JPS60181275A - Metal plated molded article of unsaturated polyester resin - Google Patents

Abstract

PURPOSE:To enable metal plating on a molded article of unsatd. polyester resin by incorporating rubber contg. butadiene combined optionally with an inorg. filler into the unsatd. polyester resin. CONSTITUTION:When a molded body of unsatd. polyester resin is coated with metal by chemical plating or electroplating, the molded body is formed by molding a mixture consisting of 100pts.wt. unsatd. polyester resin and 1-40pts.wt. rubber contg. butadiene and having 1,000-200,000 average mol.wt. such as acrylonitrile-butadiene-styrene rubber. To the mixture may be added 30-180pts. wt. inorg. filler of 0.5-20mum average particle size such as calcium carbonate, clay or aluminum hydroxide. Chemical plating or electroplating which is not applicable to a molded body of only unsatd. polyester resin can be carried out.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a metal-plated unsaturated polyester resin molded article.

Unsaturated polyester resin molding materials are characterized by their moldability,
Because of its good working environment, it is widely used in fields such as bathtubs, tanks, septic tanks, building materials, industrial parts, automobile parts, and electrical parts. However, despite attempts to apply metal plating to the surface of unsaturated polyester resin molded products to impart hardness, abrasion resistance, radiant heat resistance, conductivity, decorative properties, etc., unsaturated polyester resin still remains unsaturated. The metal plating technology for resin molded products has not been established, and there is a drawback that metal-plated molded products cannot be obtained1, so its development is strongly desired1.

In view of the above-mentioned circumstances, the present inventors investigated the amount of iron in order to obtain a metal-plated unsaturated polyester resin molded product. Metal plating with good adhesion is possible by using a method (chemical plating method) or a combination of electroless plating method and electroplating method.
The present inventors have discovered that the adhesion of metal plating can be further improved by adding an inorganic filler in addition to the rubber containing the butadiene component, and have completed the present invention.

That is, the present invention provides a metal plating characterized by having a metal plating layer on an unsaturated polyester resin layer containing an unsaturated polyester resin, a rubber containing a butadiene component, and further an inorganic filler as necessary. The present invention provides an unsaturated polyester resin molded article.

The unsaturated polyester resin used in the present invention includes α
.

It is produced by polycondensation of β-unsaturated dibasic acid or its acid anhydride, aromatic saturated dibasic acid or its acid anhydride, and glycols. Examples include those obtained by dissolving 30 to 80 parts by weight of an unsaturated polyester produced in combination with a basic acid in 70 to 20 parts by weight of an α,β-unsaturated monomer; It also includes those with vinyl-modified ends, and vinyl esters with vinyl-modified ends of epoxy skeleton.

Examples of the α,β-unsaturated dibasic acids or their acid anhydrides used in the present invention include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chlormaleic acid, and esters thereof. Examples of saturated dibasic acids and their acid anhydrides include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, halogenated phthalic anhydride, and esters thereof. Examples of aliphatic or alicyclic saturated dibasic acids include cono-phosphoric acid,
Examples include adipic acid, sebacic acid, hexahydrophthalic anhydride, and esters thereof, each of which may be used alone or in combination. Examples of glycols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1.6-butanediol, 1,4-butanediol, neopentyl glycol, triethylene glycol, 1.5-bentanediol, and 1.6-butanediol. -Hexanediol, bisphenol A1, hydrogenated bisphenol A, 2,2-di(4-hydroxypropoxyphenyl±propane, etc.), which may be used alone or in combination; in addition, oxides such as ethylene oxide, propylene oxide, etc. Also, polycondensed metals such as polyethylene terephthalate can be used as part of the glycols and acid components.As the α,β-unsaturated monomers, styrene, vinyltoluene, α-methylstyrene, chloro Styrenic compounds such as styrene,
Examples include vinyl monomers or vinyl oligomers that can be crosslinked with unsaturated polyesters such as acrylic compounds such as methyl methacrylate and allyl compounds such as triallyl cyanurate, and are used alone or in combination, but styrene is generally used. used.

Examples of the rubber containing a butadiene component used in the present invention include acrylonitrile 5-monophtadiene-styrene rubber, styrene-butadiene rubber, neoprene-butadiene rubber, and polybutadiene rubber having an average molecular weight of 1,000 to 200,000, each of which may be used alone or Used in combination.

Among these, styrene-butadiene rubber is preferred because it has good compatibility with unsaturated polyester resins. Note that the rubber containing these butadiene components can be mixed with the unsaturated polyester resin in the form of a solution dissolved in an α,β-unsaturated monomer such as styrene.

The amount of rubber containing a butadiene component used is usually 1 to 40 parts by weight, preferably 6 to 20 parts by weight, per 100 parts by weight of the unsaturated polyester resin.
If it is less than part by weight, metal plating with good adhesion cannot be obtained.
If it exceeds 40 parts by weight, the viscosity of the molding material will increase significantly;
It becomes difficult to use it as a molding material, and each is undesirable.

Inorganic fillers that can be used in the present invention include calcium carbonate, clay, and clay having an average particle size of 0.5 to 20 μm.
Examples include aluminum hydroxide, each of which may be used alone or in combination. Among these, calcium carbonate is preferred because it dissolves in a chemical etching solution such as a chromic acid mixture and particularly improves the adhesion of metal plating. The amount of the inorganic filler added is usually 0 to 300 parts by weight, preferably 30 to 180 parts by weight, based on 100 parts by weight of the unsaturated polyester resin. Incidentally, it is also possible to use conductive powder such as carbon powder or graphite powder in combination.

Furthermore, the unsaturated polyester resins can be cured using conventional curing catalysts such as benzoyl peroxide, methyl ethyl ketone peroxide, lauroyl peroxide, cumene hydroperoxide, dicumyl peroxide; t-butyl perbenzoate, dimethylaniline, cobalt naphthenate, etc. conventional curing accelerators such as cobalt octoate, diptylthine dilaurate, etc., fiber reinforcements such as glass fibers, graphite fibers, organic fibers, milled fibers, cotton flock, whiskers, etc., zinc stearate. Conventional mold release agents such as other organic or inorganic pigments, thermoplastics such as polystyrene, polyacrylates, polyvinyl acetate, saturated polyesters, low shrinkage agents such as fats, etc. can be added.

Further, the unsaturated polyester resin can be β-staged (thickened) in sheet form by adding at least one compound selected from alkaline earth metal oxides, alkaline earth metal hydroxides, and polyisocyanates. , is preferably used as a molding material. The amount added is unsaturated polyester resin 1
The amount is usually 1 to 20 parts by weight, preferably 5 to 10 parts by weight, based on 00 parts f.

Examples of alkaline earth metal oxides used here include magnesium oxide, calcium oxide, etc., examples of alkaline earth metal hydroxides include magnesium hydroxide, calcium hydroxide, etc., and polyisocyanates include, for example, Tetramethylene diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 1.6-cyclohexane diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2.4-4 lylene diisocyanate, 2.6-) lylene diisocyanate, Diisocyanates such as naphthalene diisocyanate; polyfunctional polyisocyanates such as polymethylene polyphenylisocyanate; Known and commonly used polymers such as isocyanate prepolymers may be mentioned.

The method for molding the unsaturated polyester resin molding material obtained as described above is not particularly limited, and any known unsaturated polyester resin molding method can be used.

As a method for metal plating an unsaturated polyester resin molded product, a well-known electroless plating method (chemical plating method) is used, for example, the surface of the unsaturated polyester molded product is plated with methanol, ethanol, inglobil alcohol, acetone, trichloroethane, etc. After degreasing and washing with water, chemical etching is performed. For chemical etching, a chromic acid mixture (for example, a mixture of a saturated aqueous solution of potassium dichromate and concentrated sulfuric acid), a non-chromium etching solution (for example, a mixture of permanganate and phosphoric acid), etc. can be used. can. Next, after performing pre-treatments such as sensitizing treatment and activating treatment, non-10-electrolytic plating is performed to coat nickel, chromium, silver, copper, nickel, gold (e.g. nickel-phosphorus, nickel-boron). etc. are attached to the surface of the molded product. More preferably, various metals such as copper, nickel, chromium, zinc, cadmium, tin, gold, silver, brass, bronze, etc. are electroplated,
An example is a method of completing metal plating. Note that metal plating can be performed repeatedly as necessary, and the thickness thereof is usually 0.1 to 50 μm each.

The metal-plated chemical molded product of the present invention has excellent surface hardness, abrasion resistance, radiation heat resistance, surface conductivity, radio wave reflection properties, and decorative properties, and is applicable to fields such as electrical and electronic parts, automobile parts, and industrial parts. can do.

EXAMPLES The present invention will be explained in more detail by showing Examples and Comparative Examples below. In addition, all parts and percentages in the examples are based on weight.

Example 1 Maleic anhydride 19'6# (2 mol), phthalic anhydride It
148g (1 mole), propylene glycol 228II
60 parts of an unsaturated polyester obtained by dehydrating (3 mol) in an inert gas stream at 200 to 220°C while stirring were mixed and dissolved in 40 parts of styrene with 0.005 part of hydroquinone. An unsaturated polyester resin having a value of 20 and a hydroxyl value of 15 was obtained. 60 parts of a styrene solution (concentration: 30%) of JSR8L-556 (SBR rubber manufactured by Japan Synthetic Rubber (1), butadiene content: 76%) was mixed with 100 parts of this dried sardine one-phase polyester resin. Next, 15 parts of a styrene solution (concentration 50%) of polystyrene (molecular weight 26,000) was mixed as a low shrinkage agent, and further 150 parts of calcium carbonate, 5 parts of zinc stearate, 1 part of t-butyl perbenzoate, and 1.5 parts of magnesium oxide were added. 5 parts were added and kneaded to obtain an unsaturated polyester resin compound, S
An SMC molding material having a 1-inch glass roving chop content of 25% was prepared using an MC impregnation machine. After aging for 24 hours, it was heated to 50ky/in a mold heated to 140℃.
crI? .

A 30×30α unsaturated polyester resin flat plate was molded for 4 minutes. After degreasing the flat surface of the obtained molded plate with trichloroethane, chromic acid 42[[', concentrated sulfuric acid 2oo
Chromic acid mixture (70°C) consisting of a mixture of cc and 11 parts water
It was immersed in water for 15 minutes to perform chemical etching. After washing with water,
10 g of stannous chloride and 40 cc of concentrated hydrochloric acid were added to water 11. The mixture was immersed in a solution (25°C) for 5 minutes (sensitizing), washed with water, and then 15 cc of palladium chloride 0511 concentrated hydrochloric acid was added to water 11. It was immersed (activated) in a liquid (35°C) for 2 minutes. After washing with water and aqueous phase treatment, water 17
．． 60g of nickel sulfate, 20g of sodium hypophosphite, 40I of sodium citrate! , immersed in an aqueous solution (30° C.) of 28% ammonia water 25 ee for 10 minutes, and subjected to electroless dipping (thickness: 02 μm). Then water 1
11 Copper sulfate 220 F1 Aqueous solution of 250 g of concentrated sulfuric acid (2
After electrolytic copper plating (thickness: 6 μm) was performed for 20 minutes at 6 Vb 1.5 A/dm (0°C), water was 11sf, nickel oxide was 60011, nickel chloride was 50II, and boric acid was 35.9mm. Electrolytic nickel plating (thickness: 4.5 μm) was performed in an aqueous solution (20° C.) at 6 V and IA/dm for 10 minutes. The plated plate obtained had no bulges, cracks, or wrinkles on the surface, and had good adhesion (cross cut test: 100/100).

Example 2 Maleic anhydride (19612 moles), isophthalic acid (166 moles)
,? (1 mol), propylene glycol (22813 mol)) were subjected to a condensation reaction in the same manner as in Example 1, and the acid value was 18.
An unsaturated polyester resin having a % hydroxyl value of 14 and a styrene content of 30% was obtained. This unsaturated polyester resin 10
60 parts of a styrene solution (#30%) of 14-5olprene 312 (manufactured by Philips Vetroulium Co., Ltd., SBR butadiene containing 70%) was mixed with 0 parts. Next, 150 parts of calcium carbonate, 5 parts of zinc stearate, 1 part of t-butyl perbenzoate, and 1.5 parts of magnesium oxide were added and kneaded to obtain an unsaturated polyester resin compound. This compound was made into 8MC in the same manner as in Example 1 and used as a molding material. This was press-molded under the conditions of 140°C, 50'Q/cm'', and 4 minutes to produce a 30x30cm unsaturated polyester resin flat plate.Next, electroless plating and electroplating were performed in the same manner as in Example 1. The plated plate thus obtained had no blisters, cracks, or wrinkles on its surface, and its adhesion (crosscut test 100/100) was good for insects.

Example 3 Kaolin AsP-4oop instead of calcium carbonate
A flat plate was prepared in the same manner as in Example 1, except that the plated plate (manufactured by Ueya Kaolin Kogyo ■) was used, and electroless plating and electrolytic plating were performed.
No wrinkles, adhesion (cross cut test 100/10)
0) was also good.

Example 4 A flat plate was prepared in the same manner as in Example 1, except that 2 parts of carbon powder GEST 116 (manufactured by Tokai Carbon ■) was further added to the compound of Example 1, and electroless plating and electrolytic plating were performed. The obtained plated plate has no blisters, cracks, or wrinkles on the surface, and has good adhesion (cross force test) 1
00/100) was also 1 favorable.

Example 5 To 100 parts of the unsaturated polyester resin obtained in Example 1, 30 parts of a styrene solution of JSR5L-556 (+# degree 30%) was mixed. Next, 5 parts of zinc stearate, 1 part of t-butyl perbenzoate, and 4,4 parts of diphenylmethane
6 parts of '-diisocyanate were added and kneaded to obtain an unsaturated polyester compound, and a 91-inch sheet-like molding material having a glass roving chip content of 50% was produced using an impregnation machine. A flat plate was prepared in the same manner as in Example 1 except that this molding material was used, and electroless plating and electrolytic plating were performed. The plated plate obtained has no bulges, cracks, or wrinkles on the surface, and has good adhesion (cross cut test 100/100).
) also had a good Q.

Comparative Example 1 A flat plate was prepared in the same manner as in Example 1 except that the styrene solution of JSR8L-556 was omitted, and chemical plating and electrolytic plating were performed. The plated molded plate obtained had bulges and cracks on the surface, and its adhesion (cross cut test) was 20/20.
100) was defective.

17- Comparative Example 2 0.1 part of 6% cobalt nanthenate and 1 part of 55% MEK peroxide were added to 100 parts of the unsaturated polyester resin obtained in Example 1, and a chopped self-strand mat [45011,/m2 , made by Nippon Glass Fiber ■] 3ply
Example 1 except that a molding material obtained by impregnating with
A flat plate was prepared in the same manner as above, and chemical plating and superposition plating were applied, but the plating did not adhere.

Agent: Patent Attorney Katsutoshi Takahashi 18-

Claims (1)

[Claims] A metal-plated nonwoven fabric characterized by having a metal plating layer on an unsaturated polyester resin layer containing an unsaturated polyester resin, a rubber containing a butadiene component, and optionally an inorganic filler. Saturated polyester resin molded product.