JPH0363585B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a resin plating product using a plating transparent ABS resin composition that can be subjected to wet plating. Resin-plated products obtained by plating transparent ABS resin, especially plating products that have been partially plated, have light transmittance in the unplated areas (non-plated areas), so the transmitted light intensity and It has an information display function using a change in the color of transmitted light as a signal. For example, by symbolizing the shape of the unplated portion, the state of the function identified by the symbol can be displayed. To give an example of a specific embodiment, it is applied to switches and push buttons of light electrical parts, and by converting the shape of the non-metallic part into letters, it is possible to turn on the switch or push button indicated by the letters.
−OFF status can be displayed. Although resin-plated products obtained by plating transparent ABS resin products are industrially useful, there are very few practical examples. This is due to the fact that it is difficult to treat. Resin-plated products have a large difference in linear expansion coefficient between the metal phase and the resin phase, so the plating layer tends to peel off from the resin surface as the environmental temperature changes, and this is especially noticeable in transparent ABS resin products. Generally, in order to produce transparent ABS resin, it is necessary to match the refractive index of the rubber dispersed phase and the resin continuous phase, and for this purpose, it is necessary to add methyl methacrylate to the monomer group that makes up the resin continuous phase. Usually done. However, according to the findings of the present inventors, when a compound having an ester bond is contained in the resin continuous phase, the plating adhesion of the ABS resin plating product is extremely poor. For this reason,
In order to obtain a transparent ABS resin plated product with sufficient plating adhesion for practical use, wet plating must be applied to a transparent ABS resin consisting of a resin continuous phase that does not contain a compound having an ester bond, specifically, methyl methacrylate. is necessary. As a result of intensive studies in view of the above findings, the present inventors found that ABS resin containing diene rubber having a weight average particle diameter of 150 mμ or less and general formula [] General formula [] [In the formula, R ₁ is an alkyl group, R ₂ and R ₃ are H and/or methyl groups, R ₄ and R ₅ are each H or -C(O)R ₆ (R ₆ is an alkyl group), m and n are
Each integer from 1 to 20] By using a resin composition containing a compound represented by the following, it is possible to achieve superior plating adhesion compared to conventional resin plating products made of transparent ABS resin containing methyl methacrylate. heading,
The present invention has been completed. That is, the present invention is a resin plating product made by wet plating, and the active ingredient of the product is ABS containing 5 to 30% by weight of diene rubber having a weight average particle size of 150 mμ or less.
100 parts by weight of resin and general formula [] General formula [] [In the formula, R ₁ is an alkyl group, R ₂ and R ₃ are H and/or methyl groups, R ₄ and R ₅ are each H or -C(O)R ₆ (R ₆ is an alkyl group), m and n is
Transparent with 0.1 to 10 parts by weight of a compound each represented by an integer of 1 to 20]
This is a resin plating product characterized by being made of an ABS resin composition. Hereinafter, the present invention will be explained in detail. The transparent ABS resin used in the present invention is obtained by emulsion polymerization of a monomer mixture containing a vinyl cyanide monomer and an aromatic vinyl monomer in the presence of a diene rubber latex having a specified particle size. . The diene rubbers mentioned here include poly(butadiene) poly(isobrene), poly(chloroprene), poly(butadiene-styrene), poly(butadiene-methyl methacrylate), poly(butadiene-acrylonitrile), etc. Examples of the monomer include acrylonitrile and methacrylonitrile, and examples of the aromatic vinyl monomer include styrene, α-methylstyrene, t-butylstyrene, and vinyltoluene. The diene rubber of the transparent ABS resin used in the present invention has a weight average particle diameter of 150 mμ or less, preferably
It is 100mμ or less. For ABS resins containing diene rubber with a weight average particle diameter exceeding 150 mμ,
It has poor transparency and is not suitable for the purpose of the present invention. The transparent ABS resin used in the present invention needs to contain 5 to 30% by weight of diene rubber. If the diene rubber content is less than 5% by weight, the plating adhesion will be poor, and if it exceeds 30% by weight, the fluidity will decrease, which is not preferred. The transparent ABS resin used in the present invention has a particle size of 150m.
Do not reject the mixing of diene rubber with large particle size of μ or more. In this case, the amount of large particle diameter diene rubber mixed in may be within a range that keeps the weight average particle diameter of all diene rubber in the ABS resin to 150 mμ or less.
The addition of a large particle size diene rubber often has a positive effect on plating adhesion to the product, and the following method can be used to introduce the large particle size diene rubber. That is, the first is a method in which a small particle size diene rubber latex and a large particle size diene rubber latex are mixed in advance and then subjected to emulsion graft polymerization, and the second is a method in which one of the rubber latexes is mixed during the emulsion graft polymerization or during the polymerization. After completion of the emulsion graft polymerization, the other rubber latex is added into the system to continue the emulsion graft polymerization.The third method is to separately emulsion graft polymerize a small particle size diene rubber latex and a large particle size diene rubber latex, and then This is a method of mixing both.
In the present invention, any of the above methods can be employed. Further, the transparent ABS resin used in the present invention may be a mixture of 8 to 100% by weight of ABS resin containing 5 to 62.5% by weight of diene rubber and 0 to 92% by weight of AS resin. If the diene rubber content is less than 5% by weight, the ABS resin will have poor plating adhesion to the product, and if it exceeds 62.5% by weight, silver streaks will occur on the surface of the molded product, which is undesirable. Furthermore, the applicable
AS resin is a copolymer of vinyl cyanide monomer and aromatic vinyl monomer. Here, the vinyl cyanide monomer is acrylonitrile, methacrylonitrile, etc. Examples of such substances include styrene, α-methylstyrene, t-butylstyrene, and vinyltoluene. Next, the transparent ABS resin composition that is the raw material for the resin-plated product of the present invention has the following general formula [] with respect to 100 parts by weight of the transparent ABS resin: [In the formula, R ₁ is an alkyl group, R ₂ and R ₃ are H and/or methyl groups, R ₄ and R ₅ are each H or -C(O)R ₆ (R ₆ is an alkyl group), m and n is
Each integer of 1 to 20] Contains 0.1 to 10 parts by weight of a compound represented by:
In the formula, the alkyl groups of R ₁ and R ₆ are methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, etc. However, the carbon chain may have an unsaturated bond. Also, the integers of m and n are each
If it exceeds 20, the compatibility with the transparent ABS resin will be poor, which is undesirable. Further, in the compound of the general formula [], it is particularly preferable that R ₁ is a higher alkyl group of hexyl or higher, and m and n are each an integer of 1 to 10. When the compound represented by the general formula [] is manufactured industrially, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and m and n are strictly defined as one structure or one numerical value. It is difficult to manufacture them as pure compounds, and they are usually manufactured as mixtures with different structures and/or numerical values. In the present invention, there is no problem in using a mixture of compounds represented by the general formula []. The compound represented by the general formula [] is
It is preferable to have a boiling point of 200°C or more, and if the boiling point is less than 200°C, a transparent material containing the compound
When molding ABS resin compositions, molding defects such as silver streaks are sometimes observed. In the transparent ABS resin composition that is the raw material of the present invention,
0.1 to 10 parts by weight of the compound represented by the general formula [] to 100 parts by weight of transparent ABS resin, preferably 0.5 parts by weight
-8 parts by weight, but if the content of the compound represented by the general formula [] is less than 0.1 parts by weight,
The improvement effect of product plating adhesion strength is insufficient,
If it exceeds 10 parts by weight, it is not preferable because it not only reduces the plating adhesion strength of the product but also impairs the rigidity and heat resistance of the plated product made of transparent ABS resin. Next, as a technique for applying wet plating to a product molded from the transparent ABS resin composition that is the raw material of the present invention, a known technique used for ordinary ABS resin products can be applied. In addition, wet plating may be applied to the entire product or to parts of the product. In order to partially process the product, the non-plated parts may be covered with a masking material. −
The technology is disclosed in Japanese Patent No. 124432 and the like, but the present invention is not limited to these technologies. The present invention will be specifically explained below with reference to Examples, and all parts and percentages in the Examples and Comparative Examples are expressed on a weight basis. Reference example 1 (Manufacture of ABS-1) 280 parts of pure water in an autoclave, weight average particle size
A poly(butadiene) latex with a small particle size of 60 mμ (solid content 35%) was collected to a total solid content of 100 parts, and to this was added 1.0 part of potassium stearate, 0.0075 part of ferrous sulfate, and 0.015 part of sodium ethylenediaminetetraacetate. , 0.45 part of sodium formaldehyde sulfoxylate was added, and the mixture was heated to 50° C. with stirring. Here 45 parts of acrylonitrile, styrene
A mixed solution consisting of 105 parts of t-dodecyl mercaptan, 0.9 parts of diisopropylbenzene hydroperoxide, and 0.3 parts of diisopropylbenzene hydroperoxide was continuously added over 5 hours. After the addition was completed, 0.15 part of diisopropylbenzene hydroperoxide was further added, and the mixture was stirred at 70°C for 2 hours to complete the polymerization. The yield was 98%. A calcium chloride aqueous solution was added to the obtained polymer latex to recover the graft polymer. 45 parts of this graft polymer and acrylonitrile
The mixture was mixed with 55 parts of a styrene suspension copolymer (AS resin - acrylonitrile content 25%) and fed into an extruder to form pellets. The obtained transparent ABS resin is designated as ABS-1. Reference example 2 (Manufacture of ABS-2) 560 parts of pure water in an autoclave, weight average particle size
60mμ small particle size poly(butadiene) latex 95
(as solid content - solid content 35%), large particle size poly(butadiene-styrene) with a weight average particle diameter of 550 mμ
5 parts latex (as solids - styrene content)
25%, solids 50%), potassium stearate 1.0
1 part, 0.015 part of ferrous sulfate, 0.03 part of sodium ethylenediaminetetraacetate, and 0.9 part of sodium formaldehyde sulfoxylate, and heated to 50°C under stirring.
heated to. 75 parts of acrylonitrile, 225 parts of styrene, 1.8 parts of t-dodecyl mercaptan, and diisopropylbenzene hydroperoxide.
A mixture of 0.6 parts was added continuously over 5 hours. After the addition was completed, 0.3 part of diisopropylbenzene hydroperoxide was further added, and the mixture was stirred at 70°C for 2 hours to complete the polymerization. The yield was 98%. A calcium chloride aqueous solution was added to the obtained polymer latex to recover the polymer. 72 parts of this polymer and acrylonitrile-styrene suspension copolymer AS resin-acrylonitrile content
25%) were mixed and fed into an extruder to form pellets. The obtained transparent ABS resin is designated as ABS-2. Reference example 3 (Production of ABS-3) Production of graft polymer A ₁ 560 parts of pure water in an autoclave, weight average particle size
60mμ small particle size poly(butadiene) latex
100 parts (as solids - 35% solids), 1.0 part potassium stearate, 0.015 part ferrous sulfate, 0.03 part sodium ethylenediaminetetraacetate, 0.9 part sodium formaldehyde sulfoxylate;
The mixture was heated to 50° C. with stirring. acrylonitrile here
A mixed solution consisting of 75 parts of styrene, 225 parts of styrene, 1.8 parts of t-dodecylmercaptan, and 0.6 parts of diisopropylbenzene hydroperoxide was continuously added over 5 hours. After the addition was completed, 0.3 part of diisopropylbenzene hydroperoxide was further added,
The polymerization was completed by stirring at 70°C for 2 hours. The yield is
It was 98%. Production of graft polymer B ₁ 270 parts of pure water in an autoclave, weight average particle size
550mμ large particle size poly(butadiene-styrene)
100 parts latex (as solids - 25% styrene content, 50% solids), potassium stearate 2.0
1 part, 0.005 part of ferrous sulfate, 0.01 part of sodium ethylenediaminetetraacetate, and 0.3 part of sodium formaldehyde sulfoxylate, and heated to 50°C under stirring.
heated to. Here are 25 parts of acrylonitrile, 75 parts of styrene, 0.6 parts of t-dodecylmercaptan, and diisopropylbenzene hydroperoxide.
A mixture of 0.2 parts was added continuously over 3 hours. After the addition was completed, 0.1 part of diisopropylbenzene hydroperoxide was further added, and the mixture was stirred at 70°C for 2 hours to complete the polymerization. The yield was 96%. Mixing and pelletization After mixing 28 parts of graft polymer A ₁ latex (as a solid content) and 1 part of graft polymer B ₁ latex (as a solid content) in a latex state, an aqueous calcium chloride solution is added to form a polymer. was recovered. 30 parts of an acrylonitrile-styrene suspension copolymer (AS resin-acrylonitrile content: 25%) was mixed with 70 parts of this mixed graft polymer, and the mixture was fed into an extruder to form pellets. The obtained transparent ABS resin is designated as ABS-3. Next, the pellets of ABS-1, 2, and 3 were injection molded using an IS80CN-V injection molding machine manufactured by Toshiba Machine Co., Ltd. at a molding temperature of 240°C to obtain a flat molded product of 80 x 50 x 3 mm. The total light transmittance of this molded product is
When measured in accordance with ASTM D-1003,
The percentages were 64.5%, 60.6%, and 61.9%, respectively. In addition, the melt flow index of ABS-1, 2, and 3 was determined using a method based on JIS K6870 (250℃,
When measured with a load of 5Kg), each was 18.0g/10
minutes, 19.2 g/10 minutes, and 19.4 g/10 minutes. Example 1 and Comparative Example 1 ABS-1, 2, and 3 and the compound represented by the formula [] were fed in the amounts shown in Table 1 to an extruder to obtain pellets. formula〔〕 This pellet is made into IS80CN- manufactured by Toshiba Machine Co., Ltd.
Injection molded with a V injection molding machine at a molding temperature of 240℃,
A flat molded product measuring 80 x 50 x 3 mm was obtained. The total light transmittance of this molded product was determined and summarized in Table 1. Furthermore, the letters "PLAY" were screen printed on one side of the center of the molded product using a vinyl chloride resin masking ink, and the vicinity of the corresponding area on the back side was widely covered with the same masking ink, and then wet plating was performed according to the following steps. The letters "PLAY" were clearly legible on all of the obtained metsuki products under transmitted light. "Wet plating process" Degreasing (isopropyl alcohol) room temperature x 5 seconds Etching (chromic anhydride-sulfuric acid mixture) 70℃
-15 minutes Neutralization (hydrochloric acid) room temperature x 2 minutes Catalyzing (palladium chloride-stannic chloride-hydrochloric acid aqueous solution) room temperature x 2 minutes Acceleration (sulfuric acid aqueous solution) 55℃ x 2
Minutes Chemical plating (Nickel sulfate - Sodium citrate - Sodium hypophosphite - Sodium acetate - Ammonium chloride aqueous solution) 32℃ x 5 minutes Electrolytic copper plating (20μ thickness) Electric nickel plating (7μ thickness) Chrome plating (0.3μ thickness) A resin-plated plate obtained by wet-plating the flat molded product without masking was left in an 85°C environment for 2 hours, and then immediately placed in a -30°C atmosphere for 2 hours. A transparent plate with 5 mm grids drawn on it was placed on the resin plating board after the heating-cooling cycle, and the number of grids from which the plating layer had peeled off was counted. The front and back surfaces of the resin-plated board were measured, and the number of peeled squares was totaled, which was defined as the "number of peeled-off squares." The results are summarized in Table 1. Example 2 The same procedure as in Example 1 was performed except that the compound represented by formula [] was used in the amount shown in Table 2 instead of the compound represented by formula [], and the number of plating peeled off was determined. I asked for The measurement results are summarized in Table 2. formula〔〕 Example 3 and Comparative Example 2 Except for changing the mixing ratio of the graft copolymer and AS resin of ABS-1 as shown in Table 3,
It was treated in the same manner as in Example 1. The physical property measurement results are summarized in Table 3. Comparative Example 3 Pellets were obtained in the same manner as in Reference Example 1, except that the weight average particle diameter of poly(butadiene) used in emulsion graft polymerization was 200 mμ. The total light transmittance of a molded plate obtained by molding this pellet according to the method described in Example 1 was 0%.

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Claims (1)

[Scope of Claims] 1. A resin plating product obtained by wet plating, wherein the active ingredient of the product has a weight average particle diameter of 150 m.
100 parts by weight of ABS resin containing 5 to 30% by weight of diene rubber having a particle size of less than μ and general formula [] General formula [] [In the formula, R ₁ is an alkyl group, R ₂ and R ₃ are H and/or a methyl group, R ₄ and R ₅ are each H or -C(O)R ₆ (R ₆ is an alkyl group), m and n is an integer of 1 to 20] 0.1 to 10 parts by weight of the compound represented by
A resin plating product characterized by being made of an ABS resin composition.