KR830002459B1 - Thermoplastic resin composition with excellent thermal circulation - Google Patents

Abstract

No content.

Description

Thermoplastic resin composition with excellent thermal circulation

The present invention relates in particular to a thermoplastic resin composition for plating having excellent heat cycling properties, a molded article molded from such a resin composition, and a plated article having excellent thermal cycling properties obtained by plating the aforementioned molded article.

In general, plastic plated products have a large difference in the coefficient of linear expansion between the metal side and the resin layer, and therefore, an undesirable peeling phenomenon between the plated metal layer and the resin layer due to a change in the environment in which the product is used (particularly a temperature change) It is well known that "swelling" occurs. The characteristics of plastics and plastic-plated products that cause this phenomenon are called monocyclic. In recent years, the demand for plastic plating products is increasing, the size and complexity are increasing, and they have been used under strict conditions for the purpose of light weight or cost reduction. Therefore, plastics having better de-thermal circulation, processability, and releasability are required. It became.

Conventionally, although ABS resin (acrylonitrile buradiene-styrene copolymer) is widely used as a representative resin suitable for plastic plating, this also does not fully satisfy the above-mentioned requirements. Moreover, as a means of improving salt circulation, the method of fearing a plating film (for example, copper: 40-50 micrometers, nickel: 10-20 micrometers, chromium: 0.1-0.3 micrometers) is known, but the effect is also not enough. The present inventors have made intensive studies for the purpose of developing a resin composition for plating with better thermocyclability, processability and mold release property without impairing the excellent impact resistance, heat resistance and chemical resistance of the conventional ABS resin. The present invention has been completed by finding a resin composition having excellent thermocyclability.

The gist of the present invention is 5 to 95 parts by weight of a graft polymer (A) which is grafted 10 to 90% by weight of aromatic vinyl and 5 to 50% by weight of vinyl cyanide to 5 to 80% by weight of conjugated diene rubber, and 40 to 90 of aromatic vinyl. 95 to 5 parts by weight of the copolymer (B) and 60 to 10 parts by weight of vinyl cyanide and 0.05 to 3.0 parts by weight of the organosilicon compound (C), and 5 to 80 parts by weight of the conjugated diene rubber 5 to 50 parts by weight of a graft composite (A) grafted with 10 to 90% by weight of aromatic vinyl and 5 to 50% by weight of vinyl cyanide, 40 to 90% by weight of aromatic vinyl, and 60 to 10% by weight of vinyl cyanide It exists in the thermoplastic resin composition for plating which consists of coalescing (B), 95-5 weight part, organosilicon compound (C) 0.05-3.0 weight part, and lubricant (D) 0.05-3 weight part.

Although the above-mentioned composition is excellent in circulatory property, the latter composition containing lubricant is further excellent also in workability and mold release property.

The present invention also relates to a plated product obtained by plating a molded article and a molded article molded from such a resin composition. In any of the resin compositions described above and also in any plating product, the conjugated diene rubber is prepared in such a way that it forms 5 to 60% by weight of the true weight of the composition.

The graft synthetic body (A) used in the present invention is grafted with 10 to 90 wt% of aromatic vinyl and 5 to 50 wt% of vinyl cyanide to 5 to 80 wt% of conjugated diene rubber. Although there are polymerization methods such as emulsion-suspension polymerization, block polymerization, block-suspension polymerization and solution polymerization, emulsion polymerization, suspension polymerization or glass suspension polymerization is preferred in view of the thermocyclability of a plated product.

When the graft composite body outside the above numerical range is used, not only the thermal cycling properties of the plated product but also the physical and chemical properties of the resin composition for plating are poor, which is not preferable.

Copolymer (B) is 40 to 90 weight% of aromatic vinyl and 60 to 10 weight% of vinyl cyanide, and the manufacturing method is not restrict | limited at all. When the amount of aromatic tin used is outside the range of 40 to 90% by weight, not only is the thermocyclability of the plated product, but also the physical and chemical properties of the plating resin composition is not preferable.

It is preferable that the intrinsic viscosity of a copolymer (B) is 0.4-0.8 (dimethylformamide, measured at 30 degreeC). When the intrinsic viscosity is excessively high, the workability of the thermoplastic resin composition is poor, and further, the dispersibility of the organosilicon compound is poor, and it is difficult to obtain a plating product having a homogeneous and excellent thermocyclability. On the other hand, when the intrinsic viscosity is too low, the etch resistance of the thermoplastic resin composition is bad, overetching tends to be difficult to obtain a good plated product.

Regarding each component constituting the graft polymer (A) and the copolymer (B), the conjugated diene rubber is a polyburadiene, a styrene-butadiene copolymer and / or an acrylonitrile-butadiene copolymer, and the aromatic vinyl is a styrene, α-methylstyrene, vinyltoluene and halogen substituted styrene, and vinyl cyanide is preferably acrylonitrile and or methacrylonitrile.

As the organosilicon compound (C), the formula

Polysiloxanes represented by (R ₁ to R ₄ represent lower alkyl or aryl groups), silane compounds represented by R ₁ R ₂ R ₃ R ₄ Si (R ₁ to R ₄ represent lower alkyl or aryl groups) Or organic halo silanes represented by R ₃ -nSiXn (n is an integer of 1 to 3, R is a lower alkyl or aryl group, X represents a halogen). Specifically, polysiloxanes such as polydimethylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, polydiethylsiloxane, silanes such as tetraethylsilane, trimethyl hexylsilane or triethylchlorosilane, diethyldichlorosilane, phenyl trichloro Halosilanes, such as rosilane and phenyl dichlorosilane, are preferable.

In view of the mixing operation of the graft polymer (A), the copolymer (B) and the organosilicon compound (C), the viscosity of these organosilicon compounds is preferably 10 ¹ to 10 ⁵ CPS.

As the lubricant (D), which may be mixed as desired, various lubricants described in "Plastic" No. 19, No. 2, issued by the Industrial Society, can be used, but liquid paraffin, low molecular weight polyethylene, higher fatty acids, fatty acid amides, Particular preference is given to alkylenebisfatty acid amides, lower alcohol esters of fatty acids, polyhydric alcohols of fatty acids, polyglycol esters of fatty acids and fatty alcohol esters of fatty acids. These can be used individually or in mixture of 2 or more types.

The usage-amount of a graft synthesis body (A) is 5-95 weight part. If it is less than 5 parts by weight, the amount of the copolymer (B) is relatively large, the monocyclic properties of the resin composition and the adhesion strength with the metal film are remarkably inferior, and further, the physical properties such as impact resistance are inferior, and thus cannot be put to practical use. If the amount is more than 95 parts by weight, the mobility of the resin composition, heat resistance, and the like decrease, and the thermal circulation of the plated product is also reduced.

The usage-amount of an organosilicon compound (C) is 0.05-3.0 weight part. If the amount of use is less than 0.05 part by weight, uniform dispersion cannot be obtained, and a resin composition and a plated product excellent in thermocyclability are not obtained. Moreover, when it exceeds 3.0 weight part, the completion | finish is bad at the time of addition and kneading | mixing, Furthermore, since the heat cycling property and heat resistance of the obtained plating product fall, it is unpreferable.

The usage-amount of the lubricant (D) added as desired is 0.05-3.0 weight part. If the amount used is less than 0.05 part by weight, no uniform dispersion is obtained, and releasability from the mold at the time of molding is poor. Moreover, when it exceeds 3.0 weight part, the sliding phenomenon by a lubricant will arise at the time of kneading | mixing and shaping | molding, and sufficient resin kneading can be performed. Moreover, the heat resistance etc. of a resin composition fall, and improvement of thermocyclability also cannot be desired.

The plated product excellent in the thermal cycling property which concerns on this invention is obtained by plating on the molded article formed from the above-mentioned resin composition for plating. As the shaping bob, any of the injection molding method and the extrusion molding method may be used. Moreover, as a method of plating on a molded article, the method of dreaming, for example, the method to display on the following flowchart art 1, can be used.

Flow Chard 1

Degreasing (surfactant solution) 55 ° C x 3 minutes

↓

Etching (lactic acid-chromic anhydride mixture) 67 ~ 70 ℃ × 15 minutes

↓

Neutralization (Aqueous hydrochloric acid solution)

↓

Catalyst (Palladium Chloride-Tin Chloride-Aqueous Hydrochloric Acid) Greenhouse × 2 minutes

↓

Accelerator (Lactic acid aqueous solution) 45 ℃ × 3 minutes

↓

Electroless plating (nickel plating solution mainly composed of nickel lactate, sodium hypophosphite, sodium quene acid)

↓

Electroplating (dong jade → nickel ohmium → chromic anhydride)

Copper plating is carried out in a conventional plating method such as that shown in Pulley Charat 1, but this is necessary in order to alleviate the effects due to the difference in linear expansion between the plastic and metal films. However, such copper plating is not preferable in that it causes corrosion. Therefore, the so-called double nickel plating and trinickel plating except for copper plating may be performed, but in this case, there is a contradiction that the thermal circulation is remarkably inferior. However, in the case of a molded article molded from the resin composition according to the present invention, a product having a double nickel plating or a trinickel plating is also excellent in thermocyclability.

Although an Example demonstrates this invention concretely below, this invention is not restrict | limited at all by the Example described here.

Example 1

The graft composite (A), copolymer (B) and organosilicon compound (C) were mixed at the compounding ratios shown in Table-1 to obtain compositions 1 to 12 (Kneading conditions: Benbury mixer, 190-300 ° C 5 Min). The obtained composition was injection molded using a 30 oz. Shaving molding machine to obtain 10 molded articles (radiator grill: 500 mm horizontal × 200 mm vertical) per composition. Four-layer plating of copper, nickel, and chromium was applied to the molded article obtained by the normal plating method shown in the flowchart art 1. The plated film thicknesses were copper: 20 µ, nickel: 10 µ, and chromium: 0.2 µ. The obtained thermocyclability was tested based on the following thermocycling test. The results are shown at the bottom of Table 1. Moreover, the result of having tested thermocyclability about the plated product which double-plated the molded articles of the composition 1 and 9 is shown in Table 2.

TABLE 1

B: polyburadiene A: acrylonitrile

S: Styrene α-S: Alphamethyl styrene

Concentration: 0.4% Viscosity Tube: Canon Penske

Haggins Essence: 0.375

TABLE 2

Example 2

The graft polymer (A), the copolymer (B), the organosilicon compound (C) and the lubricant (D) were mixed at the compounding ratios shown in Table-3, and compositions 13 to 25 were obtained (kneading conditions: Banbury mixer, 190 ˜200 ° C. for 5 minutes). In the same manner as in Example 1, these compositions were injection molded, and the obtained molded article was subjected to three-layer plating, and thermal cycling, processability, and releasability (test method described below) were examined for the obtained plated article. The results are shown in Table 4. In addition, the thermocyclability was tested for the plated product in which the molded articles of the compositions 13 and 21 were subjected to double nickel plating. The results are shown in Table 4.

TABLE 3

TABLE 4

Obtained water 13-25. (Training condition: Banbury mixer, 190-200 ° C. for 5 minutes) In the same manner as in Example 1, these compositions were injection molded, and the obtained molded article was plated in three layers. The test method was described in the following). The results are shown in Table 4. In addition, thermal reactivity was tested for a plated product in which the molded articles of the compositions 13 and 21 were subjected to double nickel plating. The results are shown in Table 4.

Thermocycling test

After the plating is finished, the plated product is left in the greenhouse for 15 minutes and immediately placed in a 40 ° C. cold air cooling system for 1 hour. After removing, the mixture is allowed to stand at room temperature for 15 minutes and then placed in an oven at 80 ° C. for 1 hour. Take out after 1 hour and leave at room temperature for 15 minutes. The above procedure is repeated with 1 cycle (15 minutes at room temperature-1 hour at -40 ° C-15 minutes at room temperature-1 hour at + 80 ° C). In the meantime, the sound of the plating film, the leveling of the homogenous salt, etc. are examined, and only the abnormality is passed.

Machinable mold 1/4 "x 1/2" x 5 "

Solidified Flow Tester Resin Temperature 260 ℃

210 ℃, 30Kg / cm ² Mold temperature 80 ℃

Mold Release Test Injection Time 15?

TS-100 Criminal Birth Machine Mold Cold Time 0sec.

균열이 일어나고 완전한 성형품이 얻어지지 않게 될때까지 성형을 하여 그 쇼트수를 기록한다.Do not mold continuously. With melt-out pin to molding

Mold until the cracks occur and complete molding is not obtained and record the number of shots.

Claims (1)

5 to 95 parts by weight of a graft polymer (A) grafted with 10 to 90% by weight of aromatic vinyl and 5 to 50% by weight of vinyl cyanide to 5 to 80% by weight of conjugated diene rubber, 40 to 90% by weight of aromatic vinyl, and vinyl cyanide 60 A thermoplastic resin composition comprising 95 to 5 parts by weight of the copolymer (B), and 0.05 to 3.0 parts by weight of the organosilicon compound (C).