JPH09208799A - Resin composition excellent in plating properties - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition which provides plated resin products excellent in resistance to shock and plate bulging by formulating two kinds of specific copolymers so that the molded product becomes smaller than a specified value in its coefficient of linear expansion. SOLUTION: (A) A graft polymer prepared by grafting vinyl monomers, preferably styrene, acrylonitrile or the like onto a diene rubber polymer, for example, polybutadiene and (B) a copolymer containing an aromatic vinyl compound and a vinyl cyanide as essential components are formulated so that the molded product from the objective composition may have a coefficient of linear expansion of <=7.2×10<-5> cm/cm. deg.C. In order to improve the thermal cycling properties of the plated products, an organosilicon compound having a recurring unit of the formula (R1 and R2 are each H, an alkyl; (n) is >=1) and a viscosity of 5-100,000 centistokes at 25 deg.C is preferably formulated in an amount of 0.02-0.3 pt.wt.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition having excellent plating properties, and more particularly to a resin composition having excellent plating swelling resistance.

[0002]

2. Description of the Related Art Conventionally, ABS resin has been widely used for plating as a resin most suitable for plating. In the plating on the ABS resin, the adhesion of the plating film is obtained by the anchoring effect in which the butadiene rubber of the resin surface layer is eluted by the etching treatment and the metal enters the etching holes after the butadiene rubber is removed.

Therefore, various studies have so far been made on the particle size of the butadiene rubber contained in the resin. For example, in Japanese Patent Laid-Open No. 07-157623, regarding the rubber particle diameter, large particles (average particle diameter 0.35 to 0.5
and a medium particle (average particle size 0.2 to 0.32 μm) having a two-dispersion particle size distribution, and when the average particle size of the large particles exceeds 0.5 μm, impact resistance is significantly increased. If it is less than 0.35 μm, the effect of improving the plating property is reduced. Further, it is described that when the average value of the medium particle diameter exceeds 0.32 μm, the impact resistance is lowered, and when it is less than 0.2 μm, the impact resistance is lowered and at the same time, the effect of improving the plating property is also lowered.

As described above, in the conventional plating technology, the anchoring effect to bring out the adhesion strength of the plated film has been mainly studied. However, recent resin-plated products, as represented by automobile front grilles, have complicated shapes and large sizes, and factors such as shape and dimensions complicately influence each other, and the adhesion strength alone It is becoming difficult to organize the plating properties.

The most common defect of plating is defective plating swelling, in which the plating film floats from the resin when the resin-plated product undergoes a thermal environmental change, and this defect is also the adhesion strength as described above. It cannot be sorted out by itself, and this defect has not been resolved.

[0006]

Means for Solving the Problems The inventors of the present invention have made extensive studies in view of such a situation, and as a result, by using a resin having a linear expansion coefficient smaller than a certain value for plating, the plating swelling resistance is excellent. The inventors have found that a resin-plated product can be obtained, and completed the present invention.

That is, the present invention comprises a graft copolymer [I] obtained by graft-polymerizing a vinyl monomer on a diene rubber polymer, an aromatic vinyl compound and a vinyl cyanide compound as essential components. A resin composition comprising a copolymer [II], characterized in that a molded product obtained from the resin composition has a linear expansion coefficient of 7.2 × 10 ⁻⁵ cm / cm · ° C. or less. The resin composition has excellent plating properties.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The graft copolymer [I] used in the present invention is obtained by polymerizing a vinyl monomer in the presence of a diene rubber polymer latex.

The diene rubbery polymer is butadiene 10
A homopolymer of butadiene or a copolymer of butadiene composed of 0 to 50% by weight and 0 to 50% by weight of another monomer having a group copolymerizable therewith (total 100% by weight). . Examples of such polybutadiene homopolymers or copolymers include polybutadiene; butadiene-styrene copolymers, butadiene-vinyltoluene copolymers and other butadiene-aromatic vinyl compound copolymers; butadiene-acrylonitrile copolymers. Polymer,
Butadiene-vinyl cyanide compound copolymer such as butadiene-methacrylonitrile copolymer; butadiene-methyl acrylate copolymer, butadiene-ethyl acrylate copolymer, butadiene-butyl acrylate copolymer, butadiene-acrylic Butadiene-acrylic acid alkyl ester copolymers such as acid 2-ethylhexyl copolymers; butadiene-methyl methacrylate copolymers, butadiene-
Butadiene-methacrylic acid alkyl ester copolymers such as ethyl methacrylate copolymer; and the like. Further, a terpolymer containing 50% by weight or more of a butadiene unit is also included.

These can usually be easily produced by known emulsion polymerization. The catalyst, emulsifier and the like used in the production of the diene rubbery polymer are not particularly limited and various kinds can be used.

The particle diameter of the rubber in the diene rubbery polymer latex is preferably in the range of 0.16 to 0.40 μm. If the particle size is smaller than 0.16 μm, the impact resistance decreases. Further, if the particle size exceeds 0.40 μm, the impact resistance is lowered and at the same time, plating swelling is likely to occur.

As the diene rubbery polymer latex, one having a particle size distribution of two or more dispersions can be used. In order to have a two-dispersion particle size distribution, large particles and medium particles are required, and the average particle size of each is 0.35
It is 0.5 μm and 0.2 to 0.32 μm. The ratio of large particles to medium particles is in the range of 5 to 30/95 to 70 (% by weight). If the average particle diameter of the large particles exceeds 0.5 μm, the impact resistance is significantly reduced, and if it is less than 0.35 μm, the effect of improving the plating swelling resistance is reduced. On the other hand, when the average particle diameter of the medium particles exceeds 0.32 μm, the impact resistance decreases, and when it is less than 0.2 μm, the impact resistance decreases and at the same time defective plating swelling easily occurs. Further, the amount of rubber having a particle size of 0.1 μm or less is 0 to 15% by weight, and when it exceeds 15% by weight, both the plating property and the physical properties of the material tend to deteriorate. Regarding the ratio of large particles / medium particles, when the ratio of large particles in the rubber is lower than 5% by weight, the effect of improving the plating property and large-scale moldability decreases, while when it exceeds 30% by weight, the impact resistance is high. Is reduced. Also, there is no particular limitation as to the method of giving a particle size distribution, each particle is manufactured individually, and a method of blending them in a predetermined ratio, a blending system of acid group-containing copolymers having different bloat-up abilities. , A method of enlarging small particle rubber by giving it a particle size distribution all at once.

In the present invention, the vinyl monomer used for grafting to the diene rubbery polymer is not particularly limited as long as it is a monomer which can achieve the object of the present invention, but aromatic vinyl Compounds selected from compounds, vinyl cyanide compounds and other vinyl monomers copolymerizable with these are preferably used.

In the present invention, examples of the aromatic vinyl compound which can be used for grafting to the diene rubbery polymer include styrene, α-methylstyrene, vinyltoluene, t-butylstyrene and the like.
They may be used alone or in combination of two or more. Preferred is styrene.

The vinyl cyanide compound may, for example, be acrylonitrile, methacrylonitrile or ethacrylonitrile, which may be used alone or in combination of two or more. Preferably it is acrylonitrile.

Other vinyl-based monomers copolymerizable therewith include methacrylic acid alkyl esters such as methyl methacrylate and ethyl methacrylate, acrylic acid such as methyl acrylate, ethyl acrylate and butyl acrylate. Examples thereof include alkyl esters and N-phenylmaleimide, and these can be used alone or in combination of two or more.

The amount of the aromatic vinyl compound, vinyl cyanide compound and other copolymerizable vinyl monomer used is
In the monomer mixture, the aromatic vinyl compound is 25 to 90% by weight, the vinyl cyanide compound is 10 to 45% by weight, and the other copolymerizable vinyl-based monomer is 0 to 35% by weight (however,
The total is 100% by weight. ), And out of these ratio ranges, formability, plating deposition, plating adhesion,
At least one of the plating blistering resistance becomes inferior.

The graft copolymer [I] of the present invention can be obtained by polymerizing the above-mentioned vinyl monomer by a known emulsion polymerization method in the presence of a diene rubbery polymer latex.

Further, as the copolymer [II] used in the present invention, it is preferable to use a copolymer containing an aromatic vinyl compound and a vinyl cyanide compound as essential components. As such a copolymer, an aromatic vinyl compound-acrylonitrile copolymer, an aromatic vinyl compound-acrylonitrile-methyl methacrylate copolymer,
Aromatic vinyl compound-acrylonitrile-acrylic acid lower alkyl ester copolymers, aromatic vinyl compound-acrylonitrile-N-substituted maleimide copolymers and the like can be mentioned.

The amount of the copolymer [II] used cannot be determined unconditionally depending on the rubber content in the graft copolymer [I], but the linear expansion coefficient of the molded product obtained from the resin composition is 7.
The amount is 2 × 10 ⁻⁵ cm / cm · ° C. or less, and specifically, the content of the diene rubbery polymer in the resin composition is less than 11% by weight when a filler (filler) is not added. It is preferable to mix them so that Further, when a filler is added, the content of the diene rubbery polymer in the resin composition is preferably 23% by weight or less, although it cannot be determined unconditionally depending on the type and amount of the filler used.

In the resin composition of the present invention, it is preferable to add an organosilicon compound in order to improve the thermal cycle property of the plated product. The organosilicon compound used in the present invention has a viscosity of 5 to 100 at 25 ° C.
000 centistokes, preferably a surface tension of a 0.5 wt% solution in toluene at 25 ° C. of 26.5.
It is not more than dyn / cm and has a repeating unit represented by the following general formula (I).

[0022]

Embedded image

Specific examples of the organic silicon compound used in the present invention include polydimethylsiloxane,
Polysiloxanes such as polymethylethylsiloxane, polydiethylsiloxane, polymethylphenylsiloxane, silanes such as tetraethylsilane and trimethylhexylsilane, or triethylchlorosilane, diethyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, etc. Halosilanes are mentioned, and the use of polysiloxanes is particularly preferable.

The viscosity range of the organosilicon compound is from 5 to 100,000 centistokes at 25 ° C., preferably from 50 to 50,000 centistokes. If the viscosity of the organosilicon compound is less than 5 centistokes, there are many volatile components during injection molding, which causes poor plating throwing power.
When it exceeds centistokes, the dispersion in the resin composition becomes insufficient and the intended purpose of the present invention cannot be achieved.

The amount of the organosilicon compound added is 0.01 to 0.5 parts by weight, preferably 0.02 parts by weight, based on 100 parts by weight of the total amount of the graft copolymer [I] and the copolymer [II].
０．３0.3 parts by weight. If it is less than 0.01 part by weight, the effect of improving the thermal cycleability of the plated product is small,
If it exceeds the weight part, the organosilicon compound may bleed out on the surface of the molded product, which may cause stains on the mold and poor throwing power of the plating film, which is not preferable.

The resin composition of the present invention may optionally contain various colorants such as dyes and pigments, stabilizers against light or heat, inorganic or organic granular, powdery or fibrous fillers, foaming agents and the like. It can be added.

In particular, the addition of a filler can reduce the linear expansion coefficient of the resin composition and prevent plating swelling.
The type of filler that can be used is not particularly limited, but it is preferable to use potassium titanate whiskers, calcium carbonate whiskers, zinc oxide whiskers, wollastonite, aluminum borate whiskers, talc, mica and the like. The amount of the filler used varies depending on the rubber content in the resin composition, but it depends on the graft copolymer [I] and the copolymer [I].
It is preferably used in the range of 0 to 20 parts by weight based on the total amount of 100 parts by weight with I].

The resin composition of the present invention obtained by the above-mentioned constitution can be molded by various processing methods such as injection molding and extrusion molding, and then can be plated using ordinary ABS plating process equipment.

[0029]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but these do not limit the present invention. In the examples and comparative examples, "part" means "part by weight" and "%" means "% by weight". Various physical properties in Examples and Comparative Examples were measured by the following methods.

(1) Particle Size of Rubber Latex A water-diluted solution of rubber latex was measured using a measuring device (DSL-700) manufactured by Otsuka Electronics Co., Ltd., which operates on the principle of light scattering.

(2) Coefficient of linear expansion The coefficient of linear expansion was measured by injection molding (127 mm × 12.
7 mm x 6.4 mm, bending test piece for ASTM D-790, molding temperature: 230 ° C, injection pressure: 30 kg / cm
^{2. From} the injection speed: 30%, a test piece (6 mm x 6 mm x 12 mm) with the resin flow direction as the longitudinal direction was cut out and used with a thermal stress strain measurement device of TMA / SS120 manufactured by Seiko Electronics Co., Ltd. The measurement was performed under the conditions of a measurement start temperature of -60 ° C, a measurement end temperature of 70 ° C, and a heating rate of 2 ° C / min.

(3) Plating swelling The resin composition shaped by blending was molded by an injection molding machine (cylinder temperature: 200 to 230 ° C.), dimension 100.
A test piece with a tab of mm × 100 mm × 3 mm was used. The molded test piece was plated in the steps shown below, and the thermal blotting test was performed to evaluate the plating swelling property.

(A) Plating conditions Degreasing (60 ° C. for 3 minutes) → Washing → Etching (CrO ₃
400 g / liter, H ₂ SO ₄ 200 cc / liter, 65 ° C. 15 minutes) → Washing → Pickling (room temperature 1 minute) → Washing → Catalytic treatment (25 ° C. 3 minutes) → Washing → Activation (4
0 ℃ 5 minutes) → Washing → Electroless Ni plating (40 ℃ 5
Min) → electrolytic copper plating (film thickness 35 μm 20 ° C. 60 min)
→ Dry (80 ° C 120 minutes).

(B) Thermal Cycle Test The evaluation of the plating swelling of the plated test piece is as follows.
A thermal cycle test was performed using a PG-4G constant temperature and humidity chamber manufactured by Tabai Espec Co., Ltd. The temperature conditions for one cycle are as follows, and a total of two cycles were performed.

[0035]

(C) Evaluation of plating swelling property: Visual judgment was made according to the following criteria. ◯: No plating swelling Δ: Slight swelling at the gate ×: Swelling near the gate XX: Swelling about 1/4 of the sample around the gate

The fillers and organosilicon compounds used in the examples and comparative examples are shown below.

Filler F-1: Potassium titanate fiber (manufactured by Otsuka Chemical Co., Ltd., Tismo D) F-2: Calcium carbonate whisker (manufactured by Maruo Calcium Co., Whiskal A)

Organosilicon compound Polydimethylsiloxane (manufactured by Nippon Unicar Co., Ltd., silicon oil L-45, viscosity 500 centistokes, 2
5 ℃)

1. Production Example of Graft Copolymer [I] (1) Production of Graft Copolymer [Ia] To 63.5 parts (as solid content) of polybutadiene latex having a solid content of 35% and an average particle diameter of 0.08 μm. , N-butyl acrylate unit 85%, methacrylic acid unit 15
% Of a copolymer latex having an average particle size of 0.08 μm (as solid content) of 3% was added with stirring and 3
The mixture was stirred for 0 minute to obtain an enlarged rubber latex having an average particle diameter of 0.28 μm.

Then, the obtained enlarged latex was placed in a reaction vessel, and further 20 parts of distilled water, 0.2 part of a naphthalenesulfonic acid formalin condensate (manufactured by Kao Corporation, Demol N), and 0 parts of sodium hydroxide were added. 0.02 part and dextrose 0.35 part were added and the temperature in the reaction vessel was raised to 60 ° C., then 0.006 part of ferrous sulfate and 0.2 part of sodium pyrophosphate were added, and further acrylonitrile 10.
A mixture consisting of 5 parts, 24.5 parts of styrene, 0.2 part of t-dodecyl mercaptan and 0.12 part of cumene hydroperoxide was continuously added dropwise with stirring for 90 minutes, and then the mixture was kept for 1 hour and cooled. The obtained graft copolymer latex was coagulated with dilute sulfuric acid, washed, filtered,
It was dried to obtain a graft polymer [Ia].

(2) Production of graft copolymer [Ib] (a) Synthesis of diene rubbery polymer latex [Bd-1] 1,3-butadiene 66 parts n-butyl acrylate 9 parts Styrene 25 Part Diisopropylbenzene hydroperoxide 0.2 part potassium oleate 1.0 part disproportionated potassium rosinate 1.0 part sodium pyrophosphate 0.5 part ferrous sulfate 0.005 part dextrose 0.3 part sulfuric anhydride Sodium 0.3 parts Water 200 parts The above composition was placed in a 100 liter autoclave.
Polymerized at 0 ° C. The polymerization was almost completed in 9 hours, and the conversion rate was 9
A butadiene rubbery polymer latex [Bd-1] having 7%, an average particle diameter of 0.08 μm and a pH of 9.0 was obtained.

(B) Synthesis of acid group-containing copolymer [Bs-1] for rubber particle enlargement n-butyl acrylate 85 parts methacrylic acid 15 parts potassium oleate 2 parts dioctyl sulfosuccinate 1 part cumene hydroperoxide 0.4 parts Sodium formaldehyde sulfoxylate 0.3 parts Ion-exchanged water 200 parts The above composition was polymerized in another polymerization apparatus at 70 ° C. for 4 hours to give a rubber enlargement having a conversion of 98% and an average particle diameter of 0.08 μm. A chemical acid group-containing copolymer [Bs-1] latex was obtained.

(C) Synthesis of Acid Group-Containing Copolymer [Bb-1] for Enlargement of Rubber Particles In the above-mentioned synthesis of acid group polymer [Bs-1] for enlarging rubber, 72 parts of n-butyl acrylate was used. , Methacrylic acid 2
Except for changing to 8 parts, the same operation was performed and the conversion rate was 9
An acid group-containing copolymer (Bb-1) latex for rubber enlargement having 7% and an average particle diameter of 0.10 μm was obtained.

(D) Polydisperse particle size distribution rubber latex [B
c-1] Production of diene rubbery polymer latex [Bd-
1] To 100 parts (as solid content), 2 parts of a mixed latex of the above-mentioned synthetic acid-containing copolymer for rubber enlargement (Bs-1)
/ Bb-1 = 80/20 solid ratio) was added under stirring and further stirred for 30 minutes to obtain a polydisperse particle size distribution rubber latex (Bc-1).

(E) Production of graft copolymer [Ib] Polydisperse particle size distribution rubber latex [Bc-1] (as solid content) 45 parts Styrene 39 parts Acrylonitrile 16 parts Cumene hydroperoxide 0.12 Parts disproportionated potassium rosinate 2.0 parts sodium pyrophosphate 0.2 parts ferrous sulfate 0.01 parts dextrose 0.35 parts water 200 parts With the above composition, polymerization initiation temperature 40 ° C., monomer Graft polymerization was carried out at a dropping rate of 1.3 parts / min. To the obtained polymer latex, 2 parts of butylated hydroxytoluene and 0.5 part of dilauryl thiopropionate were added as an antioxidant, coagulated with a 5% sulfuric acid aqueous solution, washed and dried to obtain a white powder. . Next, 0.1 part of a phosphite stabilizer was added to the white powder, and the mixture was mixed with a Henschel mixer for 5 minutes (30 minutes).
(00 rpm) and then extruded into pellets at a cylinder temperature of 230 ° C.

2. Production Example of Copolymer [II] (1) Production of Copolymer [II-a] 115 parts of distilled water was reacted with 1 part of tricalcium phosphate and 0.001 part of Demol P (manufactured by Kao Corporation). The kettle was charged and stirred. 30 parts of acrylonitrile, 70 parts of styrene
Part, t-dodecyl mercaptan 0.3 part, azobisisobutyronitrile 0.17 part, Gafac GB-520
(Toho Chemical Industry Co., Ltd.) 0.003 parts of a mixture was added to form a suspension, which was then raised to 75 ° C. and kept for 240 minutes to complete the polymerization. The reduced viscosity of the obtained copolymer [II-a] was 0.64.

(2) Production of Copolymer [II-b] First, the air inside the first polymerization reactor (completely mixed polymerization reactor) was removed by a vacuum pump, and then nitrogen gas was introduced into the reactor. Then, after completely purging the interior of the vessel with a nitrogen atmosphere, a mixed solution of 7 parts of N-phenylmaleimide, 42 parts of styrene and 21 parts of acrylonitrile, 30 parts of methyl ethyl ketone and a polymerization initiator (1-dibutyl peroxide-3,3,3,3).
5-trimethylsiloxane) (0.1 part) is continuously added dropwise to the first polymerization reactor through separate pipes, and the copolymerization reaction is performed under the conditions of a polymerization temperature of 100 ° C. and a residence time of 1 hour, and supplied. When the polymerization conversion rate of the charged monomers reached 41%, a polymerization reaction liquid in an amount equal to the total amount of the supplied charged monomers was continuously withdrawn from the bottom of the reactor by a gear pump to carry out continuous operation.

Then, the polymerization reaction liquid discharged from the first polymerization reactor was pushed out by a gear pump and transferred to a flow type second polymerization reactor. In the second polymerization reactor, the polymerization was further advanced to greatly reduce the amount of the residual maleimide monomer. Thereafter, the polymerization reaction product was fed from the second polymerization reactor to a two-vent type twin-screw devolatilizing extruder by a gear pump, and volatile components were removed at a barrel temperature of 250 ° C. to obtain transparent resin pellets. The resin pellet obtained was a copolymer of 20% by weight of N-phenylmaleimide, 60% by weight of styrene and 20% by weight of acrylonitrile, and had a reduced viscosity of 0.71.

Example 1 16 parts of the graft copolymer [Ia] obtained in the above production example and the copolymer [II-
a] 84 parts and 0.1 part of an organosilicon compound were mixed and mixed for 5 minutes with a super mixer (manufactured by Kawata Co., Ltd.), and then pelletized with a twin-screw extruder having a screw diameter of 37 mm. Then, using the obtained pellets, a test piece for measuring linear expansion coefficient and a test piece for plating evaluation were molded by an injection molding machine. Then, using the molded test piece, the linear expansion coefficient was measured and the plated sample was subjected to a thermal cycle test. Table 1 shows the results.

[Example 2] Physical properties were measured in the same manner as in Example 1 except that the copolymer [II-a] in Example 1 was changed to the copolymer [II-b]. . Table 1 shows the results
Shown in

[Example 3] The physical properties were the same as in Example 1 except that the graft copolymer [Ia] was changed to the graft copolymer [Ib] in Example 1. It was measured. The results are shown in Table 1.

[Example 4] In Example 1, the graft copolymer [Ia] was replaced with the graft copolymer [Ib].
Then, the physical properties were measured by performing the same operation as in Example 1 except that the copolymer [II-a] was changed to the copolymer [II-b]. The results are shown in Table 1.

[Example 5] In Example 1, the blending ratio of the graft copolymer [Ia] and the copolymer [II-a] was changed as shown in Table 1, and the filler F-1 was used. The physical properties were measured by performing the same operations as in Example 1 except that 9 parts of was added. The results are shown in Table 1.

[Example 6] The same operation as in Example 5 was carried out except that the compounding ratio of the copolymer [II-a] and the filler F-1 in Example 5 was changed as shown in Table 1. It carried out and measured the physical property. The results are shown in Table 1.

Example 7 The physical properties were measured by the same procedure as in Example 6 except that the copolymer [II-a] in Example 6 was changed to the copolymer [II-b]. . Table 1 shows the results
Shown in

[Example 8] The physical properties were the same as in Example 6 except that the graft copolymer [Ia] was changed to the graft copolymer [Ib] in Example 6. It was measured. The results are shown in Table 1.

[Example 9] In Example 6, the graft copolymer [Ia] was replaced with the graft copolymer [Ib].
Then, the physical properties were measured by performing the same operation as in Example 6 except that the copolymer [II-a] was changed to the copolymer [II-b]. The results are shown in Table 1.

[Example 10] Physical properties were measured in the same manner as in Example 5, except that the filler F-1 in Example 5 was changed to the filler F-2. The results are shown in Table 1.

[Example 11] Physical properties were measured in the same manner as in Example 6 except that the filler F-1 in Example 6 was changed to the filler F-2. The results are shown in Table 1.

[Example 12] Physical properties were measured in the same manner as in Example 7, except that the filler F-1 in Example 7 was changed to the filler F-2. The results are shown in Table 1.

[Example 13] Physical properties were measured in the same manner as in Example 8 except that the filler F-1 was changed to the filler F-2. The results are shown in Table 1.

[Example 14] Physical properties were measured by performing the same operations as in Example 9 except that the filler F-1 in Example 9 was changed to the filler F-2. The results are shown in Table 1.

Example 15 Physical properties were measured in the same manner as in Example 3 except that the organosilicon compound was not added. The results are shown in Table 1.

Example 16 The physical properties were measured by the same procedure as in Example 8 except that the organosilicon compound was not added. The results are shown in Table 1.

[0066]

[Table 1]

[Comparative Examples 1 and 2] Comparative Examples 1 and 2 were carried out except that the blending ratio of the graft copolymer [Ia] and the copolymer [II-a] in Example 1 was changed as shown in Table 2. The same operation as in Example 1 was performed to measure the physical properties. Table 2 shows the results.

[Comparative Examples 3 to 4] Comparative Examples 3 to 4 were carried out except that the blending ratio of the graft copolymer [Ia] and the copolymer [II-b] was changed as shown in Table 2 in Example 2. The same operation as in Example 2 was performed to measure the physical properties. Table 2 shows the results.

[Comparative Examples 5 to 6] Examples except that the blending ratio of the graft copolymer [Ib] and the copolymer [II-a] in Example 3 was changed as shown in Table 2. The same operation as in 3 was performed to measure the physical properties. Table 2 shows the results.

[Comparative Examples 7 to 8] Comparative Examples 7 to 8 were carried out except that the blending ratio of the graft copolymer [Ib] and the copolymer [II-b] in Example 4 was changed as shown in Table 2. The same operation as in Example 4 was performed to measure the physical properties. Table 2 shows the results.

[Comparative Example 9] The same operation as in Comparative Example 1 was carried out except that the organosilicon compound was not added, and the physical properties were measured. Table 2 shows the results.

[Comparative Example 10] Physical properties were measured in the same manner as in Comparative Example 5 except that the organosilicon compound was not added. Table 2 shows the results.

[Comparative Example 11] Physical properties were measured in the same manner as in Comparative Example 9 except that the copolymer [II-a] was changed to the copolymer [II-b] in Comparative Example 9. . Table 2 shows the results.

[Comparative Example 12] Physical properties were measured in the same manner as in Comparative Example 10 except that the copolymer [II-a] in Comparative Example 10 was changed to the copolymer [II-b]. .
Table 2 shows the results.

[Comparative Example 13] In Example 6, the blending ratio of the graft copolymer [Ia] and the copolymer [II-a] was changed as shown in Table 2, and the filler F-1 was used. Physical properties were measured by performing the same operations as in Example 6 except that the components were not blended. Table 2 shows the results.

[Comparative Example 14] In Example 7, the blending ratio of the graft copolymer [Ia] and the copolymer [II-b] was changed as shown in Table 2, and the filler F-1 was used. Physical properties were measured by performing the same operations as in Example 7 except that the components were not blended. Table 2 shows the results.

[Comparative Example 15] In Example 8, the blending ratio of the graft copolymer [Ib] and the copolymer [II-a] was changed as shown in Table 2, and the filler F-1 was used. Physical properties were measured by performing the same operations as in Example 8 except that the components were not blended. Table 2 shows the results.

[Comparative Example 16] In Example 9, the blending ratio of the graft copolymer [Ib] and the copolymer [II-b] was changed as shown in Table 2, and the filler F-1 was used. The physical properties were measured by performing the same operations as in Example 9 except that the components were not blended. Table 2 shows the results.

[Comparative Example 17] In Example 11, the blending ratio of the graft copolymer [Ia] and the copolymer [II-a] was changed as shown in Table 2, and the filler F-2 was used. Physical properties were measured by performing the same operations as in Example 11 except that the components were not blended. Table 2 shows the results.

[Comparative Example 18] In Example 12, the blending ratio of the graft copolymer [Ia] and the copolymer [II-a] was changed as shown in Table 2, and the filler F-2 was used. Physical properties were measured by performing the same operations as in Example 12 except that the compounding was not performed. Table 2 shows the results.

[Comparative Example 19] In Example 13, the blending ratio of the graft copolymer [Ib] and the copolymer [II-a] was changed as shown in Table 2, and the filler F-2 was used. Physical properties were measured by performing the same operations as in Example 13 except that the components were not blended. Table 2 shows the results.

[Comparative Example 20] In Example 14, the blending ratio of the graft copolymer [Ib] and the copolymer [II-b] was changed as shown in Table 2, and the filler F-2 was used. Physical properties were measured by performing the same operations as in Example 14 except that the components were not blended. Table 2 shows the results.

[0083]

[Table 2]

[0084]

According to the present invention, it is possible to obtain a resin-plated product which is impact resistant and has excellent plating swelling resistance.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Takaaki Shiratori Inventor Takaaki Shiratori 3816 Noborito, Tama-ku, Kawasaki City, Kanagawa Mitsubishi Rayon Co., Ltd. Tokyo Technical and Information Center

Claims (2)

[Claims] 1. A graft copolymer [I] obtained by graft-polymerizing a vinyl monomer to a diene rubber polymer, and a copolymer [A] containing an aromatic vinyl compound and a vinyl cyanide compound as essential components. II], wherein the linear expansion coefficient of the molded product obtained from the resin composition is 7.2 × 10 ⁻⁵ cm / cm · ° C. or less. Excellent resin composition. 2. An organosilicon compound having a repeating unit represented by the following general formula (I), whose viscosity at 25 ° C. is 5 to 100,000 centistokes, based on 100 parts by weight of the resin composition according to claim 1. 0.01-0.5
A resin composition having excellent plating properties, characterized by being mixed in parts by weight. Embedded image