the metal jig from being plated.

Next, the plating pretreatment method of the present invention will be described with reference to FIG. FIG. 1 is a side view showing a metal jig to which the pretreatment method of the present invention is applied and the state of use thereof.

Powder coating is applied to the non-sticking part (covering part 1 3) of the metal jig 10 according to the present invention.

The powder coating method is a well-known coating method (electrostatic coating method / fluid dipping method, etc., powder coating technology manual (3rd edition), Co., Ltd. Paint Newspaper Co., Ltd. (2005)). The heat-dissipated coating material is dispersed on the surface of the metal jig 10 corresponding to the hatched coating portion 13, and the metal jig 10 is heated to form a coating film (coating portion 13). It is a method of forming. The metal jig 10 has clamp portions 11 and 12 for fixing the formed body 20 to be plated on one end side, and also covers the clamp portions 11 and 12.

If the thickness of the coating film (covering part _{1 3} ) is 0.1 mm or more, it is possible to prevent the staking from depositing on the covering part 13 in the case of electroless staking, but it can be applied by contact during work. It is better to apply a thick layer because the film may be destroyed. Preferably it is 0.1-10 mm, More preferably, it is 0.:!-5 mm.

In this way, using the metal jig 10 to which the plating pretreatment method of the present invention is applied, for example, as described in “Method for producing a metal resin molded product” described in the examples of JP-A 2003-82138, Does not include chromic acid bath etching process, degreasing process, catalyst application process, first activation process, second activation process, nickel electroless plating In the case of attaching the thermoplastic resin molding in the order of the process, the acid activation process, and the copper electroplating process, the nickel electroless plating process is performed as follows.

First, the thermoplastic resin molded body 20 is sandwiched and fixed by the clamp parts 11 and 12 of the metal jig 10. Next, it is immersed in an electroless plating bath in this state. At this time, the portion of the covering portion 13 including the thermoplastic resin molded body 20 is immersed, but the portion 14 where the metal surface is exposed is not immersed.

After that, when pulled out from the electroless plating bath, there is adhesion on the surface of the thermoplastic resin molded body 20, but there is no adhesion on the covering portion 1 3 of the metal jig 10. . After the electroless plating as described above, the end of the metal jig 10 is connected to a power source, and the process proceeds to a copper electroplating process.

If cracks or scratches occur in the coated part 13 of the metal jig 10, the cracks and scratches can be easily repaired by placing them in a heating furnace and heating them above the melting point of the olefin resin. . Therefore, the metal jig 10 to which the pretreatment method of the present invention is applied can be used repeatedly. On the other hand, when the pre-treatment method of the present invention is not applied, precipitation cling accumulates on the surface of the metal jig 10, making it difficult to repeatedly use the metal jig 10.

When the etching process using a chromic acid bath is performed as in the conventional method (JP-A 1 0- 5 3 8 7 8 invention), it is made of a metal even during electroless plating due to the catalyst poison of chromic acid. No sticking is deposited on the surface of the jig 10, but by applying the pretreatment method of the present invention, no sticking is deposited on the surface of the metal jig 10 even if the etching process using a chromic acid bath is not performed. You can

In addition, when applying the direct plating method described in JP—A 5—2 3 9 6 6 0 and WO—A 9 8/4 5 5 0 5 (JP—B 3 2 0 8 4 1 0) There is almost no deposit on the surface of the metal jig. However, since the range of the optimum conditions when performing the direct plating method is narrow, the range of the optimum conditions when performing the direct plating method can be broadened by applying the pretreatment method of the present invention. Is advantageous. Example

Examples 1 and 2 and Comparative Example 1

Each component shown in Table 1 (in mass%) was mixed with a V-type tumbler and then melt-kneaded with a twin-screw extruder (manufactured by Nippon Steel, TEX30, cylinder temperature 160 ° C) to obtain pellets. The pellets were frozen and pulverized to prepare a hard-coating coating (average particle size 1,000,000 μm). Using the hard-to-stick coating materials of Examples 1 and 2 and Comparative Example 1, powder coating was performed on the metal jig 10 shown in FIG.

For powder coating, fluidized dipping was used. The metal jig was heated in an oven at 350 ° C, and the hard coating was immersed in a tank stirred with air. After standing for 1 minute, it was heated in an oven at 200 ° C for 5 minutes, the surface was melted and smoothed, and finally submerged and cooled.

The components having the following composition were mixed in a V-type tumbler and then melt-kneaded with a twin-screw extruder (manufactured by Nippon Steel, TEX 30, 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.). Using this thermoplastic resin molded article and the metal jig 10 shown in FIG. 1 treated with the hard-to-stick coating material of Example 1, 2 or Comparative Example 1, the stuck resin molded article was formed in the following steps. Manufactured.

(Components of molded thermoplastic resin)

Polyamide (Polyamide 6, Ube Industries, UBE nylon 6 1013B, water absorption 1.8%) 60% by mass in the total amount of resin components

AB S resin (styrene content 45 mass ⁰ /., Acrylonitrile 15 wt ^_0/0, polybut diene rubber 40 wt%, water absorption 0.2%) in the total amount of the resin component 30 wt%

Acid-modified ABS resin (styrene content 42 mass ^_0/0, Akuriro two Torinore 16 mass ^_0/0, rubber content 40 wt%, 2 wt% methacrylic acid, water absorption 0.2%) in the total amount of the resin component 10 wt%

Dipentaerythritol, 10 parts by mass per 100 parts by mass of resin component

(Plating process) (1) Degreasing process

The molded body was immersed in an aceclin A-220 (Okuno Pharmaceutical Co., Ltd.) 50 gZL aqueous solution (liquid temperature 40 ° C.) for 20 minutes.

(2) Acid contact process

1. It was immersed in 100 ml of 0N hydrochloric acid (liquid temperature 40 ° C) for 5 minutes.

(3) Catalyst application process

It was immersed for 3 minutes in a mixed aqueous solution (liquid temperature 25 ° C.) of 35 mass% hydrochloric acid 15 Oml / L and KYATALIST C (Okuno Pharmaceutical Co., Ltd.) 4 Om1 / L aqueous solution.

(4) First activation process

The molded body was immersed in a 98% by mass sulfuric acid 100 ml Z L aqueous solution (liquid temperature 40 ° C.) for 3 minutes.

(5) Second activation process

The molded body was immersed in a 15 g / L aqueous solution of sodium hydroxide (liquid temperature: 40 ° C) for 2 minutes.

(6) Nickel electroless plating process

The molded body was sandwiched and fixed with a metal jig 10 treated with the hard coating of Example 1, 2 or Comparative Example 1, and the portion of the covering portion 13 together with the molded body was bonded with chemical nickel HR-TA ( It was immersed in a mixed aqueous solution (liquid temperature 40 ° C) of 150 mlZL and chemical nickel HR-TB (manufactured by Okuno Pharmaceutical Co., Ltd.) 15 Om 1 / L for 5 minutes.

(7) Acid activation process

The molded body was immersed in 100 g / L aqueous solution (liquid temperature: 25 ° C.) for 1 minute in Topsun (manufactured by Okuno Pharmaceutical Co., Ltd.).

(8) Copper electroplating process

The molded body was immersed in the same bath (liquid temperature: 25 ° C.) as in Example 1 and electroplated for 120 minutes. table 1

The maximum values of the adhesion strength of the obtained plated resin moldings were all 1 ° 0 kPa, and the appearance was smooth and beautiful. However, even after the nickel electroless plating process, nickel plating was not deposited on the surface of the coated part 1 3 of the metal jig 10 treated with the coating material of Examples 1 and 2, but the comparative example Nickel plating was deposited on the surface of the coated portion 13 of the metal jig 10 treated with the coating material 1.

Claims

The scope of the claims

1. 0.1 to 100 parts by weight of a water-repellent resin and 0.1 to 100 parts by weight of a compound containing antimony and bismuth, if necessary, per 10 parts by weight of olefin resin Hard-to-stick coating.

2. The tacky coating agent according to claim 1, wherein the polyolefin resin is polyethylene and the water repellent resin is a fluororesin and Z ′ or a silicone resin.

3. A pretreatment method for plating, in which a non-sticking part according to claim 1 or 2 is powder-coated on a non-sticking part of a surface of a molded body.

4. Applying an insidiousness coating agent according to claim 1 or 2 to a metal jig for holding a resin molded body to be plated by powder coating, A pre-treatment method for metal plating so that metal jigs are not plated.

5. The plating pretreatment method according to claim 4, wherein the plating pretreatment method does not include a contact treatment step with an acid containing a heavy metal.