JPS6090257A - Polyphenylene ether resin composition with excellent plating properties - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyphenylene ether resin composition having poor plating sludge properties. More specifically, the present invention relates to a polyphenylene ether resin composition having excellent plating properties, which is obtained by blending a certain metal hydroxide into a mixture of a polyphenylene ether resin and a vinyl aromatic resin.

Polyphenylene ether resin is a resin with excellent heat resistance, electrical properties, and mechanical properties, and is disclosed in U.S. Patent No.
No. 506874, No. 3306875, No. 325735
It is a known resin disclosed in the specification of No. 7, No. 6257658 or No. 4011200, and Japanese Patent Application Laid-Open No. 126800/1983. Polyphenylene ether-based 41M resin has excellent heat resistance, so it is not easy to mold it, and heating is difficult, for example, as described in U.S. Patent No. 6.
As disclosed in Patent No. 386465 and No. 403.8345, it has been put to practical use as a composition with a vinyl aromatic resin.

By the way, in recent years, along with the trend of emphasis on weight reduction and decorativeness in various products such as the automobile and electronic equipment fields, plastics, which are lighter and easier to process than metals, are being used in various fields. It is expanding to Particularly in the automobile industry, weight reduction is being promoted as a measure to reduce fuel consumption, and the reality is that metals are being actively replaced by plastics. However, in the case of plastics, when exposed to light, heat, and even wind and rain, the surface glossiness decreases, discoloration, and physical property deterioration occur to varying degrees, and the durability of plastics is comparable to that of metals. The reality is that it does not come close to that. Therefore, it has become popular to plate plastics to improve their durability and make them more decorative.

The case of polyphenylene ether-based resin compositions is no exception, but even if the resin composition made of the above-mentioned polyphenylene ether-based resin and vinyl aromatic resin is directly plated, the adhesion strength of the plating film is low, making it impractical. do not have. Until now, from the application of ABS resin plating technology, it has been difficult to improve the adhesion strength of the plating film by increasing the content of the polybutadiene component in the polyphenylene ether resin composition. However, an increase in the polybutadiene component is undesirable because it causes a decrease in thermal stability, a decrease in heat distortion temperature, a decrease in flame retardancy, etc. Therefore, methods to avoid this drawback have been proposed, for example, in JP-A-5
No. 6-136841 discloses magnesium carbonate (MgC
By mixing one or more of O3), calcium carbonate (CaCO3), or magnesium oxide (MgO), a polyphenylene ether resin composition with improved plating properties without increasing the content of the polybutadiene component has been developed. j is shown. However, in this composition, unless a certain amount of carbonate and/or oxide is blended, an etching surface that has an anchoring effect for the plating film will not be formed on the surface of the molded product, and since a large amount of additives are blended, the composition It is difficult to avoid deterioration of the physical properties of objects.

The present inventors have conducted extensive research on resin compositions that can efficiently roughen the surface of molded products without increasing the content of poly-butadiene components, and have found that polyphenylene ether resin and vinyl The surface of a resin composition obtained by blending a certain metal hydroxide into a mixture with an aromatic resin is easily roughened when it comes into contact with an acid aqueous solution, and as a result, it exhibits excellent plating properties. Heading,
We have arrived at the present invention.

That is, the present invention is made by blending one or more metal hydroxides selected from the group consisting of magnesium hydroxide, calcium hydroxide, and aluminum hydroxide into an n compound of a polyphenylene ether resin and a vinyl aromatic resin. This is a polyphenylene ether resin composition with inferior plating properties.

The polyphenylene ether resin used in the present invention refers to polyphenylene obtained by polycondensing one or more monocyclic phenols represented by the general formula (I) (where R1 is a lower alkyl group having 1 to 5 carbon atoms, R2 and R3 are a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms, and a lower alkyl substituent must always be present at the ortho position of at least one of the hydroxyl groups. This refers to a graft copolymer having a polyphenylene ether as its base obtained by graft polymerization of a group compound. This polyphenylene ether may be a homopolymer or a copolymer.

Examples of the monocyclic phenol represented by the general formula (1) include 2,6-diethylphenol, 2,6-diethylphenol, 2,6-dipropylphenol, 2-
Methyl-6-ethylphenol, 2-methyl-6-propylphenol, 2-ethyl-6-propylphenol, m-cresol, 2,6-diethylphenol, 2゜6-diethylphenol, 2,5-dipropylphenol , 2-methyl-6-ethylphenol, 2-methyl-
6-propylphenol, 2-ethyl-6-methylphenol, 2-ethyl-3-propylphenol, 2-propyl-6-methylphenol, 2-propyl-5-ethylphenol, 2,5.6-)limethylphenol le,
2,5.6-Dryethylphenol, 2゜5.6-)dipropylphenol, 2,6-dimethyl-3-ethyl-
Phenol, 2,6-di-5-7'robilf alcohol, etc. are included. Examples of polyphenylene ethers obtained by polycondensation of one or more of these phenols include poly(2,6-cymethyl-1.
4-phenylene) ether, poly(2,6-dinityl-1,4-phenylene) ether, poly(2,6-diprobyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4) -phenylene) ether, poly(2-methyl-6-propyl-1,4-phenylene)ether, poly(2-ethyl-6-propyl-1,4)
-phenylene) needle, 2,6-dimethylphenol/2,5.6-drimethylphenol copolymer, 2.6
-dimethylphenol/2,5.6-driethylphenol co-combination, 2,6-dimethylphenol/2,3.
6-) Limethylphenol copolymer, 2,6-diprobylphenol/2,5. <S-) Limethylphenol copolymer, graft copolymer obtained by graft polymerizing styrene to poly(2,6-dimethyl-1°4-phenylene) ether, 2,6-dimethylphenol/2,5.6- Examples include a graft copolymer obtained by graft-polymerizing styrene onto a dolimethylphenol copolymer. In particular, poly(2,
6-dimethyl-1,4-phenylene)ether, 2,6
Preferred as the polyphenylene ether resin used in the present invention are a -dimethylphenol/2,5°6-dimethylphenol copolymer and a graft copolymer obtained by graft-polymerizing styrene to each of the former two.

The vinyl aromatic resin used in the present invention has at least 25 to 96 or more monomer structural units represented by the following general formula (Il) in its polymer (where R4 is a hydrogen atom or a lower alkyl group, 2 represents a halogen atom or a lower alkyl group, p is 0 or 1
It is a positive integer of ~5. ) resins, such as polystyrene, poly-p-methylstyrene, rubber-modified polystyrene (high-impact polystyrene), rubber-modified poly-p-methylstyrene, styrene-butadiene copolymer, styrene-butadiene-acrylonitrile copolymer, styrene-acrylic. Examples include acid rubber-acrylonitrile copolymer, styrene-α-methylstyrene copolymer, and styrene-butadiene block copolymer, and two or more of these may be used as a mixture.

The mixing ratio of the polyphenylene ether resin and the vinyl aromatic resin is generally 9515 to 5/95, preferably 90/10 to 10/90.

Regarding the magnesium hydroxide, calcium hydroxide, or aluminum hydroxide blended in the present invention, there are no particular restrictions on its properties as long as it has an etching effect with acid, but the average particle size is preferably 0.01 to 60μ, preferably A fine powder having a particle size in the range of 0.1 to 15 μm is preferably used. If the particle size exceeds the upper limit, the surface after painting or polishing will hardly become a so-called mirror surface, and the adhesion of the plating film will also be insufficient. On the other hand, if the particle size is smaller than the lower limit, the anchoring effect will not be sufficient and this is not desirable from the viewpoint of operability. The amount of these metal hydroxides is generally 5 to 25% by weight, preferably 7 to 2% by weight based on the total composition.
It is selected within a range that accounts for 0% by weight. If the amount is less than the lower limit, it will be difficult to obtain an etched surface with excellent anchoring effects, and if the amount exceeds the upper limit, the surface will become rough and the physical properties will deteriorate due to excessive etching, so the blending ratio must be carefully controlled. There must be.

Articles obtained using the resin composition of the present invention must be etched with an aqueous acid solution prior to chemical plating. Aqueous acid solutions that can be suitably used in the composition of the present invention include a mixture of chromic anhydride and concentrated sulfuric acid.

There is no restriction on the ratio of chromic anhydride to concentrated sulfuric acid as long as etching is carried out, but a saturated concentrated sulfuric acid solution of chromic anhydride is preferable.

As a method for plating the article made of the polyphenylene ether resin composition whose surface has been roughened in this manner, a method generally employed for plastic plating may be employed. In a very common method, the roughened molded part is immersed in an activating solution, then electroless plated to form a thin nickel or copper coating, and then electroplated to the desired extent. Forms a metal film.

In addition to the above-mentioned components, the resin composition of the present invention may contain various elastomer components or various additives that can be generally used in polyphenylene ether resin compositions.

The elastomer component is an elastomer in the general sense, and is described, for example, in "Properties and 5 structures" by A. V. Tobolsky.
es of Polymers” (John Wi.
ley & 5ons, Inc., 19 (50 years) 71
- You can quote the definition adopted on page 78 (Ellas) -
f- means Young's modulus at room temperature is 105 to 10' dy
nes/cml (0.1 to 1020%). Specific examples of elastomers include A-B-g
type elastomeric block copolymer, A-B-A' type elastomeric block copolymer in which the double bond in the polybutadiene portion is hydrogenated, polybutadiene, polyisoprene, copolymer of diene compound and vinyl aromatic compound , nitrile rubber, ethylene-propylene copolymer, ethylene-propylene-diene copolymer (EPDM), thiokol rubber, polysulfide rubber, acrylic acid rubber, polyurethane rubber, graft products of butyl rubber and polyethylene, polyester elastomer, polyamide elastomer, etc. Can be mentioned.

Various additives include the following.

Above all, flame retardants and stabilizers are important. Examples of the flammability agent include phosphorus-containing compounds and rogen-containing compounds. Phosphate compounds are commonly used as phosphorus-containing compounds, but phosphonate compounds and the like can also be used as long as they impart flame retardancy to the resin composition. Phosphate compounds include aromatic phosphate compounds and aliphatic phosphate compounds. Generally, the former is preferable because it has excellent heat resistance, but this does not preclude the use of the latter. Aromatic phospho-yz-zt compounds and compounds include triphenyl phosphate, tricresyl phosphate, talesyl diphenyl 7 phosphate, phosphates made from mixtures of isopropylphenol and phenol, and phosphates made from mixtures of isopropylphenol and phenol. Specific examples include a dimer of lephosphate. As the halogen-containing compound, chlorine compounds and bromine compounds are generally used, and bromine compounds are preferred. However, this does not preclude the use of the former.

Specific examples of the bromine compound include decabromo biphenyl, decabromo biphenyl ether, pentabromotoluene, brominated bisphenol A1 brominated polystyrene, polycarbonate oligomers produced using brominated bisphenol A, brominated polyphenylene ether oligomers, etc. .

Stabilizers include sterically hindered phenols, organic phosphites, phosphonites, phosphonasic acids, cyclic phosphonites, hydrazine derivatives, amine derivatives, carbamate derivatives, thioethers, phosphoric triamides, benzimidazole derivatives, metal sulfides, and the like. It will be done.

Other examples include polyolefin waxes as lubricants such as polyethylene wax and polypropylene wax; pigments such as titanium oxide, acids (lead 1, and carbon black).

The amount of these compounds added varies depending on the type of compound or the purpose of addition.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.
Unless otherwise specified, amounts are expressed on a weight basis. The tests in the examples were conducted according to the following methods. That is, there are various methods for evaluating the effect of surface roughening of a molded article by etching, but here we will use the most common method, which is the adhesion strength (adhesion strength) between the coated metal film and the base resin, as 1[1111111 (Peel strength)
We adopted the method shown below. Regarding this peel strength, 0
, 5 kg/art or more is considered to be 90% practical. Further, a problem with metal-plated resins is that, because the coefficients of thermal expansion of the resin and metal are different, drooping or cracking may occur if the temperature changes drastically. Therefore, a thermal cycle test is generally performed in which plated molded products are exposed alternately to an elevated atmosphere and a low-temperature atmosphere. The temperature conditions for the thermal cycle test are based on the base material.
ABS, which is a typical plating resin, differs depending on the lK.
In the case of resins, the temperature is between -30°C and 80°C.

In the case of the resin composition of the present invention, the heat distortion temperature differs depending on the resin composition, so considering the heat distortion temperature, -40 °C, 60 °C
The test was conducted for up to 6 cycles under conditions where one cycle was 110"C for 160 minutes.The abnormal state of the metal film after the test was observed with the naked eye, which was used as a criterion for judging the plating characteristics. Regarding the average particle diameter, the weight average diameter was measured by a light transmission centrifugal sedimentation method.

Examples 1-6 2.5. (S-)! 2,6-dimethylphenol/2,5.1 in which the proportion of methylphenol is 5 mol%.
6-) A mixture of a trimethylphenol copolymerized polyphenylene ether resin and a high-impact polystyrene resin, optionally containing an elastomeric polystyrene-polyptadiene-boris f-rene block copolymer and triphenyl phosphate, They were mixed in the proportions shown in Table-1, and various magnesium hydroxides were added to this mixture in the proportions shown in Table-1. After the mixture was preliminarily mixed in a tumbler, it was supplied to an A3-50fi twin-screw extruder (manufactured by Nakagama Seisakusho), where it was melted, kneaded, and pelletized. After drying the obtained pellet, it was supplied to a DM-40 injection molding machine (manufactured by Taki Seisakusho), and a test piece (12.5 pellets x 125 ms
It was molded to a thickness of 5 am.

After degreasing and washing the obtained test piece, chromic anhydride
400 g/-e and concentrated sulfuric acid (specific gravity 1.84') 2
Immerse in a mixed acid bath with 00a+z/Numa at 65℃ for 5 minutes,
Furthermore, it was treated with a commercially available neutralizing solution (TMP neutralizing solution and 3-200 aqueous solution sold by Okuno Pharmaceutical Co., Ltd.), and then a commercially available activating solution and chemical nickel plating solution were used. ) was subjected to chemical plating treatment.

The chemically plated test piece was coated with copper sulfate plating solution (composition:
CuSO4-5H20210grA; H2SO460
gr/4'', HC400 12 gr/-e; dextrin 0゜01 grμ; urea o, o 1
gr/-e) for 90 minutes at a current of 3°5A, and after washing with water, at 100°C.
It was dried for 1 hour to obtain a metal-coated test piece. Table 1 shows the results of measuring the peel strength of the plating film of these test pieces.
It was shown to.

Comparative Example 1 In Examples 1, 2.4, and 6, the same operations as in each Example were repeated except that magnesium hydroxide was not used, and the peel strength of the plated film of the obtained plated test piece was measured. In both cases, the value was 0.1 Yu/cIIL.

Examples 7 to 10 In Examples 1, 2.4 and 6, the same operations as in each Example were repeated except that various calcium hydroxides were used in the proportions shown in Table 2 instead of magnesium hydroxide. The peel strength of the plating film of the plated test piece was measured. The results are shown in Table-2.

Table 2 Examples 11 to 14 In Examples 7 to 1o, exactly the same operation was repeated except that magnesium hydroxide was replaced with aluminum hydroxide. The results are shown in Table-3.

Table 5 -1,4-7 Enylene) The same operation was repeated with exactly the same composition except that ether was used. The results are shown in Table 4.

Table 4 Examples 21 to 24 Same as Examples 7 to 10 except that poly(2,(S-dimethyl-1,4-phenylene) f-ter) was used instead of polyphenylene ether copolymer. The same operation was repeated with the same composition.

The results are shown in Table-5.

Table 5 Comparative Example 2 In Examples 21 to 24, the same operations as in each Example were repeated except that calcium hydroxide was not used, and the peel strength of the plated film of the obtained plated test piece was measured. It was also 0.1 to 9/cm.

Examples 29 to 31 and Comparative Example 6 42 parts and 58 parts of the polyphenylene ether copolymer and impact-resistant polystyrene used in Example 1 were used, respectively, and 10 parts of the various metal hydroxides shown in Table 6 were added. After preliminarily mixing the mixture in a tumbler, it was molded into a test piece in the same manner as in Example 1.

The obtained test piece was subjected to etching treatment and chemical plating treatment in the same manner as in Example 1, and then electroplating was applied in the following order and conditions.

The obtained plated test piece was subjected to a thermal cycle test, and changes in the plating film were observed. The results are shown in Table 6VC.

For comparison, a heat cycle test was conducted on a plated test piece using a composition containing no metal hydroxide, which was subjected to chemical plating and electroplating in the same manner as in Example 29.

The results are also listed in Table-6.

Electroplating order (1) Electrolytic copper plating solution composition: Copper sulfate 200 grμ Sulfuric acid 60 gr/chlorine ion 401n9V/8 Conditions: 20°C, 4A/dm, 45 minutes (4 Electrolytic nickel plating solution composition: Nickel sulfate 240 gr/ Nickel chloride 45 gr/13 Hydrolic acid 50 gr/g Brightener Q"7 Talin-1,5-disulfo-, [1-1') 5 gr/1 Formalin 1.5 cc/4 Conditions = 40°C, 4A/d Go, 10 minutes (5) Electrochrome plating

Claims (1)

[Claims] It has excellent plating properties and is made by blending one or more metal hydroxides selected from the group consisting of magnesium hydroxide, calcium hydroxide, and aluminum hydroxide into a mixture of polyphenylene ether resin and vinyl aromatic resin. Polyphenylene ether resin composition