JPS59142244A - Production of surface-metallized resin molding - Google Patents

Abstract

PURPOSE:To produce the titled molding having excellent plate adhesion and good surface appearance, by plating a molding composed of a blend obtd. by mixing a small quantity of a polyamide with a thermoplastic polyester resin. CONSTITUTION:1-100pts.wt. polyamide or modified polyamide such as nylon 6 is incorporated in 100pts.wt. thermoplastic polyester resin such as polyethylene terephthalate to obtain a resin compsn. which is then molded. The surface of the molding is roughened and then plated to produce a surface-metallized resin molding. By mixing a small quantity of the polyamide (modified polyamide), there can be obtd. a molding having excellent plate adhesion and good surface appearance while retaining excellent characteristics inherent to the thermoplastic polyester resin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a resin acid 1 mainly based on thermoplastic polynis-til.
The present invention relates to a method for producing a surface-metallized resin molded product with excellent plating film adhesion and (1) good surface appearance by plating a 1'9 product.

Polyethylene foam clay I and polybutylene terephthalate
Aromatic polyester resins represented by 1. have excellent mechanical properties, heat resistance, and adhesive resistance, so they are used for door applications such as electrical parts and mechanical parts. Furthermore, these aromatic polyester resin molded products are given a metallic appearance, and these metal-coated products retain the characteristics of the aromatic polyester resin itself (conventional moldings).
ABS resin and polypropylene metal-coated products have the ability to cut and tighten, and are expected to expand into new fields.

Generally, the plating treatment for plastics is (1) +iJ
Treatment, (2) Roughening treatment (etching) v (3) Sensitivity treatment (t!@ treatment (senonotaijinoku), (4)
R finishing treatment (activation process), (51) electroless plating and (6) electroplating are performed in sequence, and the steps after the above (3) are usually called the plating process. However, the roughening treatment described in item 1 (2) is important in the subsequent plating process!It is an important factor that affects the adhesion of the metal plating film.Various methods are used depending on the type of plastic. For example, AB
For S resin, a chemical etching method has been established in which the crystals are immersed in a chromic acid-sulfuric acid mixture.

% ijJ As a means of roughening the surface during plating of plastic polyester resin, the molded product is immersed in an alkaline hydroxide solution.
'M Wi method θmi (Japanese Unexamined Patent Publication No. 53-68741j' Public￥IJ,), a method of immersing a molded product in a phenol solution and then further immersing it in an alkaline aqueous solution (Japanese Unexamined Patent Publication No. 53-68
75 Publication) and a method of treating a molded article with a crystallization solution of alcohol, alkali, and water (Japanese Unexamined Patent Publication No. 54-68877).
Since the surface of a plated product cannot be eroded in one minute, it is necessary to pre-contain fillers such as Karasu Fiber 1 or carbonate lunoum in the polyester resin, and even then, the desired rough surface cannot be achieved. The adhesion of the plating film is poor, and it is practically impossible to obtain a polyester resin molded product with metalized surface.

Therefore, the inventors of the Wood Inventors conducted research with the aim of obtaining a plated product with excellent performance in surface metallization by metal plating of thermal CiJ plastic polyester resin. By plating a molded product made of a mixture of a small proportion of polyamide 1- or its modified product, the low elasticity of the thermoplastic polyester resin itself is maintained, and the plating r+
qs Surface metallization with low adhesion and good surface appearance I! 'It was discovered that a polyester molded product could be obtained.

That is, the present invention provides heat 71J WJ t? 4) After molding a resin composition containing 1 to 100 parts by weight of a modified form of boria j+-mats based on 100 parts by weight of polyester, the resin composition is subjected to a roughening treatment and then to a plating treatment. The present invention provides a method for producing a characteristic surface metallized resin acid +1g product.

The thermoplastic polyester resin used in the present invention is a polymer or copolymer containing only a dicarbono acid component and a diol component as its minor components. Here, the dicarboxylic acids referred to as -C include terephthalic acid, inophthalic acid, orthophthalic acid, 2
．． 6-7clercarbonic acid, 1. ! 4.
4′-lephenyl dicarboxylic acids and their ester-forming derivatives, adipinic acid,
Examples include alicyclic dicarboxylic acids such as sepatsunoic acid, azelaic acid, and dotecanonoic acid, and ester-forming derivatives thereof. The diol components include fats having 2 to 20 carbon atoms, namely ethylene glycol, furopyrenochlicol, 1,4-butal]-ol, neopentyl glycol, 1゜5-benotalol, 1,6-hexalol, tecamethylene glycol, cyclohexane dimethol, cyclohexane leol, etc., or long chain glycols with a molecular weight of 400 to 6,000, i.e. polyethylene glycol, poly-1,3--- Examples include propylenochlicol, polytetramethidi/glycol, and their ester 11-linked derivatives, and two or more of these can be used in combination.

Specific examples of these aromatic polyester resins include polyethylene terephthalate, polyethylene naphthalate,
Polybutylene naphthalate polypropylene terephthalate, polybutylene terephthalate, polybutylene terephthalate 1-〇 isophthalate, polybutylene terephthalate sebake-1-, polyhexamethylene terephthalate L/
-+-, sr linochlohexanodimethylenoterephthalate 1- and mixtures thereof, among which polybutylene terephthalate and polyethylene terephthalate i, which have good mechanical properties, are particularly preferably used. SajL.

The aromatic polyester resin of these 15 is 0.5% 0.
- A relative viscosity of a chlorophenol solution measured at 25° C. is preferably in the range of 1.2 to 20, particularly 13 to 1,85.

Boria 2D or a modified product thereof used in the present invention is a well-known polyamide having repeated carbonamide bonds in the polymer chain or a modified product of polyamide (7) thereof,
Examples include polyamides, copolyamides, polyesteramides, polyethyl esteramides, and mixtures thereof obtained by polymerization of lactams and aminocarboxylic acids, polycondensation of salts of raremino and dicarboxylic acids, and the like. Specific examples of these include nylon 6, nylon 66, nylon 1], nylon 12. Nylon 6/66, nylon 6/10, nylon 6/]2, boria 2 and copolyamides, and polyesteramides obtained by polycondensing terephthalic acid, 1,4-getanoneol, and 2-aminototicic acid, etc. Examples include polyamide modified products of.

, IF IJ amide maj, the amount of its modified product added is determined by heat I
jJW (1 to 100 parts by weight of colored polyester resin)
It is preferably 100 parts by weight, especially 3 to 80 parts by weight. If it is less than 1 part by weight, the effect of improving the adhesion of the plating film will be insufficient, and if it exceeds 100 parts by weight, the mechanical properties of the thermal iTJ plastic polyester resin itself will deteriorate. The heat resistance is low, so it is preferable to use it for 7 days.

In addition, when mixing thermoplastic polyester resin and polyamide or its modified product, titanium oxide, zinc oxide, magnesium oxide, silicon oxide, potassium titanate, magnesium carbonate, calcium carbonate, pyrolunum carbonate, manetium, pyrolunum metasilicate, barium sulfate, talc,
Fillers such as kaolin, clay, limestone, mica, asbestos, siloid, alumina (aluminum oxide), shirasu balloons, and shirasu balloons can be added, and by doing so, it is possible to expect even stronger plating film adhesion strength. can.

However, the amount of these fillers added is 3 to 300 parts by weight, especially 5 parts by weight, per 100 parts by weight of the thermoplastic urester resin.
The range of ~200 parts [■ parts] is preferable. In addition, other usual additives such as lubricant, mold release agent, nucleating agent, iiJ plasticizer, 5NG
Fuel, heat stabilizer, ultraviolet absorber, pigment, dye 14゛l,
A fiber 1, 11 reinforcing agent and other thermoplastic resins can be added as necessary.

The thermoplastic polyester resin, polyamide or modified product thereof, and other additives may be blended in any manner, such as a method in which they are simultaneously mixed in a screw extruder or the like.

For manufacturing resin molded products from the compound, any conventional thermoplastic resin molding methods such as injection molding, extrusion molding, and blow molding can be used, and polyester resin molded products for plating in desired shapes can be easily obtained. can.

When performing matting treatment using the method of the present invention, first perform preliminary steps such as wiping off the oil film on the surface of the molded product as necessary.
It is important to perform the i1ft treatment and then roughen the surface using an alkaline solution and an acidic solution.

The alkaline solution used for surface roughening treatment refers to 5 to 50% alkali components such as potassium hydroxide, lithium hydroxide, and magnesium hydroxide in a solvent such as water, phenols, alcohols, or a mixed solvent thereof. Among them, solutions of thorium hydroxide and potassium hydroxide are preferably used.

The conditions for this surface roughening treatment (alkaline etching) using an alkaline solution are as follows: 1.
It is recommended to soak for ~120 minutes and then thoroughly rinse.

Acidic liquids used for surface roughening treatment include sulfuric acid, hydrochloric acid, phosphoric acid,
Examples include mineral acids such as nitric acid, and organic acids that are liquid at room temperature such as formic acid, acetic acid, and trifluoroacetic acid, and these acids alone and in mixtures, as well as aqueous solutions of 5% or more, are sulfuric acid.

Hydrochloric acid, nitric acid, phosphoric acid, formic acid, etc. are preferably used.

The conditions for this surface roughening treatment (acid etching) using an acidic solution are preferably to immerse the product in an acidic solution at 20 to 95° C. for 10 seconds to 2 hours, and then thoroughly wash it.

To promote surface roughening, an appropriate oxidizing agent can be added to the alkaline solution and acidic solution.As an oxidizing agent, potassium permanganate, potassium permanganate, Dichromates, chlorates, chromates, and bromates are preferred.

In the case of molded products made of thermoplastic polyester resin, even if this alkaline or acidic treatment is applied, the surface will be eroded evenly and unevenness that is effective for plating adhesion will not occur, or the degree of surface erosion will be too high. However, when applying alkaline etching or acid etching, especially alkaline etching, to a thermoplastic polyester resin molded product containing a small proportion of polyamide or its modified product, plating treatment is necessary. A rough surface is obtained that is extremely suitable for This effect is presumed to be due to the fact that the degree of erosion becomes greater due to the difference in solubility (decomposition) in alkali and acid between the thermoplastic polyester resin and the polyamide or its modified product.

By subsequently subjecting the resin molded product subjected to the surface roughening treatment in this manner to a conventional plating treatment, it is possible to obtain a surface metallized polyester resin molded product with extremely excellent plating film adhesion and a good surface appearance.

Plating processes include, for example, electroless copper or nickel plating (electroplating), electroless copper or nickel plating (electroplating), electroless copper or nickel plating (electroplating), electrolytic plating (electroplating), electroless copper or nickel plating (electroplating), electroless copper or nickel plating (electroplating), electrolytic plating (electroplating), electroless copper or nickel plating (electroplating), electroless copper or nickel plating (electroplating), electroless copper or nickel plating (electroplating), electrolytic plating with parareum chloride solution A conventional chemical plating method can be applied.

The effects of the present invention will be further explained below with reference to Examples.

Example 1 Polyzothyrenoterephthalate (P) with a relative viscosity of 1.575
BT)', the polyamides and their modified products shown in Table 1, and other additives were blended in the proportions shown in Table 1, and melt-kneaded and chimped using a screw extruder set at 250°C. It became.

Next, this chip was set at 250°C and submitted to a T-co injection molding machine, and the mold temperature was 80°C, 80 questions x 80 questions x 3'
A square plate test piece of .wm was molded.

100 parts by weight of polyethylene terephthalate (PET) with a relative viscosity of 1.425 was blended with the same pJ of polyamide, its modified product, and other additives in the types and proportions shown in Table 1, and extrusion melt-kneaded to chip. A square plate test piece was formed by injection molding. In this case, the temperature of the extruder and injection molding machine was 280°C, and the temperature of the gold plate was 30°C.
The temperature was ~40°C.

Next, the specimen marked "-" was immersed in a 30% I-lium hydroxide aqueous solution at 70°C for 3 minutes, further immersed in a 20% hydrochloric acid aqueous solution at 70°C for 2 minutes, and then thoroughly washed under running water to roughen the surface. A test piece was obtained.

This roughened test piece was subjected to plating treatment by the method shown below.

■Cenonotidinog: test piece with 30g of stannous chloride
, 5Qcc of hydrochloric acid (38%) and 1,000cc of water
Immerse in a solution consisting of for 2-5 minutes at 25°C.

■ Washing with water ■ Activating Nog...Pass the test piece with palladium chloride 0
．． 1 g, hydrochloric acid (38%) lQcc and water 1.000
Immerse in a solution consisting of c c for 1-3 minutes at 25"C.

■Water washing■Electroless copper plating... test piece with copper sulfate (5% hydrate)
10v, formalin (37%) 40cc, hydroxide I・
Rium 10g, Rotunel J1. ．． A chemical cuprate consisting of 20 g of T and 1.000 c of water.

Liquid (pT (10.0 to 11.5)) D Soaked at 25 to 30°C for 10 minutes.

■Water washing■Electroplating...The test piece was washed with 50g of concentrated sulfuric acid, copper sulfate (50g)
% hydrate) 200p, brightener (UBAC Ebara Corellai 1 ~ Co., Ltd. product) 4cc and water 1.000cc
Placed in an acidic steel plating bath consisting of
Electroplating was performed for 60 minutes under conditions of current density 4 A/d, , i' to form a copper plating film with a thickness of about 60 mm.

Regarding the plated products thus obtained, the adhesion of the plating film was measured and the surface appearance was visually judged. The adhesion strength of the plating film was determined by measuring the force (g) when peeling the ILyR width adhesive surface in the 90' direction at a speed of 20 mm/min.

These results are shown in Table 1.

As is clear from the results in Table 1, by blending a small proportion of polyamide 6 and its modified product, the adhesion strength of the plating films of polyester resin molded products increases dramatically.

Patent applicant Higashi Shikikai Co., Ltd.

Claims (1)

[Claims] A resin composition comprising 100 ffi parts of thermoplastic polyester and 1 to 1'00 ffi parts of polyamide or a modified product thereof is molded, then roughened, and then plated. A method for manufacturing a surface metallized resin molded product.