JPH11130825A - Rubber-modified thermoplastic resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a rubber-modified thermoplastic resin composition having improved balance of impact resistance, chemical resistance, colorability, weatherability, appearance of molding product and moldability and processability. SOLUTION: This rubber-modified thermoplastic resin composition is obtained by subjecting a vinyl-based monomer component of at least one selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound and another copolymerizable vinyl-based monomer to graft polymerization in the presence of two or more rubber-like polymers having different tanδ peak temperatures. At least a part of prepared rubber dispersion particles forms a compatibilized material of the two or more rubber-like polymers and shows a single tanδ peak temperature in the middle of the rubber-like polymers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber-modified thermoplastic resin composition having an excellent balance of impact resistance, chemical resistance, coloring property, weather resistance, molding appearance and molding workability.

[0002]

2. Description of the Related Art The most effective means for improving the impact resistance of a thermoplastic resin is to introduce a rubber component into the resin. As this method, mechanical blending of a rubber component and a resin component, graft polymerization of a resin component to a rubber component, and the like are widely performed, and ABS having improved impact resistance by introducing a polybutadiene rubber is used. Rubber-modified thermoplastic resins represented by resins and HIPS resins are well known. Further, in order to improve the weather resistance, there is a weather resistant resin such as an AES resin into which an ethylene-α-olefin rubber or a hydrogenated rubber having substantially no double bond is introduced, and further to improve the chemical resistance. And an acrylic rubber-modified thermoplastic resin in which an acrylic rubber is introduced. As described above, the properties of the rubber component greatly affect the performance of the thermoplastic resin into which the rubber component is introduced, and a great advantage can be obtained, but there are disadvantages. For example, an ABS resin modified with a butadiene rubber is excellent in impact resistance and molding processability, but inferior in weather resistance and has an AES
While the resin has the property of having excellent weather resistance, impact strength,
A thermoplastic resin modified with an acrylic rubber is inferior in molding appearance and excellent in weather resistance and chemical resistance, but is inferior in impact resistance and molding processability.

In order to improve these drawbacks, in the conventional method, the drawbacks are generally compensated for by blending each characteristic rubber-modified thermoplastic resin. A heat that sacrifices the properties of the modified thermoplastic resin or does not sufficiently improve the defects, and improves the balance of impact resistance, chemical resistance, colorability, weather resistance, molded appearance, and moldability. There is a need for a plastic resin.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and has been developed in the presence of two or more specific rubbery polymers having different performances. By graft-polymerizing a rubber-modified thermoplastic resin, which is a rubber component that is substantially compatible with the rubbery polymer and becomes a composite, impact resistance, chemical resistance, coloring, weather resistance, An object of the present invention is to provide a rubber-modified thermoplastic resin composition having an improved balance between molding appearance and molding processability.

[0005]

SUMMARY OF THE INVENTION The present invention is directed to different tans.
In the presence of two or more rubbery polymers having a peak temperature of δ, at least one selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound, and other copolymerizable other vinyl monomers. Graft polymerization of a kind of vinyl monomer component, at least a part of the obtained rubber dispersed particles form a compatibilizer of the two or more rubbery polymers,
It is another object of the present invention to provide a rubber-modified thermoplastic resin composition characterized by exhibiting a single intermediate tan δ peak temperature of the rubbery polymer. Here, as the two or more rubbery polymers, one rubbery polymer has a tan δ peak temperature of −30 ° C. or less, and the other rubbery polymer has a tan δ of tan δ.
The peak temperature of which exceeds -30 ° C is preferred. The rubber-modified thermoplastic resin composition of the present invention preferably has a graft ratio of 10 to 150% by weight and a rubber dispersed particle diameter of 0.1 to 1 μm.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The rubbery polymer used in the present invention uses two or more rubbery polymers having different tan δ peak temperatures in combination. Here, as the two or more rubbery polymers, a rubbery polymer (a) having a tan δ peak temperature of −30 ° C. or less and a rubbery polymer (b) exceeding −30 ° C. are used in combination. Is preferred. Examples of the rubbery polymer (a) include diene rubbers such as butadiene rubber, styrene-butadiene rubber, and acrylonitrile-
Butadiene rubber, butyl rubber, isoprene rubber and the like, and non-diene rubbers such as silicon rubber, and hydrogenated aromatic vinyl compound-conjugated diene block copolymers.
The following rubbery polymers may be mentioned.

Among them, cis-polybutadiene having a cis content of 80% or more, styrene-butadiene rubber having a styrene content of 20 to 60% by weight, and acrylonitrile content of 5 to 25%.
% By weight of acrylonitrile-butadiene rubber and hydrogenated aromatic vinyl compound-conjugated diene block copolymer having the following structure are preferred. That is, the hydrogenated product of the aromatic vinyl compound-conjugated diene block copolymer has a double bond portion of the polymer block A composed of the aromatic vinyl compound unit and the polymer block composed of the conjugated diene-based compound unit of 95. It is a block copolymer comprising a polymer block B obtained by hydrogenating at least mol%. The ratio of the A block which is an aromatic vinyl compound unit of the block copolymer is 10 to 60 in the block copolymer.
% By weight, more preferably 13 to 40% by weight.
It is. When the amount of the polymer block of the aromatic vinyl compound is less than 10% by weight, the surface appearance of the resin is deteriorated, which is not preferable.
On the other hand, when it exceeds 60% by weight, impact resistance is not exhibited, which is not preferable. The aromatic vinyl compound used for the block copolymer is the same as the aromatic vinyl compound used for the vinyl monomer component described below.

Further, the block B of the above block copolymer
Comprises a hydrogenated portion of a conjugated diene polymer block, and has a hydrogenation rate of 95 mol% or more, preferably 96 mol% or more. If the amount is less than 95 mol%, a gel is generated during the graft polymerization, and the polymerization cannot be carried out stably. The 1,2-vinyl bond content of the block B is 10 to 90 mol%
Is preferable, and 30 to 80 mol% is more preferable. 10
If it is less than mol%, rubber properties are lost and impact resistance is lowered, which is not preferable. On the other hand, if it exceeds 90 mol%, chemical resistance is not exhibited, which is not preferable.

The conjugated diene compound used in the block B includes 1,3-butadiene, isoprene,
Examples thereof include 1,3-pentadiene and chloroprene. Of these, 1,3-butadiene and isoprene are preferable in order to obtain a hydrogenated diene-based rubbery polymer that can be used industrially and has excellent physical properties. The molecular structure of the block copolymer may be branched, radial, or a combination thereof. Further, as a block structure, diblock, triblock,
Alternatively, it may be a multi-block or a combination thereof.

On the other hand, rubbery polymers (b) include ethylene-α-olefin rubber, urethane rubber, acrylic rubber, acrylonitrile-butadiene rubber and the like.
Rubbery polymers having a tan δ peak temperature exceeding −30 ° C. are exemplified. Among them, as the ethylene-α-olefin rubber, the weight ratio of ethylene / α-olefin is 90%.
/ 10-20 / 80, preferably 85 / 15-40 / 6
0, ethylene in the range of 0 to 40 in terms of iodine value;
Propylene copolymer or ethylene-propylene-
Non-conjugated diene copolymers (EPDM), rubbery polymers such as ethylene-butene copolymer and ethylene-octene copolymer, and acrylonitrile-butadiene rubber having an acrylonitrile content of 25 to 50% by weight are preferred.

The weight average molecular weight of the rubbery polymers (a) to (b) is preferably from 60,000 to 300,000, more preferably from 70,000 to 250,000. If it is less than 60,000, impact resistance is not exhibited, while if it has a high molecular weight exceeding 300,000,
It is not preferable because the compatibility is lowered and the balance between the impact strength and the appearance of the molded product is deteriorated.

In the present invention, an aromatic vinyl compound and a cyanide compound are added in the presence of two or more rubbery polymers having different tan δ peak temperatures, for example, the above rubbery polymers (a) to (b). At least one vinyl monomer component selected from the group of vinyl compounds and other copolymerizable vinyl monomers is graft-polymerized, and at least a part of the obtained rubber dispersed particles has two or more of the above-mentioned two or more types. The effect of the present invention can be obtained by forming a compatibilized product of the above rubbery polymer and exhibiting a single peak tan δ temperature in the middle of the above rubbery polymer. That is, two or more types of rubbery polymers having different tan δ peak temperatures are used in the rubbery polymer used by the fact that these rubbery polymers are substantially compatibilized and present as composite rubber particles during graft polymerization. Shows a single tan δ peak temperature in the middle of the polymer.

In order to obtain composite rubber particles having such new properties, two or more rubbery polymers to be used,
For example, in addition to the rubber structure in which the rubbery polymers (a) and (b) themselves are easily compatible with each other, the selection of an organic peroxide and a solvent that allows the graft polymerization to proceed uniformly during graft polymerization, and the rubbery polymer (A) and (b) are dissolved in a homogeneous solution to initiate polymerization, or those previously melt-kneaded are dissolved in a solution to undergo solution polymerization or bulk polymerization, or re-emulsified is emulsion polymerization or suspension. By devising a polymerization method such as polymerization, the desired composite graft rubber particles can be obtained.

Among the vinyl monomer components used in the above graft polymerization, aromatic vinyl compounds include styrene, α-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene and dibromostyrene. , Fluorostyrene,
Examples thereof include pt-butyl styrene, ethyl styrene, and vinyl naphthalene, and these can be used alone or in combination of two or more. Preferred aromatic vinyl compounds are styrene or those containing 50% by weight or more of styrene in the aromatic vinyl compound. The amount of the aromatic vinyl compound to be used is preferably 10 to 80% by weight, more preferably 20 to 70% by weight, in the vinyl monomer component. If it is less than 10% by weight, the thermal stability of the resin will be reduced, while if it exceeds 80% by weight, the toughness of the resin will be undesirably reduced.

Further, among the above vinyl monomer components, examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and acrylonitrile is preferable. The amount of the vinyl cyanide compound to be used is preferably 5 to 50% by weight, more preferably 10 to 35% by weight, in the vinyl monomer component. If the amount is less than 5% by weight, the chemical resistance and impact strength decrease, while if it exceeds 50% by weight, the mechanical strength decreases and the color tone of the resin deteriorates.

Further, among the above vinyl monomer components,
Other copolymerizable vinyl monomers include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate,
Alkyl acrylates such as phenyl acrylate, methyl methacrylate, ethyl methacrylate,
Propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate,
Methacrylic acid alkyl esters such as cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, and benzyl methacrylate; unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; unsaturated acids such as acrylic acid and methacrylic acid; Imide compounds of α, β-unsaturated dicarboxylic acids such as -methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and the like, preferably methyl methacrylate, N-phenylmaleimide, N-cyclohexylmaleimide Is mentioned. These other copolymerizable vinyl monomers are used alone or as a mixture of two or more, and are used in such an amount that the effect of the present invention is not impaired.

The proportion of the rubbery polymer and the vinyl monomer component used is preferably the total amount of two or more rubbery polymers, for example, the total of the rubbery polymers (a) to (b). ~ 4
0% by weight, more preferably 10 to 35% by weight.
If it is less than 5% by weight, impact resistance is not exhibited, while if it exceeds 40% by weight, the surface gloss is undesirably reduced.

The graft ratio of the rubber-modified thermoplastic resin composition of the present invention is preferably from 10 to 150%, more preferably from 20 to 100%, and particularly preferably from 35 to 60%. If the graft ratio is less than 10%, the impact strength is low, while if it exceeds 150%, the balance between the appearance and the impact resistance is poor, which is not preferable. The graft ratio can be adjusted by the type and amount of the polymerization initiator, the polymerization temperature, and the concentration of the monomer component. Here, the graft ratio (%) is a value determined by the following equation, where x is the weight of the rubber component in 1 g of the rubber-modified thermoplastic resin composition, and y is the weight of the methyl ethyl ketone insoluble matter. Graft ratio (%) = [(y−x) / x] × 100

The rubber dispersed particle diameter in the rubber-modified thermoplastic resin composition of the present invention is preferably 0.1 to 1 μm,
More preferably, it is 0.2 to 0.7 μm. 0.1μ
If it is less than m, the impact strength is significantly reduced, while if it exceeds 1 μm, the gloss is reduced. Here, the rubber dispersion particle diameter can be arbitrarily adjusted, for example, in the case of solution polymerization, by the amount of solvent, the amount of rubber, and the shearing force during the polymerization. In addition, in the case of emulsion polymerization, by adjusting the shear force of an emulsifying and dispersing device such as a homomixer, the type and amount of an emulsifier, and the type and amount of a dispersing agent, by emulsifying and redispersing in advance,
It can be adjusted arbitrarily.

The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the methyl ethyl ketone soluble component, which is a matrix component of the rubber-modified thermoplastic resin composition of the present invention, is preferably 0.2 to 0.7 dl. / G, more preferably 0.22 to 0.65 dl / g, particularly preferably 0.23 to 0.6 dl / g. This intrinsic viscosity [η]
Is less than 0.2 dl / g, the impact strength is low. On the other hand, when it exceeds 0.7 dl / g, flow marks are generated and gloss is undesirably reduced. The intrinsic viscosity [η] can be easily controlled by changing the types and amounts of the polymerization initiator, the chain transfer agent, the emulsifier, the solvent, and the like, and further, the polymerization time, the polymerization temperature, and the like.

The rubber-modified thermoplastic resin composition of the present invention comprises:
In the presence of two or more rubbery polymers having different tan δ peak temperatures, the above vinyl monomer component is subjected to radical graft polymerization by emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, etc. can do. Preferred is solution polymerization. For the radical graft polymerization, a polymerization solvent (in the case of solution polymerization), a polymerization initiator, a chain transfer agent, an emulsifier (in the case of emulsion polymerization) and the like are used. Further, the rubbery polymer and the monomer component used for producing the rubber-modified thermoplastic resin composition may be polymerized by adding the monomer component all at once in the presence of the entire amount of the rubbery polymer. ,
Polymerization may be carried out in divided or continuous additions. Moreover, you may superpose | polymerize by the method which combined these. Further, the whole or a part of the rubbery polymer may be added during the polymerization to carry out the polymerization.

In the solution polymerization method, a solvent is used. This solvent is an inert polymerization solvent used in ordinary radical polymerization, for example, aromatic hydrocarbons such as ethylbenzene and toluene, ketones such as methyl ethyl ketone and acetone, and halogenated hydrocarbons such as dichloromethylene and carbon tetrachloride. Are used. The amount of the solvent used is preferably 20 to 200 parts by weight, more preferably 50 to 150 parts by weight, based on 100 parts by weight of the total of the rubbery polymer and the vinyl monomer component.

As the polymerization initiator, a general initiator suitable for a polymerization method is used. At the time of solution polymerization, for example, an organic peroxide such as ketone peroxide, dialkyl peroxide, diacyl peroxide, peroxyester, or hydroperoxide is used as a polymerization initiator. Further, the polymerization initiator can be added to the polymerization system all at once or continuously. The amount of the polymerization initiator to be used is generally 0.05 to 2% by weight, preferably 0.2 to 0.8% by weight, based on the vinyl monomer component. Also,
In the case of emulsion polymerization, as polymerization initiators, organic hydroperoxides represented by cumene hydroxy peroxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide and the like, sugar-containing pyrophosphoric acid formulations, sulfoxylate formulations, etc. A redox system in combination with a reducing agent to be used, or a peroxide such as persulfate, azobisisobutyronitrile, benzoyl peroxide or the like is used. Preferably, an oil-soluble initiator, cumene hydroperoxide, diisopropylbenzene hydroperoxide,
A redox system using a combination of paramenthane hydroperoxide and a reducing agent represented by a sugar-containing pyrophosphate formulation, a sulfoxylate formulation and the like is preferred. Moreover, you may combine the said oil-soluble initiator and a water-soluble initiator. When combined, the addition ratio of the water-soluble initiator is preferably 50% by weight or less, more preferably 25% by weight of the total amount.
It is as follows. Further, the polymerization initiator can be added to the polymerization system all at once or continuously. The amount of the polymerization initiator to be used is usually 0.1 to 1.5% by weight based on the monomer component,
Preferably it is 0.2 to 0.7% by weight.

Examples of the chain transfer agent include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, t-tetradecyl mercaptan, tetraethylthiuram sulfide, and the like. Examples include hydrocarbons such as carbon tetrachloride, ethylene bromide and pentaphenylethane, or dimers of acrolein, methacrolein, allyl alcohol, 2-ethylhexylthioglycolate, and α-methylstyrene. These chain transfer agents can be used alone or in combination of two or more. The method of using the chain transfer agent may be any of batch addition, divisional addition, and continuous addition. The amount of the chain transfer agent used is usually about 2.0% by weight or less based on the monomer component.

When an emulsifier is used, anionic surfactants, nonionic surfactants, and amphoteric surfactants can be used. Among them, examples of the anionic surfactant include a sulfate of a higher alcohol, an alkylbenzene sulfonate, a fatty acid sulfonate, a phosphate,
Fatty acid salts and the like. As the nonionic surfactant, an alkyl ester type, an alkyl ether type, an alkyl phenyl ether type or the like of ordinary polyethylene glycol is 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. The use amount of the emulsifier is usually about 0.3 to 5.0% by weight based on the monomer component. The polymerization temperature at the time of the graft polymerization is 10 to 160 ° C, preferably 30 to 120 ° C.

The rubber-modified thermoplastic resin composition of the present invention comprises:
Depending on the purpose, the following other polymers can be blended. That is, as other polymers, for example, ethylene, propylene, butene-1, 3-methylbutene-1,
Examples thereof include homopolymers of α-olefins such as 3-methylpentene-1 and 4-methylpentene-1, and copolymers thereof. Typical examples are high density, medium density,
Low density polyethylene, linear low density polyethylene, ultra high molecular weight polyethylene, ethylene-vinyl acetate copolymer,
Polyethylenes such as ethylene-ethyl acrylate copolymer, propylene homopolymer, propylene-ethylene-
Examples thereof include polypropylenes such as a diene compound copolymer, polybutene-1, and poly-4-methylpentene-1. Of these, crystalline polyethylene and crystalline polypropylene are preferred.

As the crystalline polyethylene, commercially available high-density polyethylene, medium-density polyethylene, low-density polyethylene, and linear low-density polyethylene having crystallinity can be used. Although the molecular weight of polyethylene is not particularly limited, the number average molecular weight is 1,000 to 20,
000 is preferred. Further, as the crystalline polypropylene, for example, a so-called propylene block copolymer composed of an isotactic propylene homopolymer having crystallinity and a copolymer part of an ethylene-propylene copolymer having a small ethylene unit content is used. A block copolymer of substantially crystalline propylene and ethylene, or each homopolymerized or copolymerized portion of the block copolymer, which is commercially available as a coalescence, further contains an α-olefin such as butene-1. Consisting of copolymerized ones,
Preferable examples include substantially crystalline propylene-ethylene-α-olefin copolymers.

The other polymer includes a rubber-modified styrene resin other than the rubber-modified thermoplastic resin composition of the present invention. Examples of the rubber-modified styrene resin include high impact polystyrene, ABS
Resin, AES resin, ACS resin, acrylic rubber reinforced AS
Resins. These resins may be functional group-modified styrene resins modified with a small amount of functional groups.
Among them, ABS resin, AES resin and acrylic rubber reinforced AS resin are preferred. Further, as the other polymer, polyvinyl chloride, polyphenylene ether, polycarbonate, polyethylene terephthalate,
Examples thereof include polybutylene terephthalate, polyacetal, polyamide, polyvinylidene fluoride, polystyrene, styrene-methyl methacrylate copolymer, styrene-maleic anhydride copolymer, and chlorinated polyethylene.
These other polymers can be used alone or in combination of two or more.

The rubber-modified thermoplastic resin composition of the present invention and a composition using the same are added to a hindered phenol-based, phosphorus-based, sulfur-based antioxidant, a light stabilizer,
Usually used additives such as an ultraviolet absorber, a lubricant, a coloring agent, a flame retardant, and an enhancer can be blended.

The rubber-modified thermoplastic resin composition of the present invention comprises
The other polymers and additives can be compounded by kneading the components using various extruders, Banbury mixers, kneaders, rolls, feeder ruders and the like. A preferred production method is a method using an extruder and a Banbury mixer. When kneading the respective components, the respective components may be kneaded all at once, or may be added and kneaded several times. For kneading, kneading may be carried out in an extruder in a multi-stage addition manner, or kneading may be carried out using a Banbury mixer, a kneader, or the like, and then, pelletizing may be performed using an extruder.

The thus obtained rubber-modified thermoplastic resin composition of the present invention can be molded into various molded articles by injection molding, sheet extrusion, vacuum molding, heterogeneous molding, foam molding, injection press, press molding, blow molding, etc. Can be molded into The rubber-modified thermoplastic resin composition of the present invention has an excellent balance of impact resistance, chemical resistance, coloring property, weather resistance, molding appearance and molding workability. It can be used for various parts, housings, chassis, trays, etc. in the fields of electricity, electronics, miscellaneous goods, sanitary, automobile, etc.

[0032]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. In the examples, parts and% are by weight unless otherwise specified. The various evaluations in the examples were measured as follows.

Weight average molecular weight (molecular weight): 150C gel permeation chromatography (GPC) manufactured by WATERS, Inc.
The measurement was performed at 120 ° C. using an H-type column manufactured by Tosoh Corporation using o-dichlorobenzene as a solvent. The obtained molecular weight is a standard polystyrene conversion value. The hydrogenation rate was measured at a concentration of 15% using ethylene tetrachloride as a solvent. It was calculated from the decrease in the spectrum of the unsaturated bond in the ¹ H-NMR spectrum of 100 MHZ.

Styrene (block) content Using ¹³ C-NMR, ST (styrene block) and E
It was determined from the composition ratio of B (an ethylene-butylene block in which the butadiene portion was hydrogenated). The ethylene content ethylene -α- olefin copolymer, ¹ H-NM
Using R and ¹³ C-NMR, the composition ratio of ethylene / α-olefin was determined, and a calibration curve showing the relationship between the composition ratio and the result of infrared analysis previously determined was prepared. The composition of the obtained copolymer was determined based on this calibration curve.

Graft ratio A certain amount (x) of the graft copolymer (rubber-modified thermoplastic resin composition) is put into acetone, and shaken for 2 hours with a shaker to dissolve the free copolymer. Using a centrifuge, this solution is centrifuged at 15,000 rpm for 30 minutes to obtain an insoluble content. Next, by vacuum drying, 120
Dry at 1 ° C. for 1 hour to obtain an insoluble matter (y). The graft ratio was calculated from the following equation. Graft ratio (%) = {[(y)-(x) x rubber fraction of graft copolymer] / [(x) x rubber fraction of graft copolymer]} x 100 intrinsic viscosity methyl ethyl ketone (MEK) The solution is dissolved in MEK at 30 ° C.
Was measured. Rubber dispersed particle size graft copolymer (rubber-modified thermoplastic resin composition) 30
mg was dissolved in 30 ml of acetone and measured with a particle size distribution analyzer LA-910 manufactured by Horiba, Ltd. The median diameter (μm) was taken as the rubber dispersed particle diameter.

A test piece (2.2 × 5.2 × 5) pressed at a peak temperature of tan δ of 180 ° C.
mm) with a DMTA dynamic viscoelasticity meter (Polymer
Laboratories) under the following conditions. Measurement temperature; −80 ° C. to + 100 ° C. Straining rate; 10 Hz Heating rate; 3 ° C./min

The Izod impact strength was measured in accordance with ASTM D256 (1/4 cross section).
1/2 inch, notched). Using a falling weight impact strength DuPont impact tester, hitting rod tip R = 1
/ 2 ″, the falling weight impact strength of a 1.6 mm thick molded product was measured.

Exposure to a sunshine weatherometer [WEL-6XS-DC, manufactured by Suga Test Instruments Co., Ltd.] using a weather-resistant carbon arc as a light source for 1,000 hours, and measuring Izod impact strength,
The retention was calculated. Test conditions; Black panel temperature 63 ± 3 ° C Humidity in the chamber 60 ± 5% RH Rain cycle 18 minutes every 2 hours Carbon exchange cycle 60 hours Izod impact strength ASTM D256

The coloring graft copolymer (rubber-modified thermoplastic resin composition) was blended according to the following formulation and colored pellets were obtained through an extruder. This was further molded to obtain a color tone evaluation plate. In addition, about the coloring property of the black compound, the lightness was measured with a color difference meter, and it was represented by the Munsell color value (the larger the value, the worse the coloring property). For other coloring formulations, the saturation was visually determined. Black composition; resin 100 parts Carbon black 0.5 part Calcium stearate 0.3 part Red composition: Resin 100 parts Bengala 1.0 part Calcium stearate 0.3 part Judgment criteria; ◎: Very clear. ；: Clear. Δ: between ○ and × ×; lack of sharpness XX; lack of sharpness.

Using an injection molding machine with a flow mark mold clamping pressure of 120 tons, a wall thickness of 2.5
A flat plate having a length of 150 mm and a width of 150 mm was formed (molding temperature: 210 ° C.), and the occurrence of flow marks was visually determined. ；: No flow mark was generated. X: Flow mark is generated. The surface gloss was measured according to the method of ASTM D523 (450).

A molded article made of chemically resistant black blended pellets (blended resin 100 parts, carbon black 0.5 parts, calcium stearate 0.3 parts) was immersed in JIS No. 6 kerosene (kerosene temperature 80 ° C.) for 1 hour. After leaving, wipe off the surface and dry,
Evaluation was made by the following visual judgment. ；: No change and no decrease in gloss. C: Deterioration such as whitening and gloss reduction is observed.

Reference Example (Production of Rubbery Polymer) Rubbery polymers used in Examples and Comparative Examples were prepared as follows. Rubbery polymer-1 (hydrogenated styrene-butadiene block copolymer); 400 parts of cyclohexane, 15 parts of 1,3-butadiene, 0.05 parts of tetrahydrofuran, 0.0 parts of n-butyllithium in a nitrogen-purged autoclave.
After adding 4 parts and polymerizing at 60 ° C. for 4 hours, adding 10 parts of styrene, polymerizing at 60 ° C. for 4 hours, further adding 65 parts of 1,3-butadiene, polymerizing at 60 ° C. for 4 hours, and finally styrene. Was added and polymerized at 60 ° C. for 4 hours. The resulting active polymer was deactivated with methanol, the polymer solution was transferred to a jacketed reactor, and hydrogenated as 2,2
0.15 parts of 6-di-tert-butyl-p-cresol, bis (cyclopentadienyl) titanium dichloride 0.0
7 parts, 0.15 part of n-butyllithium and 0.28 part of diethylaluminum chloride were added, and reacted with hydrogen gas at a pressure of 10 kg / cm ² for 1 hour. The solvent was removed by steam stripping, and after drying, a hydrogenated block copolymer was obtained. The weight average molecular weight of this rubbery polymer-1 was 150,000, the degree of hydrogenation was 99.9%, and the styrene block content was 20%. FIG. 1 shows the relationship between the temperature of the obtained rubbery polymer-1 and tan δ.

Rubbery polymer-2 (hydrogenated styrene-butadiene block copolymer); 400 parts of cyclohexane, 15 parts of styrene, 0.05 parts of tetrahydrofuran, 0.5 parts of n-butyllithium in an autoclave purged with nitrogen.
After adding 4 parts and polymerizing at 60 ° C for 4 hours, 1,3-
A rubbery polymer was prepared in the same manner as the rubbery polymer-1, except that 70 parts of butadiene was added, polymerization was carried out at 60 ° C for 4 hours, and finally, 15 parts of styrene was added and polymerized at 60 ° C for 4 hours.
2 was obtained. The weight average molecular weight of this rubbery polymer-2 is 1
50,000, hydrogenation rate 99.9%, styrene block content 3
It was 0%.

Rubbery polymer-3 (hydrogenated styrene-butadiene block copolymer); 500 parts of cyclohexane and 70 parts of 1,3-butadiene were charged into a nitrogen-purged autoclave, and 0.1 part of n-butyllithium was added. 05 parts were added, and polymerization was carried out at 50 ° C. After the polymerization conversion reached 31%, 0.25 parts of tetrahydrofuran was added and 8
Polymerization was performed at 0 ° C. for 4 hours. After the polymerization conversion reached almost 100%, rubber-like polymer-3 was obtained in the same manner as in rubbery polymer-1, except that 30 parts of styrene was added and reacted for 1 hour. The weight average molecular weight of this rubbery polymer-3 was 120,000, the degree of hydrogenation was 99.9%, and the styrene block content was 30%.

Rubbery polymer-4 (ethylene-propylene copolymer); 8 liters of purified toluene, 4 liters of purified toluene
60mmo in terms of aluminum atoms dissolved in 0ml
l of methylalumoxane, the mixture was heated to 40 ° C., and then 1.5 liters / hour of ethylene and 3.5 parts of propylene
Liters / hour were fed continuously. Next, 12 micromoles of dicyclopentadienyl zirconium dichloride dissolved in 12 mmol of purified toluene was added to initiate polymerization. During the reaction, the temperature was maintained at 40 ° C., and the reaction was carried out for 20 minutes while continuously supplying ethylene and propylene. Thereafter, methanol was added to stop the reaction, and a crumb-like rubbery polymer-4 was recovered by steam distillation. The weight average molecular weight of this rubbery polymer-4 is 20
The ethylene content was 78%.

Rubbery polymer-5 (ethylene-butene copolymer): Rubbery polymer-5 was obtained in the same manner as in rubbery polymer-4 except that propylene was changed to 1-butene.
The weight average molecular weight of this rubbery polymer-5 was 190,000 and the ethylene content was 80%. FIG. 1 shows the relationship between the temperature of the obtained rubbery polymer-5 and tan δ. Rubbery polymer-6 (ethylene-octene copolymer); rubbery polymer-4 except that propylene was replaced with 1-octene
In the same manner as in the above, rubbery polymer-6 was obtained. This rubbery polymer-6 had a weight average molecular weight of 200,000 and an ethylene content of 80%.

Rubbery polymer-7 (hydrogenated styrene-butadiene block copolymer); 500 parts of cyclohexane and 70 parts of 1,3-butadiene were charged into a nitrogen-purged autoclave, and then 0.1 g of n-butyllithium was added. 05 parts were added, and polymerization was carried out at 50 ° C. After the polymerization conversion reached 31%, 15 parts of styrene and 0.1 part of tetrahydrofuran were added.
25 parts were added and polymerized at 80 ° C. for 4 hours. After the polymerization conversion reached almost 100%, 15 parts of styrene was added,
A rubbery polymer-7 was obtained in the same manner as the rubbery polymer-1, except that the reaction was carried out for 1 hour. The weight average molecular weight of this rubbery polymer-7 was 140,000, the degree of hydrogenation was 99.9%, and the styrene block content was 30%.

Rubbery polymer-8 (random styrene-butadiene copolymer); 500 parts of cyclohexane and 70 parts of 1,3-butadiene in a nitrogen-purged autoclave.
After charging 30 parts of styrene and 0.05 part of n-butyllithium, polymerization was carried out at 50 ° C. Water was added to deactivate the catalyst, followed by dissolving to obtain a rubbery polymer-8. This rubbery polymer-8 had a weight average molecular weight of 150,000 and a styrene content of 30%.

Rubbery polymer-9 (styrene-butadiene block copolymer); 500 parts of cyclohexane, 1,3-butadiene 70 in a nitrogen-substituted autoclave.
After charging, 0.05 part of n-butyllithium was added, and polymerization was carried out at 50 ° C. Almost 100% polymerization conversion
Then, 15 parts of styrene was added and reacted for 1 hour. Water is added to deactivate the catalyst, and the polymer is de-dissolved to give a rubbery polymer
9 was obtained. The weight average molecular weight of this rubbery polymer-9 was 1
50,000, styrene block content was 30%. Table 1 shows the tan δ peak temperatures (° C.) of the rubbery polymers-1 to 9 described above.

[0050]

[Table 1]

Example 1 13 parts of rubbery polymer-1, 13 parts of rubbery polymer-5, 13 parts of rubbery polymer-5, 52 parts of styrene and acrylonitrile were placed in a stainless steel autoclave having a ribbon-type stirring blade and having a capacity of 10 liters. 22 parts and 120 parts of toluene were charged, and after stirring, the temperature was raised to completely dissolve the rubbery polymer to obtain a uniform solution. Next, 0.1 part of t-dodecyl mercaptan, 0.5 part of benzoyl peroxide and 0.1 part of dicumyl peroxide were added, and the polymerization reaction was carried out at a stirring rotation speed of 200 rpm while constantly controlling the temperature at 95 ° C. Was. From the 6th hour after the start of the reaction, the temperature was raised to 120 ° C. over 1 hour, and the reaction was further performed for 2 hours to complete the reaction. The polymerization conversion was 97%. After cooling to 100 ° C., 0.2 parts of 2,2-methylenebis-4-methyl-6-butylphenol was added, the reaction mixture was extracted from the autoclave, and unreacted substances and the solvent were distilled off by steam distillation. After the pulverization, the volatile matter was substantially distilled off using a 40 mmφ vented extruder (220 ° C., 700 mmHg vacuum), and the polymer was pelletized. The obtained pellets were used for the above evaluation. Table 2 shows the results. FIG. 1 shows the relationship between the temperature of the obtained graft copolymer (rubber-modified thermoplastic resin composition) and tan δ. As is clear from FIG. 1, in the graft copolymer (rubber-modified thermoplastic resin composition) obtained in Example 1, the rubbery polymer-1 and the rubbery polymer-5 formed a compatibilized product. And a single tan δ peak temperature in the middle of the rubbery polymer.

Examples 2 to 8 Resins of the respective examples were obtained by changing the type and amount of the rubbery polymer used and the composition ratio of the monomer components used. Table 2 shows the results.

Comparative Example 1 A graft copolymer (rubber-modified thermoplastic resin) was obtained in the same manner as in Example 1 except that only rubbery polymer-1 was used. Table 3 shows the results. Comparative Example 2 A graft copolymer (rubber-modified thermoplastic resin) was obtained in the same manner as in Example 1, except that only the rubbery polymer-2 was used. Table 3 shows the results. Comparative Example 3 The graft copolymers produced in Comparative Examples 1 and 2 were blended at a weight ratio of 1/1 and evaluated. Table 3 shows the results. Comparative Examples 4 to 5 The type of the rubbery polymer used, the charged monomer component, the amount of the organic peroxide, the amount of the molecular weight regulator, the polymerization temperature, etc. were adjusted, and the respective graft copolymers (rubber-modified thermoplastic resin compositions) were adjusted. ) Got. Table 3 shows the results.

Each of the rubber-modified thermoplastic resin compositions of the present invention (Examples 1 to 8) has an excellent balance of physical properties such as impact resistance, weather resistance, and molded appearance. On the other hand, Comparative Examples 1 and 2 are each examples using only one kind of rubbery polymer. Comparative Example 1 has a low impact strength, and Comparative Example 2 has a poor molded appearance. In Comparative Example 3, the graft copolymers obtained in Comparative Example 1 and Comparative Example 2 were blended at a weight ratio of 1/1, and tan δ after blending indicates one intermediate tan δ peak temperature. Tanδ peak temperature of each of the two graft copolymers, and thus the composite rubber particles were not the intended composite rubber particles of the present invention, and the impact strength and the molded appearance were inferior to those of Example 1. . In Comparative Examples 4 and 5, the compatibility of the two rubbery polymers used was poor, the rubber was not composited after the graft polymerization, the tan δ peak temperature was not one, and the impact resistance was low. The balance between the strength and the appearance of the molded product is poor.

[0055]

[Table 2]

[0056]

[Table 3]

[0057]

The rubber-modified thermoplastic resin composition of the present invention is substantially obtained by graft-polymerizing a vinyl monomer component in the presence of two or more specific rubbery polymers having different properties. A rubber-modified thermoplastic resin in which the rubbery polymer is compatible and becomes a composite rubber component.
Excellent balance of chemical resistance, colorability, weather resistance, molded appearance, and moldability.

[Brief description of the drawings]

FIG. 1 is a graph showing the relationship between the temperature of a rubbery polymer or a graft copolymer (rubber-modified thermoplastic resin composition) and tan δ.

Claims (3)

[Claims] 1. The method of claim 2, wherein the peak temperature of the tan δ is different.
At least one vinyl monomer selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds and other copolymerizable other vinyl monomers in the presence of at least one rubbery polymer At least part of the resulting rubber-dispersed particles form a compatibilized form of the two or more rubbery polymers, and a single tan δ intermediate between the rubbery polymers. A rubber-modified thermoplastic resin composition exhibiting a peak temperature. 2. The rubber-modified thermoplastic resin composition according to claim 1, wherein one of the rubbery polymers has a tan δ peak temperature of -30 ° C. or less, and the other rubbery polymer has a tan δ peak temperature of more than -30 ° C. Stuff. 3. The rubber-modified thermoplastic resin composition according to claim 1, wherein the graft ratio is 10 to 150% by weight and the particle size of the dispersed rubber is 0.1 to 1 μm.