JPS5829852A - Polyester resin composition capable of plating - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which has good moldability and gives plated moldings having excellent bond strength by conventional methods, consisting of a mixture composed of two specified kinds of thermoplastic polyester resin. CONSTITUTION:The titled compsn. contains 0-100pts.wt. reinforcing fiber per 100pts.wt. mixture consisting of a thermoplastic polyester resin (A) in which the combined amount x of sulfoisophthalic acid and/or sulfoterephthalic acid based on the total amount of the acid component is within the range of 02<x<= 100mol%, the amount y of terephthalic acid is within the range of 0<=y<= 99.8mol% and alcohol component consists mainly of ethylene glycol, and a thermoplastic polyester resin (B) composed mainly of ethylene terephthalate repeating units in such a proportion that the amount of said sulfoisophthalic acid and/ or sulfoterephthalic acid based on the total amount of the acid component in said polyester resin mixture (A+B) is 0.2-20mol%.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyester resin composition that has excellent adhesion to metal plating films.

Polyethylene terephthalate resin has excellent mechanical properties,
It has heat resistance, chemical resistance, and resistance to chemicals, and is used as an engineering plastic in various electrical and mechanical parts, but metal-plated products that give it a metallic appearance are similar to conventional ABS resin. It is expected that it will be applied to new fields that require heat resistance and mechanical strength that were not available with polypropylene resin plated products.

When plating resin, surface roughening (etching) is required before plating. Since polyester resin is relatively stable against acidic solutions, it is possible to roughen the surface by contact treatment with an alkaline solution. However, it is possible to plate this polyester resin treated with an alkaline solution. The adhesion between the plating film and the polymer was weak, posing a practical problem.

The present inventors completed the present invention as a result of various studies to solve this problem.

In the present invention, the total amount X of isophthalic acid sulfonate and/or terephthalic acid sulfonate is 0 with respect to the total amount of acid components.
．． 2 (x≦100 mol% and the amount y of terephthalic acid is 0
≦Y<99.8 mol%, and mixture 1 of thermoplastic polyester resin A whose alcohol component is mainly ethylene glycol and thermoplastic polyester resin B whose repeating units are mainly ethylene terephthalate.
00 parts by weight, the fibrous reinforcing material is 0 to 100 parts by weight, and the converted amount of isophthalic acid sulfonate and/or terephthalic acid sulfonate in the polyester resin mixture (A+B) is 0 to 100 parts by weight relative to the total amount of the acid component. .2-20
It is a polyester resin composition for metal plating, characterized in that it is mol%.

The thermoplastic polyester resin A used in the present invention contains at least one compound of the following formula and terephthalic acid as an acid component, and a major amount of ethylene glycol as an alcohol component. The total amount X of the sulfonates is 0.2 (x≦100 mol%, preferably x =
1 to 60 mol%, and the amount y of terephthalic acid is 0≦Y<
Al at 99.8 mol%. The amount of ethylene glycol is generally 75 mol% or more, especially 80% by mole based on the total alcohol content.
It is preferably mol% or more. Polyester resin A further includes:
Other acid components such as isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, adipic acid, sebacic acid, etc., and other alcohol components such as trimethylene glycol, propylene glycol, tetramethylene glycol, neopentyl glycol, hexamethylene glycol, etc. , dodecamethylene glycol, etc., may each be contained in small amounts. The intrinsic viscosity of resin A is preferably 0.3 or more, particularly 0.5 or more.

The chilled resin B of the other thermoplastic polyvarnish used in the present invention consists of ethylene terephthalate in the main amount of repeated monochrome, preferably 75 mol% or more, and the following copolymer components are used. It will be done. Examples of dicarboxylic acid components include isophthalic acid,
Adipic acid, sebacic acid, p-β-oxyethoxybenzoic acid, diphenyl ether-4,4'-dicarboxylic acid,
Diphenoxyethane-4,4'-dicarboxylic acid, etc. or alkyl ester derivatives thereof, etc.; examples of glycols include propylene glycol, butanediol, hexamethylene glycol, neopentyl glycol, cyclohexane dimetatool, etc.; The intrinsic viscosity of resin B is 0.6
Above, 0.5 or more is particularly preferable.

By mixing thermoplastic polyester resins A and B, the equivalent amount of isophthalic acid sulfonate and/or terephthalic acid sulfonate in this resin mixture (A + B) is 0.2 to 20 mol% based on the total amount of acid components. is important. If the amount of sulfonate is less than 0.2 mol %, the effect of the present invention is insufficient, and if it exceeds 20 mol %, the moldability will be significantly reduced.

The polyester resin composition of the present invention may further contain a fibrous reinforcing material in addition to the resins A and B described above. Typical examples include glass fiber, carbon fiber, and asbestos fiber. The amount of these added is 0 to 1 per 100 parts by weight of the thermoplastic polyester resin mixture (A and B).
00 parts by weight, preferably 0 to 80 parts by weight.

The mechanical strength tends to increase as the amount of fiber reinforcing material added increases, but if it exceeds 100 parts by weight, it becomes difficult to manufacture and mold the polyester resin composition, making it impossible to obtain a plated product with a good appearance. .

The polyester resin composition of the present invention may further contain silicic acid and/or silicate using inorganic light Q+ as an agent. Addition of an inorganic filler can prevent deformation during molding. The amount added is 0 to 90 parts by weight per 100 parts by weight of the polyester resin mixture (A+B). If you add more than this,
The mechanical strength of the molded product decreases, and the appearance of the plated product also becomes poor. Examples of silicates include kaolin, Merck,
Clay, white carbon, carplex, etc. are used. Two or more types of inorganic fillers may be used in combination.

The composition of the present invention comprises the thermoplastic polyester resin A
and B, a fibrous reinforcing material and an inorganic filler are mixed in a conventional manner. Various methods are used for mixing, but each component is kneaded uniformly using an extruder,
Dispersion is preferred.

The thermoplastic polyester resin composition of the present invention may contain additives other than those mentioned above, such as colorants, crystal nucleating agents, plasticizers, and lubricants, for the purpose of improving various other properties, as long as they do not impair the effects of the present invention. , blowing agents, flame retardants, stabilizers, fillers, etc. can be added.

Conventional methods can be used to plate the polyester resin composition of the present invention, for example, as follows.

A molded article is produced from a polyester resin composition by a conventional method, and the article is first degreased. For this purpose, for example, an organic agent such as methyl ethyl ketone or acetone or a surfactant is used. Although degreasing is not necessarily necessary, degreasing is particularly preferred when the surface of the molded product is contaminated with a mold release agent, oil, or the like. After degreasing and washing with water, etching is performed by immersing it in an alkaline solution such as caustic soda, caustic potash, or aqueous ammonia. Next, after neutralizing the alkali, a catalyst for chemical plating is provided.

Methods for providing a catalyst include a sensitization-activation method, a catalyst-accelerator method.

In the former case, first a relatively strong reducing agent such as stannous chloride, hypophosphorous acid, or hydrazine chloride is adsorbed onto the resin surface.
Next, the resin is immersed in a catalyst solution containing noble metal ions such as gold, silver, palladium, etc. to precipitate the noble metal on the resin surface and provide a catalyst.

On the contrary, it is also possible to first immerse the resin in a solution containing noble metal ions to adsorb the noble metal ions, and then reduce the resin in a reducing agent solution to precipitate the noble metal on the resin surface and provide a catalyst.

This method is typically a catalyst application method in which the resin is immersed in a tin-palladium mixed catalyst solution and then activated with an acid such as hydrochloric acid or sulfuric acid to precipitate palladium on the resin surface.

For chemical plating performed after catalyst provision, a known chemical plating bath generally consisting of components such as a metal salt, a reducing agent, and a pH adjuster can be used. Examples of metals that can be plated include copper, nickel, silver, tin, cobalt, and tin-cobalt alloys, and copper and nickel are excellent in terms of liquid stability and adhesion.

Next, electroplating is performed by a conventional method. Examples of metals that can be electroplated include copper, nickel, and chromium, and known electroplating baths can be used. The liquid components, additives, and film thickness can be changed depending on the purpose, and it is also possible to form a multilayer electroplated film.

The polyester resin composition of the present invention has good moldability, and by using this molded product, a plated molded product having excellent adhesion strength can be obtained by the above-mentioned plating method.

Example 1 0.1 to 100 mol% of isophthalic acid m-sulfonate, isophthalic acid 〇-sulfonate or terephthalic acid sulfonate as acid components and 999 to 999 mol% of terephthalic acid
Polyethylene terephthalate B is mixed in a predetermined ratio to thermoplastic polyester A consisting of 0 mol % alcohol and 100 mol % ethylene glycol (see Table 1). Note that both polyesters A and B were previously dried with hot air at 140° C. for 4 hours.

To 100 parts by weight of this polyester resin mixture (A+B), 0.2 parts by weight of a crystal nucleating agent and 25 parts by weight of chopped glass fibers having a length of 3 mW were added, mixed in a tumbler, and then mixed using a 901RrILφ extruder. The strands are melted and combined at a cylinder temperature of 260° C., and the strands coming out of the die are cooled and cut to produce pellets for molding. Using this pellet, a test molded product is injection molded in a 6-ounce injection molding machine under the conditions of a cylinder temperature of 270°C, a resin pressure of 500 kg/CIrL2, a mold temperature of 160°C, and a molding cycle of 40 seconds.

The obtained molded product was heated at 60°C for 5 minutes using a commercially available degreasing liquid (Engrate PC-4526097, e manufactured by Enson).
Degrease for a minute and rinse with water. Next, it is immersed in a 5N aqueous solution of sodium hydroxide at 60°C for 15 minutes, and then in a 10% by volume aqueous hydrochloric acid solution at 26°C for 5 minutes. The molded product whose surface has been roughened in this manner is subjected to electrolytic copper plating according to the conventional method shown below.

a) Catalyst Imposition The surface-roughened molded product is immersed in a commercially available catalyst solution (Catalyst A-30 manufactured by Okuno Pharmaceutical Co., Ltd.) at 35° C. for 4 minutes, and then washed under running water. Then, it was immersed in a 10% by volume H2SO4 aqueous solution at 40°C for 3 minutes, and thoroughly washed under running water.

b) Chemical nickel plating Chemical nickel plating solution (Okuno TMP manufactured by Yoyaku Okuno Co., Ltd.)
After soaking at 35°C for 5 minutes, wash with water.

C) Electrolytic copper plating In an aqueous solution containing 200 g/2 copper sulfate, 50 g/sulfuric acid, and 1 cc/1 brightening agent (Niecilite Co., Ltd. Nivac 1) at a temperature of 20'C1 and a current density of 4 A/+]m"
Electrolytic copper plating is carried out under the conditions of: and 60 minutes to form a plating film with a thickness of about 4 μm on the resin molded product.

Table 1 shows the film adhesion strength of the plated molded product thus obtained. The adhesion strength is measured by pulling a 1-inch wide plating film with a tensilon at a pulling speed of 5 mm for 7 minutes, and the strength when the tension is balanced is defined as the adhesion strength.

From Table 1, it is clear that when the converted value of isophthalic acid sulfonate or terephthalic acid sulfonate in the polyester mixture (A+B) increases, a molded article with high adhesion strength to the plating film can be obtained. However, if this amount is too large, molding becomes difficult.

Example 2 Polyester A in which 10 mol% of isophthalic acid m-sulfonate was copolymerized with ethylene terephthalate was
Dry with hot air at 40°C for 4 hours. This polyester A and
Polyethylene terephthalate (B) which has been previously dried with hot air at 140° C. for 4 hours is mixed in so/sO (weight ratio).

Isophthalic acid m- in polyester mixture (A+B)
The equivalent value of sulfonate is 5 mol%. Next, to 100 parts by weight of the mixture (A+B), 0 to 100 parts by weight of an inorganic filler shown in Table 2, further 0.2 parts by weight of a crystal nucleating agent, and 20 parts by weight of chopped glass fiber having a length of 611 were added, After mixing in a tumbler, pellets for molding are produced using a 55 m 1 φ extruder at a cylinder temperature of 260°C. Using this pellet, the cylinder temperature was 265℃.
, injection pressure 500kg/cIrL2 and mold temperature 130
Injection mold specimens for plating at °C. Using this test piece, degreasing, etching, catalyst application, chemical plating, and electroplating are performed in the same manner as in Example 1. The adhesion strength, amount of molding warpage, and appearance of the metal coating of the plated molded product obtained were
Shown in the table. Adhesion strength was measured in the same manner as in Example 1.

The amount of molding warpage is 1l10x110x2 under the above molding conditions.
A square plate of No. 1 was molded, and it was calculated from the diagonal length of the molded product and the warp height using the following formula.

Table 2 From the results shown in Table 2, it is recognized that by adding an inorganic filler, the amount of warpage is reduced and the adhesion strength is also slightly increased.

Example 3 Polyester A, which is obtained by copolymerizing 6 mol% of terephthalic acid sulfonate with respect to ethylene terephthalate, is mixed with polyethylene terephthalate B at a ratio of 5°150 (weight ratio). The converted value of terephthalic acid sulfonate in the polyester mixture (A+B) is 6 mol%. A plated molded article was produced in the same manner as in Example 1 except that the amount of glass fiber added to the mixture (A1B) 1 oO weight parts was changed. Table 3 shows the adhesion strength and appearance.

Table 6 From the results in Table 6, it is clear that the addition of glass fibers improves the adhesion strength. However, if the amount of glass fiber added is too large, the appearance will be poor.

Applicant: Mitsubishi Rayon Co., Ltd. Agent: Patent attorney Masao Kobayashi

Claims (1)

[Claims] 1. The total amount X of isophthalic acid sulfonate and/or terephthalic acid sulfonate based on the total amount of brewing ingredients is 0.
2 < X6 100 mol% and the amount y of terephthalic acid is 0
≦Y<99.8 mol%, and 100 parts by weight of a mixture of thermoplastic polyester resin A whose alcohol component is mainly ethylene glycol and thermoplastic polyester resin B whose repeating units are mainly ethylene terephthalenite. 0 to 100 parts by weight of the fibrous reinforcing material, and the converted amount of isophthalic acid sulfonate and/or terephthalic acid sulfonate in the polyester resin mixture (A+B) is 0.0 to 100 parts by weight based on the total amount of the acid component. 2～
A polyester resin composition for metal plating, characterized in that the content is 20 mol%. 2. Thermoplastic polyester resin mixture (A and B) 100
The composition according to claim 1, characterized in that it contains 90 parts by weight or less of silicic acid and/or silicate based on the weight of the composition.