JPS62201959A - Impact-resistant thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled resin compsn. which has excellent light transmission properties and is platable, by blending a specified graft copolymer derived from 1,3-butadiene, an arom. vinyl monomer and a vinyl cyanide monomer with a copolymer. CONSTITUTION:A thermoplastic resin compsn. is obtd. by blending a blend of a graft copolymer (I) having a graft ratio of 20-180%, obtd. by polymerizing a monomer mixture (B) of an arom. vinyl monomer and a vinyl cyanide monomer in the presence of a latex of synthetic rubber (A) obtd. from 1,3-butadiene or a mixture thereof with styrene and a copolymer (II) obtd. from an arom. vinyl monomer and a vinyl cyanide monomer with a graft copolymer (III) having a graft ratio of 20-100%, obtd. by graft-polymerizing a monomer mixture of an arom. vinyl monomer and a vinyl cyanide monomer onto a butadiene rubber latex in such a proportion that the resulting compsn. contains 0-15wt% butadiene rubber (C).

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a novel impact-resistant thermoplastic resin composition that can be layered translucently and plated. [Prior Art] Recently, in the field of audio parts, automobile front panels, etc., a display method that illuminates from the inside using a single character or graphic LED rung has been used to more clearly confirm the operating status of a function. A switch neck is used. For such a material, it is preferable to use RjJJ plastic resin from the point of view of freedom in design, but it is essential to apply plating for the purpose of creating a metallic feel in addition to translucency. Conventionally, such pleasure products have been made of double-molded products made of translucent polystyrene or acrylic resin and ABS resin, which has good plating properties, but this requires a special mold. Because of this, it is not possible to respond to diversified designs, the molding operation is complicated, and there is a tight gap at the interface between polystyrene or acrylic resin and ABS resin. In addition, although conventional ABS resin has poor plating properties, it has poor translucency, so we have developed an impact-resistant thermoplastic resin that is both translucent and plateable, which can solve these problems at once. It was hoped that it would appear. On the other hand, transparent ABS resin is known as a special grade of ABS resin (US Patent No. 2,843,561,
029223 specification and Japanese Patent Publication No. 35-4889), however, these resins use methyl methacrylate monomer for the purpose of matching the refractive index of the rubber and the matrix resin1)5, resulting in poor plating properties. Therefore, it cannot be used for the above purpose. [Points to be solved by the invention] In view of the above-mentioned current situation, the present inventors have developed an excellent light transmitting property,
As a result of intensive studies to obtain an impact-resistant heat-plastic at-fat composition that has good plating performance even during high-temperature molding,
It has been found that the desired objective can be achieved when the particle size and crosslinked structure of the rubber used, as well as the grafting ratio, are set within a specific range. [Means for solving the problems] The gist of the present invention is that 1,3-butashun 50-100ii
Synthetic rubber (A) Latin 2115-80 μg with a gel fraction of 6096 or more and an average particle size of 0.04-0.15p obtained from Daken and Methi 1F 0-50 μg
Monomer mixture I consisting of 60 to 80 weight ft% of aromatic vinyl monomer and 20 to 40 weight ft% of cyanide vinyl monomer per 100 parts by weight (as solid content)
A graft copolymer μt having a grafting rate of 20 to 180 mounds obtained by graft polymerizing BI 20 to 85 parts by weight [(A) and (total weight per second is 100 parts by weight)], and an aromatic The copolymer μll obtained from 60 to 80% by weight of vinyl monomer and 20 to 40% by weight of vinyl cyanide monomer is the synthetic rubber ( N's content pupil is 5-3
Formulations formulated to cause 0-fold ulcers and 0.2 to 0
．． Butadiene thread rubber (C) with an average particle size of 4μ, based on 15 to 75 heavy seams (as solid content), aromatic vinyl monomer 60 to 80% and vinyl cyanide monomer 20 to 40 heavy seams. A monomer mixture f
DI 25-85 heavy I part [(C) and D) total intake is 10
20 to 100 obtained by graft polymerization of
a graft copolymer μl having a grafting rate of 96,
Toro t of butadiene rubber + C1 in the whole composition is 0 to 1
This is an impact-resistant thermoplastic resin composition having good translucency and plating properties, which is formulated in such a manner that the synthetic rubber (N gel fraction and graft copolymer (The grafting rate of il and (fuki) is defined as follows. Gel fraction: Agglomerated and dried rubber is collected on a constant scale.). Leave it to stand. Separate the toluene-insoluble aggregated rubber, dry it, and eat it by weight (Wl). The gel fraction is expressed by the following formula: O Grafting rate = # Seize the dried grafted rubber at a constant h1 ShikukuWo
), reflux for 2 hours at 60 °C in acetone at 50 °C. 1) Separate the acetone-insoluble graft rubber by centrifugation, dry it, and weigh it (Wl). Assuming that the synthetic rubber (A) in the grafted rubber is naturally ejected, the grafting rate is calculated by the following formula. W − (W X”−) +0100 Graft rate (%) =
t% and methylene 0 to 50% by weight, with a gel fraction of 60 or more and 0.04 to 0.1
It has an average particle size of 5μ. These synthetic rubbers are produced by (1) cleaving, usually by known emulsion polymerization. When the particle size exceeds 0.15, the translucency decreases significantly,
Moreover, if the particle size becomes 0.04/J without grooves, the impact strength will decrease, which is not preferable. Furthermore, if the gel content (8) is 60% final groove, the shape of the rubber will be the main shape when it is made. The surface gloss will deteriorate. The graft polymerization field monomer mixture (B) is 20 to 85 parts by weight, preferably 35 to 70 parts by weight, relative to 65 parts by weight.
Used in the beak of the If the amount of synthetic rubber is less than 15 parts by weight, productivity will be poor and impractical; if it exceeds 80 parts by weight, the graft copolymer (I) will be used as an aromatic vinyl hepta-vinyl cyanide monomer copolymer. Coalescence and optionally 11) graft copolymer f
Graft copolymer (I) is dispersed in a resin composition obtained by bath melt mixing with -8(l), which may deteriorate the molded appearance, translucency, and plating properties, so it is preferable. No, graft polymerization monomer mixture f131 is a mixture of aromatic vinyl monomer and cyanide vinyl monomer [
Aromatic vinyl monomer (7)-1-60-8°tIL preferably 65-75% and vinyl cyanide monomer 2
It is used in graft polymerization at a mixing ratio of 0 to 40% by weight, preferably 25 to 35% by weight. As the aromatic vinyl monomer 1, for example, styrene, α
Examples include -methylstyrene, styrene with an alkyl nucleus, and styrene is preferred. Examples of vinyl cyanide monomers include acrylonitrile and methacrylonitrile, with acrylonitrile being preferred. If the graft polymerization is carried out at a mixing ratio of vinyl cyanide monomers exceeding 40 parts by weight, a vinyl cyanide homopolymer will be produced during the graft polymerization, which will cause discoloration of the resulting composition, which is undesirable. Furthermore, if the graft polymerization is carried out at a mixing ratio of 20% vinyl cyanide monomer, it is not preferable because the plating properties of the resulting composition will deteriorate. In this emulsion graft polymerization, generally known emulsifiers, initiators and chain transfer agents are used. In addition, the graft polymerization field monomer mixture (the stage is - in the rubber latex)

[A]Although addition may be carried out in one portion or continuous addition, one portion addition or continuous addition is preferable. Insertion of milk floss, initiator, chain transfer agent, etc. A1. The method of adding the abrasive and the method of adding the nitrate are selected so that the resulting graft copolymer (I) has a graft ratio of 20 to 180%. If the grafting ratio is less than 20%, it is not preferable because the permeability tends to decrease significantly and the plating adhesion strength tends to deteriorate. Furthermore, if the grafting ratio exceeds 180%, the impact strength will drop significantly and the fluidity will also deteriorate, so it is necessary to control the grafting ratio of the graft copolymer (I) within the range of 20 to 180%. . Aromatic vinyl monomer-vinyl cyanide monomer copolymerization K flIl is a combination of aromatic and vinyl monomers 60 to 80 times 1
′! 1196. Preferably 65-751if@Akira and 20-40@1% of vinyl cyanide monomer. Preferably, it is a copolymer obtained by polymerizing 25 to 35%. Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, and alkyl-substituted styrene, with styrene being preferred. Examples of vinyl cyanide monomers include acrylonitrile and methacryl σ nitrile, with acrylonitrile being preferred. As in the case of the graft polymerization monomer mixture, if the ratio of cyanide and nil monomers exceeds 40% by weight, coloring tends to occur, and 20'jl (Q16 weight) is not preferable because the plating properties deteriorate. The method of polymerizing the aromatic vinyl monomer-vinyl cyanide monomer copolymer flit is not particularly limited, and a known bulk polymerization method, suspended A polymerization method, or emulsion polymerization method can be used.Thermoplastic resin composition of the present invention The product is the above graft copolymerization h
The basic composition is a mixture of (I) and an aromatic vinyl monomer-cyanated vinyl monomer copolymer within the above-mentioned specific range. Further, to this formulation, butane diene thread rubber FCL latex 15-75 having an average particle size of 0.2-0.4μ is added.
Aromatic vinyl monomer 60 to 80 weight percent and cyanide vinyl monomer 20 to 4 weight percent based on weight (as solid content)
A graft copolymer with a graft ratio of 20 to 100% obtained by graft polymerization of a monomer mixture fD125 to 85 0 tm% [total of [C] and D 100 parts is 14 parts]] μl of graft copolymer (I
). The content of butadiene rubber FCL constituting the graft copolymer (■) in the total composition consisting of aromatic vinyl monomer-vinyl cyanide monomer copolymer and graft copolymer (ml) is 15 times RL + or less By blending J: l) as desired so that the properties of the thermoplastic resin composition, particularly the impact resistance, can be further improved. Butadiene rubber f constituting the graft copolymer ill
Examples of cl include polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, butadiene-acrylic acid alkyl ester copolymer, and butadiene-methacrylic acid alkyl ester copolymer. These butadiene-based rubbers can be produced by conventional emulsion polymerization. If the particle size is less than 0.2μ, it will not be possible to obtain a sufficient impact strength for light;
If it exceeds 4μ, the light transmittance will decrease, which is not preferable. In graft polymerization IC, butadiene rubber fc115
~75 parts by weight, the monomer mixture for graft polymerization (D+ is 25 to 85 parts [C11D+)] The total l is 10
0jushabu] Noha is used. Butadiene rubber (if q is less than 15 parts, impact strength is poor and 75 parts)
If the heavy I part is exceeded, graft copolymerization K (Il and aromatic vinyl monomer cyanated vinyl monomer copolymerization K ff
This is not preferable because it causes poor dispersion of fl into the blend and deteriorates the molded appearance. The upper Zummer mixture vA(II)l for graft polymerization is a mixture of aromatic vinyl monomers and cyanide monomers, with 60 to 80% of aromatic vinyl monomers, preferably 65 to 75% of vinyl monomers, and vinyl cyanide monomers. 20～
It is used in graft polymerization at a mixing ratio of 40% by weight, preferably 25-35% by weight. Examples of aromatic vinyl monomers include 1, such as styrene, α-
Examples include methylstyrene and alkyl-substituted styrene, with styrene being preferred. Examples of vinyl cyanide monomers include eva-acrylonitrile and methacrylonitrile, with acrylonitrile being preferred. If the graft polymerization is carried out at a mixing ratio of vinyl cyanide monomers exceeding 40% by weight and 1i1%, a vinyl cyanide homopolymer will be produced during the graft polymerization, causing discoloration of the resulting composition, which is undesirable. In addition, vinyl cyanide monomer is 20
If graft polymerization is carried out at a mixing ratio of less than % weight, the plating properties of the resulting composition will deteriorate, which is not preferable. In this emulsion graft polymerization, generally known emulsifiers, initiators and chain transfer agents are used. Incidentally, the monomer mixture 0) for graft polymerization may be mixed in the rubber latex, and may be added in portions or continuously, but addition in one portion or continuously is preferable. Emulsification, start column. Regarding the method of adding ridges such as chain transfer agents, additives, and seven polymers, they are selected so that the resulting graft copolymer has a grafting rate of 20 to 100%.If the grafting rate is less than 20%, If the grafting ratio exceeds 100%, the impact strength 1■ decreases, so the grafting ratio of the graft copolymer μl should be set to 20%.
It is necessary to control +JI within the range of ~100%. The definition of the graft ratio is the same as in the case of graft copolymer i11. The thus obtained t-graft copolymer (I) and the aromatic and vinyl monomer-vinyl cyanide monomer copolymer are combined into a synthetic rubber ( The N content is blended so that the amount of 5 to 30 parts is 96, and to this blend, μl of the graft copolymer is added to the total composition vA [graft copolymer [), μl of the copolymer and graft copolymer] The content of butadiene rubber + C1 in the combined illumination is 0 to 15% by weight and is 111%, and the composition of l:I is an impact-resistant thermoplastic resin that is impervious to translucency and plating properties. When the content of synthetic rubber IAI in the total amount of graft copolymer (I) and copolymer (■) is less than 5%, the plating properties deteriorate and the impact resistance deteriorates. If it exceeds 30, the translucency and plating properties will decrease, and the mobility and processability of 151 will also deteriorate, so it is not desirable. However, the total composition vA [graft copolymer μl
If the content of butadiene rubber fcl in the total of copolymer (II) and graft copolymerized Hill exceeds 15% by weight, the haze value will increase, which is practically undesirable. The graft copolymer (copolymer) may be used alone or with 2 or more grafts whose gel fraction and particle size of the rubber are within the above-mentioned specific ranges. 1 (Polymer (Process 1) can be used as a mixture. A vinyl monomer-vinyl cyanide monomer copolymer may also be used in combination with 2 or more. Furthermore, the graft copolymer ill can be used as a mixture. It can be used alone or as a mixture of 263 or more graft copolymers (II1) in which the particle size of the rubber, the graft polymerization monomer heel, the graft ratio, etc. are within the above-mentioned specific ranges. In order to blend the graft copolymer + Il with the aromatic vinyl hepanomer-cyanated vinyl monomer copolymer (till) and the graft copolymer C), if the copolymer compound is produced by emulsion polymerization, It is possible to mix them in the form of an emulsion.In addition, the three components can be mixed as powder, or by combining the powder with beads, pellets, etc. The resin composition of the present invention may contain an antioxidant, an eraser, etc., if necessary.
Common auxiliary agents such as coloring agents, antistatic agents, dispersant additives, etc. can be added. [Example] In the following examples, "part" and "%" mean weight@part and weight means %, respectively. Impact strength 1y is AsTM D-25
6 to 1'I, optical properties are ASTM D-1003-
61, a sample of plate I9.1.51 was measured using an integrating sphere type haze meter manufactured by Nippon Seimitsu Gengakutoku. The molded appearance and plating characteristics were measured by the following methods. Appearance of molding: Using a 5-j screw type injection molding machine (Yamae Kozueki Co., Ltd., Fu), the cylinder temperature was 250°C and 290°C.
A flat plate with a thickness of 3 cm was molded at a C1 mold temperature of 60° C., and the color A circumference and gloss were observed. Plating characteristics: +1 using a flat test piece for molded appearance evaluation! Jl! ! Approximately 35
After applying μ magnetic copper plating, the surface appearance was inspected, and the strength of the back adhesion was measured as the plating peeled off in the right angle direction at a rate of 30 fl/min. Example 1 Synthesis of synthetic rubber (A-1): 1.3-butadiene 75 parts Styrene 25 parts 1.3-butylene dimethacrylate 0.5 parts Potassium oleate 1.0
Disproportionated potassium rosinate 1.
0 parts a bilbenzene peroxide
0.2 M ferrous sulfate
0.005 part sodium bis phosphate
0.5 parts dextrose
0.3 part water
200 parts 100/? according to the above composition Using an autoclave, 50
Polymerization was carried out at ℃. The polymerization was almost completed in 9 hours, and the m content was 98% and the particle size was 0.092μ. A rubber latex with a gel fraction of 99% was obtained. Synthesis of graft copolymer (G-1): Rubber latex (A-1) 30 parts (as solid decoy) Styrene 49 parts Acrylonitrile 21 parts Disproportionated potassium rosinate 1.0 parts Cumene hydroperoxide 0.35 Part ferrous sulfate 0,010 0 parts Sodium picrate 0.2 parts Dextrose 0,35 parts t-dodecyl mercaptan 0.7 gas7k
A graft copolymer was synthesized according to the above composition using 200 parts of rubber latex (A-1) (including water in the rubber latex). Polymerization temperature is 70'C, polymerization time is 4
It's an insult. Styrene, acrylonitrile, cumenehydronoxylate, and t-dodecylmercagdan were dissolved in a mixed bath and added dropwise to this rubber latex (A-1) over 2 hours. The polymerization rate was 97,296. Graft rate is 519
It was 6. To the obtained graft copolymer latex were added 2 parts of butylated human acetoluene and 0.5 parts of dilaurylthiopropione as antioxidants, and the mixture was coagulated with a 5% aqueous sulfuric acid solution. It was washed and dried to form a white powder. Synthesis of styrene-acrylonitrile copolymer (M-1) ÷Styrene
70 parts acrylonitrile
30 parts calcium phosphate 1
．． 0 part GAFACGB520 0.
0.003 parts (dispersion aid, Toho Higaku ■ / Mochi) Lauryl peroxide 0.6 parts t-dodecyl mercaptan 0.5
Quantity of water 20
A styrene-acrylonitrile copolymer was synthesized according to the above composition. The polymerization temperature change is go'c, and the polymerization time is 6 hours. The polymerization rate was 9896. Special purpose and physical property evaluation of resin composition: 50 parts of the graft copolymer (G-1) and styrene
Acrylonitrile and 1 combined IJ-(M-' 1)5
0 parts were mixed in a Henschel mixer at 3000 rpm for 5 minutes to reduce the spitting content of the synthetic rubber (A-1) in the entire composition to 15
It was shaped into a J, jl pellet using an extruder (cylinder temperature: 230°C). Using this pellet, various test pieces were prepared by injection molding. Various physical properties were evaluated. The results are shown in Table 3. Comparative Example 1 50 parts of the above graft copolymer (G-1). Styrene-acrylonitrile copolymer (M-1”135
and polymethyl methacrylate (acrivet vH
1 Blend 15 parts of Mitsubishi Rayon (II”, 1J),
A test piece was molded in the same manner as Example 1 on the husband side, and various physical properties were evaluated. The results are shown in Part 2 and Table 3. This tree composition had poor plating properties. Comparative Example 2 Synthesis of styrene-acrylic nitrile-methyl medacrylate symbiotic combination (M-2): Styrene 50 parts Acrylonitrile 20 g (S Methyl methacrylate 30 parts Calcium phosphate 1.0 part GA
F'ACGB520 0.003g
(Dispersion aid, manufactured by Toho Chemical ■) gIl Lauryl peroxide 0.6 parts t-dodecyl mercaptan 0.5 g
(S water 20
A styrene-acrylonitrile-methyl methacrylate copolymer was synthesized according to the above composition. The polymerization temperature was so'c and the polymerization time was 6 hours. The polymerization rate was 96.496. 50 parts of the graft copolymer (G-1) and styrene
Acrylonitrile-methyl methacrylate copolymerization! ,k
(M-2) 50 g (l) was mixed and evaluated in the same manner as in Example 1. The results are shown in Table ff13. Like Comparative Example 1, this resin composition also had poor plating properties. Examples 2 to 5 and Comparative Examples 3 to 4 Synthetic rubbers (A-2 to A-
5 and B-1 to B-2). Graft copolymerization (*(G-2 to G-5 and H-1 to
H-2) was cut. The polymerization rate, average particle diameter, gel fraction of the obtained synthetic rubber, the polymerization rate of the graft copolymer, and the graft copolymer
They are summarized in the table. Table 3 shows the results of evaluation of resin compositions containing each graft copolymer in the same manner as in Example 1. - Space below - Comparative Example 5 Synthesis of synthetic rubber f B-3): 1.3-Butadiene 75 parts Styrene 25 parts Potassium oleate 0.5 parts Disproportionated potassium rosinate 0.5 parts Potassium persulfate 0.3 t-dodecyl mercaptan 0.4 g water
50
10 (l) of the above ingredients were placed in an autoclave. Polymerization '8'' was started at 60°C with stirring at 80 rpm. Polymerization ← When the discharge rate reached 3096, the stirring rotation speed was increased to 14.
When the polymerization rate exceeds 50%, the stirring speed is lowered to 100 rpm, and the stirring speed is increased to 100 rpm.
．． A mixture of 0 parts, 1.0 parts of disproportionated potassium rosinate, and 15 parts of water was added intermittently to the polymerization system. -1 in 45 hours
1 (coupled to completion, 1 polymerization rate: 97°, 5 parts, 1 particle diameter: 0.28μ)
A rubber latex with a gel fraction of 8,596 was obtained. Using this synthetic rubber (B-3), one graft copolymer (H-3) was produced under the same conditions as in Example 1. The polymerization rate was 97.3%, and the graph l-rate was 51%. The properties of the resin composition containing the graft copolymer (H-3) are shown in Section 3K. Examples 6 to 8 and Comparative Example 6 Synthetic rubber obtained in the same manner as Example 1/fUH2 (8-2
) and under the polymerization conditions shown in Table 2, the graft copolymer (
G-6 to G-8 and H-4) were synthesized. Styrene-acrylonitrile copolymer (M-1) obtained in the same manner as in Example 1 was added to the obtained graft copolymer so that the amount of synthetic rubber (A-2) in the total composition was 15%. The mixture was blended at the blending ratio shown in the third section so that the following results were obtained. Table 3 shows the properties of each resin composition. 1 or less margin 1 Table 2 implementation full 9 α-methylstyrene-acrylonitrile copolymer (M-
Synthesis of 3): α-Methylstyrene 70 parts Acrylonitrile 30 parts Potassium oleate 2.0 parts Cumenic acid 0.5 parts Ferrous sulfate 0.01 g Sodium heptabirophosphate 0.2 parts Dextrose 0.35 parts t-dodecyl mercaptan 0.5 volume water
An α-methylstyrene-acrylonitrile copolymer (M-3) was synthesized according to the 250 parts composition. Polymerization IAA temperature is 65°C and polymerization time is 4 hours. The amount of acrylonitrile was reduced by 1 kg in 2.5 hours, and the polymerization rate was 94%. Styrene-acrimitrile co-IF combination c M-1)
α-methylstyrene-acryloni) instead of l) IJ
The properties of the resin composition were evaluated using 1 m of the resin composition (IVI-3) in the same manner as in Example 1.2-
The results are shown in Table 3. Examples 10-11 and Comparative Examples 7-8 The graft copolymer (G-7) used in Example 7 was blended with styrene-acrylonitrile copolymer it (M-1) at the blending ratio shown in Table 3. . The properties of these resin compositions were evaluated in the same manner as in Example 1, and the results are shown in Table 3. Comparative Examples 9 to 10 The procedure was carried out in the same manner as in Example 1, except that the styrene/acrylonitrile copolymer (M-1) was replaced with a copolymer (M -4 or M-5) 4 was synthesized and blended with the graft copolymer (G-1). The results obtained in the third
9. The symbols in Table 3 have the following meanings. St Styrene AN Acrylonitrile PMMA Polymethyl methacrylate Evaluation of molded appearance and surface appearance = (Q: Good against skin ○: Good △: Slightly poor ×: Poor plating adhesion reinforcement evaluation (C) = 1□5 h /cm or more ■=1.0~
1.5 Kg/K: 0.5~1.0 Kg/crtrK: 0~0.
5Kf/α -hereinafter referred to as white- Examples 12 to 14 Synthesis of graft copolymer CG-9): Rubber latex (A-1) 45 parts (as solid content)
Styrene 38.5 parts Acrylonitrile 16.5 parts Disproportionated potassium rosinate 1.0 parts Cumene hydroperoxide
0.2 M ferrous sulfate o, o
o s part Sodium birophosphate 0.2
part dextrose 0.4 part t-
Dodecyl mercaptan 0.5 parts 71
Using 160 parts (including water in the rubber latex) of the rubber latex obtained in Example 1 + A-1), graft together according to the above composition. Synthesized. Union IM leaf is 65℃
One polymerization time is 5 hours. During the graft polymerization, cumene-human σ-peroside and t-dodecylmerkabutanke were mixed and dissolved in the above styrene and acriminitrile, and this was added dropwise to the rubber latex (A-1) over a period of 3 hours. The polymerization rate was 97.5%, and the grafting rate was 83%F. To the obtained graft copolymer latex were added 2 parts of butylated human α-gicitoluene and 055 parts of dilaurylthioprobionate as antioxidant I, solidified with 5% aqueous sulfuric acid, washed, and dried to form a white powder. I got it. Graft copolymer (G-10) to ((, -11)
: Example 1 Blood Using the rubber latex (A-1) obtained in Example 1,
The graft copolymer (G
-10) to (G-11') were synthesized. G-10G-11 Rubber latex (A-1) 45 parts 30 parts (
(as solid + m) Styrene 38.5 parts 4
9 parts acrylonitrile 16°5M21
N-disproportionated potassium rosinate 1.0 part
1.0 part cumene hydroperoxide 0.2
81i0.35 part 1 cup sulfuric acid
0.0100 parts by weight 0.0100 parts by weight Sodium birophosphate 0.2 parts 0.2
0.4 parts dextrose
0.4 part t-dodecyl mercaptan 0.3
part 0.0 part water
160 parts 160 parts (contains water in rubber latex (including water in rubber latex)) Polymerization temperature 65°C
65℃ Polymerization time 4 hours 5 hours Dripping time 120M1Jl 180F@Suppressor Polymerization rate 97.0%97.396 Grafting rate
120% 17096 In addition, during the above graft polymerization, cumene hydroveroxide and t-dodecyl mercaptan were mixed and dissolved in the above specified amounts of styrene and acriminitrile, and each was added to rubber latex (A-1
) at a predetermined dropping time. The obtained graft copolymer latex was treated in the same manner as the graft copolymer (G-9) to obtain white powders. Characteristics and physical property evaluation of resin composition: Each of the above graft copolymers (G-9), (G-10) and (G-11) and styrene-acrylic nitrile tt-polymerization 1jl obtained in Example INJ 1 -(M-1) in Henschel Mickey using the formulation shown in Table 4.
These pellets were mixed for 5 minutes using an extruder (cylinder @ 230°C), and the synthetic rubber (A-1) content in the total composition was 15%. For injection molding, various test pieces were prepared and various physical properties were evaluated. The results are shown in Table 4. Comparative Example 11 Synthesis of Graft Copolymer (H-5): Using the rubber latex (A-1), a graft copolymer (H-5) was synthesized according to the composition and polymerization conditions described below. Rubber latex (A-1>30 parts 11 parts as solid content) Styrene 49 parts Acrylonitrile 21 parts Disproportionated potassium rosinate 1.0 parts Cumene hydroperoxide 0.5 parts Ferrous sulfate
0.0100 parts by weight Sodium birophosphate 0.2 parts Dextrose 0.4 parts t-dodecyl mercaptan o, o q water
160 parts (including water in rubber latex) Polymerization temperature: 70°C Polymerization time:
6 hours drip time 4
Time polymerization rate: 97.4% Grafting rate: 200 96 For the above graft polymerization, cumene hydromiperoxide and t-dodecyl mercaptan are mixed and dissolved in the above-described styrene and acryl-α nitrile, and each is added to rubber latex (A-
1) was carried out at a predetermined dropping time. The obtained graft copolymer latex was treated in the same manner as the graft copolymer (G-9). l! L, each obtained a white powder. 50 parts of this graft copolymer K()l-5) and the styrene-acrylonidyl copolymer (M-1') obtained in Example 1
50PA were mixed in a Henschel mixer at 3000 rpm for 5 minutes each, and the synthetic rubber (A-I
) is 15%. Jl) were each made into pellets using an extruder (cylinder warm temperature: 230°C). Using this beret, J,
, l) Each test piece was prepared and various physical properties were evaluated. The results are also shown in Table 4. As is clear from the results in Table 4, Comparative Example 11 was found to have poor Izot impact strength (L) and poor fluidity. Comparative Example 12 Synthesis of synthetic rubber (B-4): 1.3-butadiene 75 parts styrene 25 parts potassium oleate t,o
gt+disproportionated potassium rosinate 1.0
Part diisoglopylbenzenebaokindo 0.
2 parts ferrous sulfate 0.
00505 parts Sodium pyrophosphate 0
．． 5 parts dextrose 0
．． 3! Rt-dodecyl mercaptan
1.0 Volume of water
Polymerization was carried out at 50° C. using a 1001 autoclave according to the composition of 200 parts. In 9 hours, 111 polymerization resulted in a 1-polymerization rate of 96% and an average particle size of 0.
094μ, a rubber latex membrane with a gel fraction of 52% was obtained. Synthesis of graft copolymer (H-6): Rubber latex CB-4) 458111 (as solid content) Styrene 38.
5 parts acryl nitrile 16.
5 parts heterogeneous potassium rosinate 1.0
part cumene hydroperoxide 0.3
M ferrous sulfate 0.01
00 parts by weight Sodium pyrophosphate
0.2 Part Degistrose
0.3 part t-dodecyl mercaptan
A graft copolymer (H-6) was synthesized according to the above composition using 0.3 to 1 ff (160 parts of water (including water in the rubber latex) using the rubber latex CB-4). Polymerization part 1 temperature was G5℃, polymerization time & 5 hours at home. At the time of graft polymerization, cumene hitomi peroxide and t-dodecyl mercaptan are mixed and dissolved in the above styrene and acryl alpha nitrile, and this is mixed into rubber latex (
B-4) was added dropwise over 2 hours. The polymerization rate was 97.0% and the grafting rate was 120%. The obtained graft copolymer latex was treated in the same manner as the graft copolymer ((, -9)) to obtain a white powder of graft copolymer fH-6. 50 parts of this graft copolymer (H-6) and 50 parts of the styrene-acrylonitrile copolymer CM"-1) obtained in Example 1.
0 parts were mixed in a Henschel mixer at 300 Orpm for 5 minutes to bring the content of synthetic rubber (B-4) in the entire composition to 15 m.
It was cut into sweet potatoes, and then immersed in pellets using an extruder. 1 (cylinder fI degree 230°C). Using this bellet, central Jal
Table 1 also shows the results of I) evaluation of various physical properties by the same method as in Example 111. From the results in Table 1, it is clear that synthetic rubber (B-1)
It can be seen that when the gel fraction is less than No. 60, the appearance becomes poor. Examples 15-20. Comparative Examples 13 to 15 Synthesis of graft copolymer (G-12): Using the rubber latex (A-1) obtained in Example 1, graft copolymer (G-12) ff was prepared according to the following composition and polymerization conditions. Synthesized. Rubber latex (A-1) 45 parts (as solid content) Styrene 38.5 parts Acriminitrile 16.5 parts Disproportionated potassium rosinate 1.0 parts Cumene hydroperoxide 0.2 1 flI Ferrous sulfate 0. 0100 parts by weight piσ
Sodium phosphate 0.2 parts Dextrose 0.4 parts t-dodecylmercagtan 0.15 parts Water
160 parts (including water in rubber latex) Polymerization @ degree 65・c Polymerization 51
5 hours drip time
3 hour polymerization rate: 97.3 reduction Grafting rate: 150 reduction In addition, in the above-mentioned graft polymerization, cumene hydroxide a / A-1
) at a predetermined dropping time. The obtained graft copolymer latex was treated in the same manner as graft copolymerization 1 (G-9) to obtain a white powder. According to the above composition and polymerization conditions, the graft copolymer (I
I-1) to (II-5) were synthesized. Incidentally, the above-mentioned graft polymerization 15σ) dropping is a mixture of cumene hydroperoxide and t-dodecyl mercaptan dissolved in styrene, ``!''ri') lonitrile as specified in 11 above. Do not use the specified drop times on poly 1,3-budadiene latex. To each latex of the obtained graft copolymer, 2 parts of butylated human a-xytoluene and 0.15 parts of dilaurylthioprobionate were added, coagulated with a 5% aqueous sulfuric acid solution, washed, and dried to obtain a white powder. Preparation and production of resin composition and evaluation of physical properties: Graft copolymers (G-1) obtained in Examples 1 and 12
, (G-9) and the graft compound 11 (combination (G-12)) obtained by the above method and the styrene-acrylonitrile monomer (M-1) obtained in Example 1 were synthesized as shown in Table 5. The graft copolymer (II-1) obtained by the above method (M5) was added to the mixture containing rubber (A-1) so that the content was 15% as shown in Table 5. Graft copolymer (I-1) in the whole composition
The rubber content based on (l [-5) was changed to hl (hl) and blended for 5 minutes at 300° rpm, and then formed into pellets using an extruder. Using these pellets, various tests were performed using an injection molding machine. A specimen was prepared and various physical properties were evaluated.The results are shown in Table @5.As is clear from the results in Table 45, Examples 15 to 20 showed poor Izot impact strength, translucency, and plating properties. I understand. In Comparative Example 13, graft copolymerization [4(II-
Since the graft ratio of 5) is as high as 130%, the fluidity is rather poor and sufficient impact strength cannot be obtained. In Comparative Example 14, the grafting rate of the graft copolymer (II-4) was as low as 15%, so the surface gloss was rather poor and the translucency was poor. In addition, in Comparative Example 15, the butadiene rubber content of the graft copolymer (LIT-2) in the entire composition was 20%, which was crystalline, so although the impact strength was sufficient, the mechanical properties were poor. I understand. [Effects of the Invention] The thermoplastic surface Il1 composition of the present invention particularly has the following advantages compared to conventionally known thermoplastic resin compositions. (II 1) Conventional transparent ABS resins do not provide good plating properties, whereas 5 they maintain the same brightness and gloss as ordinary ABS resins, while having significantly higher translucency. (A ) In the case of double-molded products of polystyrene and ABsttt fingers, which are conventionally used to mold display switches with a feeling of fraud, the molding mold is complicated and the molding operation is complicated, resulting in high molding costs and a wide variety of designs. The molding process cost can be reduced and the design can be diversified.

Claims (1)

[Claims] 1,3-butadiene 50-100% by weight and 0 styrene
Synthetic rubber (with a gel fraction of 60% or more obtained from ~50% by weight and an average particle size of 0.04 to 0.15μ)
A) 20-85 parts by weight of a monomer mixture (B) consisting of 60-80% by weight of an aromatic vinyl monomer and 20-40% by weight of a vinyl cyanide monomer based on 15-80 parts by weight of latex (as solid content) [(A ) and (B) in a total amount of 100 parts by weight].
Graft copolymer (I) with a grafting rate of 180%
) and a copolymer (II) obtained from 60 to 80% by weight of an aromatic vinyl monomer and 20 to 40% by weight of a cyanated vinyl monomer, the total of the graft copolymer (I) and the copolymer (II) The content of synthetic rubber (A) in the amount is 5 to 30
% by weight and 0.2 to 0.
A monomer mixture consisting of 60-80% by weight of an aromatic vinyl monomer and 20-40% by weight of a vinyl cyanide monomer based on 15-75 parts by weight (as solid content) of a butadiene-based rubber (C) latex having an average particle diameter of 4μ. (D
) 25 to 85 parts by weight [total amount of (C) and (D) is 100
20 to 100% obtained by graft polymerizing [parts by weight]
The graft copolymer (III) having a graft ratio of
The content of butadiene rubber (C) in the whole composition is 0 to 1
An impact-resistant thermoplastic resin composition having good translucency and plating properties, which is blended in an amount of 5% by weight.