JP3173378B2 - Powder composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a rubber-rich rubber-modified thermoplastic resin which has improved blocking properties during powder storage and can be stored for a long period of time, and further contains another thermoplastic resin in the powder composition. The present invention relates to a powder composition in which a molded article of a thermoplastic resin composition obtained by blending is excellent in impact resistance, gloss, and molded appearance, and in which the phenomenon of fish eye generation is significantly improved.

[0002]

2. Description of the Related Art ABS resins and AES resins are widely known as rubber-modified thermoplastic resins, and are used in large quantities industrially. As a method for producing an ABS resin, the following two methods are generally known. A method obtained by polymerizing 75 to 95% by weight of a monomer composed of styrene and acrylonitrile in the presence of 5 to 25% by weight of a rubbery polymer. An ABS resin having a high rubber content (hereinafter referred to as "rubber-rich ABS resin") obtained by polymerizing 55 to 60% by weight of a monomer composed of styrene and acrylonitrile in the presence of 40 to 45% by weight of a rubbery polymer, Separately, a method of obtaining an ABS resin by blending with a styrene-acrylonitrile copolymer (AS resin) obtained by polymerization and adjusting the content of the rubbery polymer in the blend to 5 to 25% by weight ( The ABS resin obtained by this method is hereinafter referred to as “blend type ABS”.
Resin)). The above method uses rubber-rich ABS
By appropriately selecting the amount of the resin and by appropriately selecting the type of the AS resin, various types of ABSs having various qualities can be obtained.
Resin can be manufactured with high productivity. But AB
In the S resin industry, further cost reduction is required. As a measure to reduce this cost, Rubber Rich A
A method of increasing the productivity of the blend type ABS resin by further increasing the rubber content of the BS resin and increasing the compounding amount of the low-cost AS resin having excellent productivity. However, when the rubber content of the rubber-rich ABS resin is increased as compared with the conventional product, blocking tends to occur remarkably during storage of the resin powder, handling property in a post-process is poor, and the resin powder in which blocking occurs occurs. When an ABS resin is obtained by blending with an AS resin, there is a problem that fish eyes are generated in a final product because the resin is not sufficiently dispersed. Further, further improvement in impact resistance of ABS resin is also expected.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of a rubber-rich ABS resin having a high rubber content, and is free from blocking during powder storage, and can be stored for a long period of time. The thermoplastic resin composition obtained by blending this thermoplastic resin composition with another thermoplastic resin is excellent in impact resistance, gloss, molding appearance, and significantly reduces fish eye defects. It is an object of the present invention to provide an improved rubber-rich ABS resin-based powder composition.

[0004]

The present invention is obtained by polymerizing an aromatic vinyl compound (b) and a vinyl cyanide compound (c) in the presence of a rubbery polymer (a), wherein (a) The content of the component is 50 to 80% by weight, the content of the component (b) is 5 to 48% by weight, and the content of the component (c) is 2 to 45% by weight.
[However, (a) + (b) + (c) = 100% by weight] and the Q value by the measurement method specified below is 30.
(B) 0.01 to 6 parts by weight of silicone oil, and (C) silicone oil with respect to 100 parts by weight of (A) the rubber-modified thermoplastic resin powder which is from × 10 ^{-4 to} 500 × 10 ^-4 cc / sec. It provides a powder composition containing 0.1 to 20 parts by weight of a lubricant other than the above. Measurement method of Q value (A) The rubber-modified thermoplastic resin used for measurement is 110
Volatile substance content at 0.1 ° C x 60 min.
Use the one adjusted below. Q value measurement conditions Measuring device: Shimadzu flow tester CAPILLARY RHEOMETER CFT-5
00 Measurement conditions: sample amount; 1.8 g plunger area; 1.0 cm ² die size; 2.0 mm length × 1.0 mm φ preheating temperature and time; 200 ° C. × 5 minutes measurement temperature; 200 ° C. load; cm ²

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The rubber-modified thermoplastic resin powder (A) of the present invention comprises an aromatic vinyl compound (b) and a vinyl cyanide compound (c) in the presence of a rubbery polymer (a). Obtained by polymerization, the content of the component (a) is 50 to 80% by weight,
The component (b) content is 5 to 48% by weight, the component (c) content is 2 to 45% by weight, and the Q value is 30 × 10 ^{−4 to} 500 ×.
10 ^-4 cc / sec, a rubber-rich rubber-modified thermoplastic resin powder.

The rubbery polymer (a) used as the base rubber of the rubber-modified thermoplastic resin powder (A) of the present invention includes, for example, polybutadiene, polyisoprene, styrene-butadiene copolymer (styrene content 5 to 60% by weight). % Is preferred), styrene-isoprene copolymer, acrylonitrile-butadiene copolymer, ethylene-α-olefin-based copolymer, ethylene-α-olefin-polyene copolymer, acrylic rubber, butadiene- (meth) acrylic acid Examples include an ester copolymer, polyisoprene, a styrene-butadiene block copolymer, a styrene-isoprene block copolymer, a hydrogenated styrene-butadiene block copolymer, a hydrogenated butadiene-based polymer, and an ethylene-based ionomer. In addition, the styrene-butadiene block copolymer and the styrene-isoprene block copolymer include those having an AB type, ABA type, a taper type, a radial teleblock type, and the like. further,
The hydrogenated butadiene-based polymer is, in addition to the hydride of the block copolymer, a styrene block and a styrene-butadiene random copolymer block, and a 1,2-vinyl bond content in polybutadiene of 20% by weight. % Or less, and a hydride of a polymer comprising a polybutadiene block having a 1,2-vinyl bond content of more than 20% by weight. These rubbery polymers (a) have the following properties:
Used alone or in combination of two or more. Preferred (a)
The component is at least one conjugated diene rubber selected from polybutadiene and styrene-butadiene (styrene content is preferably 5 to 60% by weight) copolymer,
More preferably, it is a mixture having a ratio of polybutadiene / styrene-butadiene copolymer = 50 to 99/1 to 50 (% by weight).

The aromatic vinyl compound (b) used in (A) the rubber-modified thermoplastic resin powder includes, for example, styrene, t-butylstyrene, α-methylstyrene,
p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-p-aminoethylstyrene, N, N-diethyl-p-aminomethylstyrene, vinylpyridine, vinylxylene, monochlorostyrene, dichlorostyrene , Monobromostyrene, fluorostyrene, ethylstyrene, vinylnaphthalene, and the like, and styrene and α-methylstyrene are particularly preferable. These aromatic vinyl compounds may be used alone or in combination of two or more. Examples of the vinyl cyanide compound (c) include acrylonitrile and methacrylonitrile.

For the purpose of the present invention, the above (b) to (b)
In addition to the component (c), other vinyl monomers can be used as long as they do not cause any trouble. As other vinyl monomers, for example, methyl acrylate, ethyl acrylate,
Acrylic esters such as propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate and benzyl acrylate; methyl methacrylate
G , ethyl methacrylate , propyl methacrylate,
Butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, methacrylic acid esters such as benzyl methacrylate; maleic anhydride, itaconic anhydride, citraconic anhydride and the like Unsaturated acid anhydrides; unsaturated acids such as acrylic acid and methacrylic acid; maleimide, N-methylmaleimide, N-butylmaleimide;
Α- such as N- (p-methylphenyl) maleimide, N-phenylmaleimide and N-cyclohexylmaleimide
Or an imide compound of β-unsaturated dicarboxylic acid (also referred to as a maleimide monomer); glycidyl methacrylate;
Epoxy compounds such as allyl glycidyl ether; unsaturated carboxylic amides such as acrylamide and methacrylamide; acrylamine, aminomethyl methacrylate,
Amino group-containing unsaturated compounds such as aminoethyl methacrylate, aminopropyl methacrylate, aminostyrene,
3-hydroxy-1-propene, 4-hydroxy-1-
Butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy-2-
Examples include a hydroxyl group-containing unsaturated compound such as methyl-1-propene, 2-hydroxyethyl acrylate, and 2-hydroxyethyl methacrylate; and an oxazoline group-containing unsaturated compound such as vinyl oxazoline. These other vinyl monomers are used alone or in combination of two or more. The content of the other vinyl monomer is preferably 20% by weight or less, more preferably 10% by weight or less in the components excluding the component (a).

(A) The content of the rubbery polymer (a) component in the rubber-modified thermoplastic resin powder is 50 to 80% by weight, preferably 52 to 75% by weight, more preferably 56 to 7% by weight.
4% by weight. When the content of the component (a) is less than 50% by weight, the effect of improving the productivity is not sufficient.
If the ratio exceeds the above range, fish eyes are likely to be generated, the appearance and impact resistance are significantly reduced, and even if the component (B) is blended, blocking of the powder may not be prevented in some cases. The content of the aromatic vinyl compound (b) in the rubber-modified thermoplastic resin powder (A) is 5 to 48% by weight, preferably 5 to 46% by weight, and more preferably 1 to 46% by weight.
3 to 41% by weight. The content of the vinyl cyanide compound (c) is 2 to 45% by weight, preferably 2 to 4% by weight.
It is 3% by weight, more preferably 3 to 31% by weight.
When the component (b) is less than 5% by weight, when the component (b) exceeds 48% by weight, when the component (c) is less than 2% by weight,
In any case in which the component (c) exceeds 45% by weight, at least one of the effect of improving the poor phenomenon of fish eye generation, the effect of improving appearance, and the effect of improving impact resistance is not sufficient. All three cannot be maintained at the desired level.

(A) The Q value of the rubber-modified thermoplastic resin powder is 30 × 10 ^{−4 to} 500 × 10 ⁻⁴ cc / sec, preferably 50 × 10 ^{−4 to} 400 × 10 ⁻⁴ cc / sec. More preferably, 70 × 10 ^{−4 to} 400 × 10 ⁻⁴ cc.
/ Sec. Also Q value is less than 30 × ¹⁰ -4 cc / sec, even beyond the 500 × ¹⁰ -4 cc / sec, both off
Generation of Isshu eye is increased, is inferior, not impact resistance sufficient appearance. When the Q value exceeds 500 × 10 ⁻⁴ cc / sec, even if the components (B) and (C) are blended, the powder composition does not sufficiently improve the blocking and retain the impact resistance, and furthermore, this composition When pelletizing, the strands are easily cut, and pelletization becomes difficult.

The conditions for measuring the Q value are shown below. (A) The rubber-modified thermoplastic resin powder used for the measurement is 1
The volatile substance content under the condition of 10 ° C. × 60 minutes is 0.1
Adjust to less than weight%. Measurement conditions of Q value Measuring device; Shimadzu flow tester CAPILLARY
RHEOMETERCFT-500 Measurement conditions; Sample amount: 1.8 g Plunger area: 1.0 cm ² Die size: 2.0 mm length × 1.0 mm φ Preheating temperature and time: 200 ° C × 5 minutes Measurement temperature: 200 ° C Load: 60 kg / cm ²

The graft ratio of the rubber-modified thermoplastic resin powder (A) is 5% by weight or more, preferably 10% by weight or more. When the graft ratio is less than 5 wt%, fit
Generation of shoe eye often, poor appearance and impact resistance. The graft ratio is measured by the following method. Here, the graft ratio refers to the ratio of the copolymer component directly graft-bonded to the rubber-like polymer with respect to the rubber amount in the rubber-modified thermoplastic resin powder (A). This graft ratio is determined by the amount of polymerization initiator,
It can be controlled by the polymerization temperature and the like. As a specific method of obtaining the graft ratio, first, 2 g of the rubber-modified thermoplastic resin powder (A) of the present invention is charged into acetone at room temperature, and sufficiently stirred to obtain an insoluble matter (w). On the other hand, the amount of the rubbery polymer in the insoluble matter (w) can be calculated based on the polymerization recipe. The calculated total amount of the rubbery polymer is represented by R
And the graft ratio is determined from the following equation. Graft ratio (% by weight) = [(w−R) / R] × 100

In the case of emulsion polymerization, the latex of the rubbery polymer (a) used in the rubber-modified thermoplastic resin powder (A) preferably has an average particle size of 50 to 600 nm.
It is more preferably from 100 to 500 nm, particularly preferably from 150 to 450 nm, and when it is within this range, the thermoplastic resin composition obtained by using the (A) rubber-modified thermoplastic resin powder of the present invention has an Izod impact strength, It becomes excellent in gloss.

Here, the average particle diameter is determined by treating a rubber-like polymer (a) latex with osmic acid and subjecting it to, for example, a laser particle size analysis system LPA manufactured by Otsuka Electronics Co., Ltd.
Using -3100 in an electron micrograph (magnification: 30,000 times), the particle diameter was measured for 100 or more particles, and the value was calculated from the number average. The average particle size of the latex of the rubbery polymer (a) is determined by the amount of the emulsifier, the amount of the polymerization initiator,
By selecting the polymerization temperature and the like, a desired latex can be obtained by combining these.

In the present invention, the gel content of the latex of the rubbery polymer (a) used in the rubber-modified thermoplastic resin powder (A) is preferably 50 to 100% by weight.
More preferably, it is 60 to 95% by weight. When the gel content is less than 50% by weight, the amount of deformation of the rubber is large, and the glossiness of the thermoplastic resin composition obtained by using the (A) rubber-modified thermoplastic resin powder of the present invention is preferably reduced. Absent. In particular, when the gel content is 60 to 95% by weight,
The resulting thermoplastic resin composition has impact resistance, weld,
It is suitable for grades requiring appearance such as gloss, for example, electric appliances and OA equipment.

Here, the gel content means that a latex film (Ag) of the rubbery polymer (a) is immersed in 100 ml of toluene at 50 ° C. for 2 hours with stirring, and
Filter using a 0 mesh wire mesh, and a part of the filtrate (Cml)
Is accurately collected and evaporated to dryness, and the obtained residual solid content (toluene-soluble matter; Bg) is weighed, and the gel content is determined by the following equation. Gel content (% by weight) = ｛[AB × (100 / C)] /
A｝ × 100

The adjustment of the gel content can be easily carried out by selecting the type and amount of the molecular weight modifier. In addition, the adjustment of the gel content includes addition of a cross-linking agent, selection of the amount of a polymerization initiator during polymerization, polymerization initiation temperature, and the like. By combining these, it is possible to obtain a target rubber-like polymer (a) latex. it can.

The content of the components (a), (b) and (c) in the rubber-modified thermoplastic resin powder (A) can be appropriately adjusted by the charged amounts of these components during polymerization. In addition, (A) in the rubber-modified thermoplastic resin powder (A)
The component, component (b), and component (c) content can be determined from the charged amounts of these components and the polymerization conversion. As another method, it can be determined by a known quantitative analysis method. (A) The Q value of the rubber-modified thermoplastic resin powder is adjusted by appropriately selecting the type and amount of a chain transfer agent and an initiator used during polymerization, by appropriately selecting the polymerization temperature, and by adjusting the rubber-like polymer. It can be carried out by appropriately selecting the gel content and molecular weight of (a).

The intrinsic viscosity (methyl ethyl ketone, 30 ° C.) of the (A) rubber-modified thermoplastic resin powder of the present invention is preferably 0.1 to 0.5.
dl / g, more preferably 0.15 to 0.4 dl / g
It is. If it is less than 0.1 dl / g, the impact resistance of the obtained rubber-modified thermoplastic resin powder (A) decreases, while
When it exceeds dl / g, generation of fish eyes is increased and molding appearance is inferior. This intrinsic viscosity can be easily adjusted by appropriately selecting the type and amount of the chain transfer agent and the polymerization initiator and the polymerization temperature.

The method for producing the rubber-modified thermoplastic resin powder (A) is not particularly limited, but a preferred polymerization method is an emulsion polymerization method. In the emulsion polymerization, a polymerization initiator, a chain transfer agent, an emulsifier, and the like are used.

Various organic peroxides are used as the polymerization initiator used in the production of the rubber-modified thermoplastic resin powder (A) of the present invention. Examples of the organic peroxide include ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, and percarbonates. Further, a polymerization initiator such as potassium persulfate and azobisisobutyronitrile can also be used. The organic peroxide is also used in combination with a reducing agent such as a sugar-containing iron pyrophosphate formulation, a sulfoxylate formulation, or a mixed formulation of a sugar-containing iron pyrophosphate formulation / sulfoxylate formulation. Among the above organic peroxides,
More preferred are hydroperoxides, alkyl peresters, and percarbonates. These organic peroxides can be used alone or in combination of two or more. Also, -O-
When an organic peroxide having two or more O-bonds is used, the effect of the present invention can be further improved.

The initiator is used in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the total of the rubber component and the monomer component.
Preferably it is 0.1 to 2 parts by weight. If the amount is less than 0.01 part by weight, the monomer conversion is low, and a large amount of unreacted monomer remains, which is not preferable in production. On the other hand, if it exceeds 5 parts by weight,
The molecular weight of the grafted copolymer is remarkably reduced, sufficient impact resistance is not obtained, and the color tone of the obtained thermoplastic resin is remarkably deteriorated.

Examples of the chain transfer agent include halogenated hydrocarbons (eg, chloroform, bromoform, etc.), mercaptans (eg, n-dodecyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan, n-hexadecyl) Mercaptan), mercaptopropionate (eg, dodecylmercaptopropionate, octylmercaptopropionate, etc.), terpenes (eg, dipentene, terpinolene, etc.), and α-methylstyrene dimer. The amount of the chain transfer agent to be used is preferably 2 parts by weight or less, more preferably 1.0 part by weight, based on 100 parts by weight of the total of the rubber component and the monomer component.
5 parts by weight or less. When the amount of the chain transfer agent exceeds 2 parts by weight, the molecular weight of the grafted copolymer decreases, sufficient impact resistance cannot be obtained, and the powder composition has blocking resistance (B), ( Even if components such as component (C) are blended, there is no improvement.

The emulsifier used in the emulsion polymerization includes an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant. Among them, examples of the anionic surfactant include a higher alcohol sulfate, an alkylbenzene sulfonate, a fatty acid sulfonate, and a phosphoric acid type. As the nonionic surfactant, an alkyl ester type, an alkyl ether type, an alkyl phenol type or the like of polyethylene glycol is usually used. Further, examples of the amphoteric surfactant include those having a carboxylate, a sulfate, a sulfonate, or a phosphate as an anion portion, and an amine salt, a quaternary ammonium salt, or the like as a cation portion. Specific examples of the amphoteric surfactant include:
Betaines such as lauryl betaine and stearyl betaine, and amino acid types such as lauryl-β-alanine, stearyl-β-alanine, lauryl di (aminoethyl) glycine, and octyl di (aminoethyl) glycine are used. These emulsifiers can be used alone or in combination of two or more. The amount of the emulsifier used is usually about 0 to 5 parts by weight based on 100 parts by weight of the total of the rubber component and the monomer component.

In the graft polymerization, in addition to a polymerization initiator, an emulsifier, a chain transfer agent, etc., if necessary, various electrolytes, a pH adjuster and the like are used in combination to obtain a rubber component (in terms of solid content) and a monomer component. With respect to 100 parts by weight of the total, usually, water is used in an amount of 100 to 500 parts by weight, the polymerization initiator , the emulsifier, the chain transfer agent and the like in the above range, and usually,
Polymerization is performed under the conditions of a polymerization temperature of 5 to 120 ° C and a polymerization time of 0.1 to 20 hours.

Usually, the rubber-modified thermoplastic resin powder (A) of the present invention is produced by coagulating a latex obtained by the above-mentioned emulsion polymerization by a conventional method, washing the obtained powder with water, and drying it. Is done. The particle size of the rubber-modified thermoplastic resin powder (A) thus obtained preferably satisfies the following conditions in the measurement by dry classification using a standard sieve. φ0.15 mm (= 150 μm) or less (for 100 mesh passes) is 40% by weight or less of the whole. φ0.85mm or more (18.5 mesh pass-on) accounts for 10% by weight or more of the whole. Within this range, when the components (B) and (C) are blended, a sufficient blocking improving effect can be obtained. on the other hand,
If the particle size of the rubber-modified thermoplastic resin powder (A) is out of the above range, pulsation by an extruder or the like is required when pellets or the like are obtained alone or mixed with (D) another thermoplastic resin. This may cause unstable operation or increase the fisheye of the final product, which is not preferable. The particle size can be easily adjusted by the type and amount of the coagulant at the time of coagulation, the temperature, and the like.

The obtained rubber-modified thermoplastic resin powder (A) can be pelletized by a kneading machine such as an extruder. The resulting pellet shape is cylindrical,
Prismatic or spherical, in the case of ~, base area 3
３０30 mm ² , preferably 4-9 mm ² , height 2-10
mm, preferably about 3 to 4 mm, the volume is 4 mm.
１６165 mm ³ , preferably about 6.4-36 mm ³ . In general rubber-rich ABS resin, the strand is not drawn in the extrusion process, it is difficult to pelletize, and pulsation easily occurs inside the extruder, and the resin stays,
Burns and foreign matter are generated. However, (A) of the present invention
The rubber-modified thermoplastic resin powder has a Q value within the above range and is excellent in fluidity. Therefore, at the time of pelletizing, for example, the molten strand extruded from the melting die does not pulsate, and is easily applied to the pelletizer. Can be introduced and pelletized. Therefore, since the rubber-modified thermoplastic resin powder (A) of the present invention can be pelletized, it can be blended with a simple mixer in a blending step with another thermoplastic resin, and high-quality Product is obtained,
Also, it has excellent blend productivity.

Next, the silicone oil (B) can prevent blocking of the rubber-rich (A) rubber-modified thermoplastic resin powder and can improve the impact resistance of the component (A). Examples of the silicone oil (B) include organopolysiloxanes represented by polydimethylsiloxane, polydiethylsiloxane, polymethylphenylsiloxane, or modified products thereof. (B) The silicone oil preferably has a molecular weight of 2,300 to 6 from the viewpoint of dispersibility and handling.
000, kinematic viscosity is preferably 30 to 10,000c
s (25 ° C.). (B) The silicone oil is
It can be added to any of the latex system after polymerization of the component (A), the finishing step in the coagulation / drying step, and the powder. (B) The addition amount of the silicone oil is 0.01 to 6 parts by weight, preferably 0.02 to 5 parts by weight, based on 100 parts by weight of the component (A). At less than 0.01 parts by weight,
Poor blocking prevention effect and no improvement in impact resistance. On the other hand, when the amount exceeds 6 parts by weight, poor discharge in an extruder and an increase in fish eyes in a final product are caused.

Next, the lubricant (C) is used together with the silicone oil (B) to further improve the impact resistance of the component (A) and to improve the rubber-rich (A) rubber-modified thermoplastic resin powder. Long-term powder storage becomes possible. Examples of the lubricant (C) include fatty acids such as stearic acid and behenic acid, fatty acid metal salts such as zinc stearate, magnesium stearate, aluminum stearate, calcium stearate, barium laurate, and cadmium myristate; oleic acid amide; Acid amide,
Fatty acid amides such as ethylenebisstearylamide, ethylenebispalmitic acid amide, and ethylenebisoleic acid amide; sorbitan stearate such as butyl stearate, stearyl stearate, and sorbitan monostearate; and pentaerythritol stearin such as pentaerythritol tetrastearate Acid esters, glycerin fatty acid esters such as oleic acid monoglyceride, fatty acid esters such as hydrogenated castor oil, higher alcohols such as stearyl alcohol, and the like, are preferably used in combination with a fatty acid metal salt and a fatty acid amide.

(C) The amount of the lubricant added is (A) 100%
0.1 to 20 parts by weight, preferably 0.2 to 20 parts by weight,
１５15 parts by weight. If the amount is less than 0.1 part by weight, the effect of further improving the impact resistance of the rubber-modified thermoplastic resin powder and keeping it for a long period of time is poor. It causes poor appearance of molded products such as fogging and burns. The lubricant (C) can also be added to any of the latex system after the polymerization of the component (A), the finishing step in the coagulation / drying step, and the powder.

The powder composition of the present invention contains (A) a rubber-modified thermoplastic resin powder, (B) a silicone oil and (C) a lubricant as main components. D) Other thermoplastic resins may be blended to form a thermoplastic resin composition. (D) Other thermoplastic resins include, for example, AB having a rubbery polymer content of less than 50% by weight.
S resin, AES resin, AAS resin, AS resin, HIP
Styrene resins such as S and PS; olefin resins such as polyethylene and polypropylene; PA6, PA66,
Polyamide resins such as PA46 and PA12; Polyester resins such as polybutylene terephthalate, polyethylene terephthalate, and polyarylate; Polyphenylene ether-based resins such as polycarbonate resin, polyphenylene ether or polyphenylene ether / styrene-based resin; Polyacetal, vinyl chloride resin, polysulfone, PPS , Polyether sulfone, ethylene-vinyl acetate copolymer, EVOH and the like, and these can be used alone or in combination of two or more.

Preferred (D) other thermoplastic resins include the following, alone or in combination with each other. In the presence of the rubbery polymer, at least two selected from the group consisting of an aromatic compound, a vinyl cyanide compound, a (meth) acrylate ester, and a maleimide monomer
Other rubber-modified thermoplastic resins obtained by polymerizing monomers of a group of species and having a rubbery polymer content of less than 50% by weight. Here, the rubbery polymer and monomer here include those described above. Further, the intrinsic viscosity (in methyl ethyl ketone, at 30 ° C.) of the methyl ethyl ketone soluble portion of the rubber-modified thermoplastic resin is preferably 0.1 to 1 dl / g, more preferably 0.2 to 0.6 dl / g. is there. Aromatic vinyl compound, vinyl cyanide compound,
It is obtained by polymerizing at least two kinds of monomers selected from the group of (meth) acrylic acid esters and maleimide monomers, and has an intrinsic viscosity (measured at 30 ° C. using methyl ethyl ketone as a solvent). Preferably 0.2-1.3d
1 / g) More preferably 0.3 to 1 dl / g, particularly preferably 0.35 to 0.7 dl / g.

As the above, for example, ABS resin, A
Examples thereof include an ES resin, an AAS resin, and an MBS resin. Among them, an ABS resin and an AES resin are preferable. Examples of the above include the following copolymers. (A) A copolymer of an aromatic vinyl compound and a vinyl cyanide compound. The preferred composition ratio is such that the former monomer is 50 to 9
9 % by weight , the latter being 1 to 50% by weight. (B) A copolymer of an aromatic vinyl compound and a (meth) acrylate. (C) A copolymer comprising an aromatic vinyl compound, a maleimide-based monomer and, if necessary, a vinyl cyanide compound and / or a (meth) acrylate. In addition, an unsaturated acid anhydride monomer is used in place of the maleimide-based monomer, and the obtained copolymer is imidized, and the obtained post-imide type copolymer is also included herein. The aromatic vinyl compound, vinyl cyanide compound, (meth) acrylic acid ester, and maleimide-based monomer here are the same as those described above.

(A) Rubber-modified thermoplastic resin powder and (D)
The composition ratio of each component in the thermoplastic resin composition containing another thermoplastic resin is such that (A) the rubbery polymer (a) in the rubber-modified thermoplastic resin powder is preferably 3% in the composition. ~ 3
Each component is appropriately blended so as to be contained at 5% by weight. More preferably, the content of the component (a) is 5 to 5.
25% by weight. If the content of the component (a) is less than 3% by weight, sufficient impact resistance cannot be obtained. On the other hand, 35
Exceeding the weight percentage makes the molded product soft, which is not preferred.
On the other hand, (D) the other thermoplastic resin according to the present invention (A)
When a rubber-modified thermoplastic resin other than the rubber-modified thermoplastic resin powder is used, the rubber-like polymer contained in the other rubber-modified thermoplastic resin (hereinafter referred to as “component (a ′) component”)
Is handled as follows. The component (a ') is also regarded as the component (a) and satisfies the following conditions. [(A)
+ (A ')] is 3 to 35% by weight, and the content of (a) is 3 to 35% by weight. Preferably [(a) +
(A ')] is 5 to 25% by weight, and the content of (a) is 5 to 25% by weight.

The above-mentioned thermoplastic resin composition comprises the powder composition of the present invention [(A) + (B) + (C)], the above-mentioned (D) other thermoplastic resin, and various additives as required. It is manufactured by kneading agents. As a kneading method, there is a method using an extruder, a roll, a Banbury mixer, a kneader, or the like. A preferable method is a method using an extruder, and examples of the extruder include a single screw extruder and a twin screw extruder. the above,
When kneading various components using a kneading method, all components may be kneaded all at once, some components may be kneaded first, and the remaining components may be kneaded or divided and added and kneaded. You may. Various additives can be added to the rubber-modified thermoplastic resin (A), if necessary. When kneading is required, kneading can be performed by the method described above. As various additives, known colorants, pigments, weathering agents, antistatic agents, antioxidants, flame retardants,
Examples include a heat aging inhibitor, a plasticizer, and an antibacterial / antifungal agent. The powder composition of the present invention is usually blended with the other thermoplastic resin to form a thermoplastic resin composition, which is subjected to injection molding, sheet extrusion, vacuum molding, profile extrusion, injection press, foam molding, and blow molding. Various molded articles can be molded by molding, hollow molding, or the like.

[0036]

The present invention will now be described more specifically with reference to examples. In the examples, parts and% are based on weight unless otherwise specified. Further, various evaluations in the examples are values measured as follows, and each component,
It was prepared as follows.

[Evaluation Method] Measurement of Q Value (A) The rubber-modified thermoplastic resin used for measurement was 110
The volatile matter content was adjusted to 0.1% or less under the conditions of ° C. × 60 minutes. Measurement condition of Q value Measurement device: Shimadzu flow tester CAPILLARY RHEOMETER CFT-5
00 Measurement conditions: Sample amount; 1.8 g Plunger area; 1.0 cm ² Die size; 2.0 mm length × 1.0 mm φ Preheating temperature and time; 200 ° C. × 5 minutes Measurement temperature; 200 ° C. Load: 60 kg / cm ²

The free flow index “Chemical Engineering” (Chemical Engineering)
Engineering, published Jan. 18, 1965, pp. 163-168, the four angles of repose, compression, spacherer angle and uniformity (or cohesion).
The two measured values were obtained for the obtained powder composition, and the values were scored according to the integration table, and evaluated by an index represented by the sum of these points. The larger the measured value, the better the fluidity. A constant load (2 kg / c) is applied to 30 g of the obtained powder composition.
m ² ) and multiply by the block (shape = columnar, size = 5c)
mφ × approximately 3 cm), and a constant vibration (frequency = 60 Hz) is applied to this block for 100 seconds to be collapsed. Of the collapsed powder, the weight of the powder of the 16 mesh pass is used as the total weight of the original block. Expressed as a percentage (%). The larger the value, the harder the blocking.

(A) a rubber-modified thermoplastic resin powder and
How to mix components (B) and (C) with (D) another thermoplastic resin
Method (A) Rubber-modified thermoplastic resin powder and (B), (C)
The components, (D) other thermoplastic resin and additives were mixed at the ratios shown in Tables 2 to 5 using a Henschel mixer, and the mixture was extruded with a cylinder set temperature of 200 ° C by an extruder.
A pellet was obtained. Test Piece Molding Method Using the pellet obtained by the above method as a molding material, a test piece for measuring gloss and a test piece for measuring Izod impact strength were molded under the following molding conditions. Molding machine: 80 tons In-line screw type molding machine Mold temperature: 50 ° C. ± 5 ° C. Molding machine setting conditions: Cylinder set temperature: 200 ° C. Injection pressure: Primary pressure 75 to 95 kg / cm ² G, secondary pressure 5
0 kg / cm ² G Back pressure: 5 kg / cm ² G Molding cycle : injection 15 seconds, loading 10 seconds, curing 40 seconds, cycle start 2 seconds

Measurement of glossiness Digital gonio-gloss meter [ DIGIT manufactured by Suga Test Instruments Co., Ltd.]
AL VARIABLE GLOSS METER U
With GV-5D], the angle of incidence and the light receiving angle was measured at 45 °. Measurement of Izod impact strength ASTM D256 (1/4 ", with notch, unit = kg
f · cm / cm). The presence of gels, foreign matter, and black haze on the surface of the test piece for measuring the appearance of the molded gloss was observed. Those having no defects were evaluated as "good", and those having the presence were evaluated as "defective". Fish Eye Measurement Method A fish eye measurement sheet sample was prepared by the following method, and fish eyes were measured. A 50-ton press machine heated at 220 ° C. is prepared. The pellet obtained by the above method was used for a SUS mold plate (30 cm × 30 cm ×
0.5 mm) (10 to 15 g). It is sandwiched between presses as it is, and a pressure of 0 to 0.5 kg / cm ² G is applied thereto and heated for 5 minutes. Apply pressure slowly (10kg
/ Cm ² G ) Slowly pull out the pellet sample (molten) that has protruded from between the mold plates. The sample is drawn out in the form of a film, and is drawn out at a thickness of about 10 to 30 μm as thin as 1 m or more. On the film sample to draw a circle with a diameter of 3.57 cm (area 10 cm ^2), off in the circle
Count the Isshu eye (more than a diameter of 0.2mm).
The above is performed at three points, and the total is divided by the area to obtain the number per 1 cm ² , which is evaluated as fisheye . The case where the number was 1 or less was evaluated as good, and the case where the number exceeded 1 was evaluated as bad.

Reference Example 1 [(A) Rubber-modified thermoplastic resin A
Preparation of BS-1 to 8] In a flask, 50 parts of polybutadiene rubber latex in terms of solid content and 10 parts of styrene-butadiene copolymer rubber latex in terms of solid content are added, and ion-exchanged water 15
0 parts, 7 parts of styrene, 3 parts of acrylonitrile, and 0.2 part of t-dodecyl mercaptan were further added, and the temperature in the flask was raised to 60 ° C.
2 parts, ferrous sulfate heptahydrate 0.01 part, glucose 0.4
A solution prepared by dissolving the above solution in 20 parts of ion-exchanged water was added, and 0.1 part of cumene hydroperoxide was further added to initiate polymerization, and the temperature of the hot bath was maintained at 70 ° C. After polymerizing for 1 hour, 21 parts of styrene, 9 parts of acrylonitrile, 0.5 part of t-dodecylmercaptan, and 0.2 part of cumene hydroperoxide are continuously added over 2 hours, and further polymerized for 1 hour. Was completed. The obtained copolymer latex was coagulated using sulfuric acid, washed with water and dried. ABS-1 shown in Table 1 was obtained.

ABS-2 and ABS-3 in Table 1 represent A
Instead of cumene hydroperoxide of BS-1, t
Polymerization was carried out under the same conditions as for ABS-1, except that -butylperoxyisopropyl carbonate and di-t-butylperoxyhexahydroterephthalate were used. ABS-4 to 8 in Table 1 are ABS-1 formulations, and the rubber amount and t-dodecyl mercaptan amount are appropriately varied.
Performed under the same conditions as BS-1.

[0043]

[Table 1]

Reference Example 2 [Preparation of components (B) and (C)] (B) Silicone oil; KF96-100: Shin-Etsu Silicone Co., Ltd., dimethylpolysiloxane [Kinematic viscosity = 100 cs (25 ° C.), molecular weight] SH200: Toray Dow Corning Co., Ltd., dimethylpolysiloxane [Kinematic viscosity = 5,000 cs (25 ° C.),
(Molecular weight = about 40,000) (C) Lubricant; ethylenebisstearylamide [hereinafter may be abbreviated as “EBS”. ] Magnesium stearate Calcium stearate

Reference Example 3 [(D) Preparation of Other Thermoplastic Resin] AS-1; a copolymer of 75% styrene and 25% acrylonitrile, [η] (the limiting viscosity of methyl ethyl ketone soluble matter ) ) = 0.4 dl / g AS-2; copolymer of 75% styrene and 25% acrylonitrile, [η] = 0.6 dl / g

Examples 1 to 9 and Comparative Examples 1 to 3 In Examples 1 to 9, the (A) rubber-modified thermoplastic resin having a Q value within the range of the present invention was added to the (B) silicone resin within the range of the present invention. A powder composition containing oil and (C) a lubricant, and a thermoplastic resin composition containing (D) another thermoplastic resin. Further, Comparative Examples 1 to 3 are powder compositions in which (B) a silicone oil and (C) a lubricant are blended with (A) a rubber-modified thermoplastic resin having a Q value outside the range of the present invention and within the range of the present invention. And (D) a thermoplastic resin composition containing another thermoplastic resin. Tables 2 and 3 show the formulation and evaluation results. As is clear from the comparison with Comparative Examples 1 to 9, Examples 1 to 9 are less likely to cause blocking during powder storage, can be stored for a long period of time, and have a thermoplastic resin composition using this composition. The molded article is excellent in gloss, impact resistance and molded appearance, and also has improved fish eye generation failure.

Example 1 and Examples 10 to 12 and Comparative Examples 4 to 8 In Examples 1 and 10 to 12, the (A) rubber-modified thermoplastic resin having a Q value within the range of the present invention was added to the present invention. And (D) a thermoplastic resin composition in which (B) silicone oil and (C) a lubricant are blended, and (D) another thermoplastic resin is blended. Comparative Examples 4 to 8
Is a powder composition obtained by blending (A) a rubber-modified thermoplastic resin having a Q value within the range of the present invention with (B) a silicone oil and (C) a lubricant outside the range of the present invention; Is a thermoplastic resin composition containing the above thermoplastic resin. Table 2 and Tables 4 and 5 show the formulation and evaluation results. As is clear from the comparison with Comparative Examples 4 to 8, Examples 1 and 10 to 12 are less likely to cause blocking during powder storage, can be stored for a long period of time, and can be used as a heat source using this composition. The molded article of the plastic resin composition is excellent in gloss, impact resistance, and molded appearance, and also has improved fish eye generation failure.

[0048]

[Table 2]

[0049]

[Table 3]

[0050]

[Table 4]

[0051]

[Table 5]

[0052]

According to the powder composition of the present invention obtained by blending (A) a rubber-modified thermoplastic resin powder with (B) a silicone oil and (C) a lubricant, the (A) component has a high rubber component content. However, no blocking occurs and long-term storage is possible, and a molded product obtained by blending this powder composition with (D) another thermoplastic resin has excellent gloss, molded appearance, and impact resistance. In addition, the defect phenomenon of fish eye occurrence has been greatly improved. And since the powder composition of the present invention has a high rubber component content, the effect of improving the impact resistance can be obtained with a small amount, so that it is easy to cope with the expandability. In addition, thermoplastic resins such as AS resins are excellent in productivity and low in cost. By blending them, it is possible to mass-produce low-cost ABS resins excellent in productivity.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08L 83:04) (72) Inventor Takao Morikawa 2--11-24 Tsukiji, Chuo-ku, Tokyo Inside Japan Synthetic Rubber Co., Ltd. (56) References JP 4-3355052 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 55/02 C08K 5/09 C08K 5/10 C08K 5/20 C08L 83/04

Claims (1)

(57) [Claims] 1. An aromatic vinyl compound (b) and a vinyl cyanide compound (c) in the presence of a rubbery polymer (a)
Wherein the content of the component (a) is 50 to 80% by weight, the content of the component (b) is 5 to 48% by weight, and the content of the component (c) is 2 to 45% by weight. [However, (a) +
(B) + (c) = 100% by weight] .
Q value by the measurement method is 30 × 10 ^{-4 to} 500 × 10 ^-4
(A) Rubber-modified thermoplastic resin powder 100 cc / sec.
A powder composition comprising (B) 0.01 to 6 parts by weight of silicone oil and (C) 0.1 to 20 parts by weight of a lubricant other than silicone oil with respect to parts by weight. Measurement method of Q value (A) The rubber-modified thermoplastic resin used for measurement is 110
Volatile substance content at 0.1 ° C x 60 min.
Use the one adjusted below. Q value measurement conditions Measuring device: Shimadzu flow tester CAPILLARY RHEOMETER CFT-5
00 Measurement conditions: sample amount; 1.8 g plunger area; 1.0 cm ² die size; 2.0 mm length × 1.0 mm φ preheating temperature and time; 200 ° C. × 5 minutes measurement temperature; 200 ° C. load; cm ²