JPH11302338A - Rubber-modified thermoplastic resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a rubber-modified thermoplastic resin with excellent impact resistance, weatherability, appearance after molded, chemical resistance, scratch resistance and slidability. SOLUTION: This rubber-modified thermoplastic resin with a graft percentage of 10-100% and the intrinsic viscosity [η] of methyl ethyl ketone solubles of 0.2-0.8 dL/g, is obtained by graft polymerization of at least one monomer component selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds and other vinyl monomers copolymerizable therewith in the presence of (A) a rubbery polymer >=70 deg.C in melting point Tm composed of ethylene, a 3-20C α-olefin and a non-conjugated diene in the weight ratio of (5-95):(95-5):(0-30) and (B) a 2nd rubbery polymer <70 deg.C in melting point Tm or with no Tin in the weight ratio A/B of (10-90):(90-10).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a rubber-modified thermoplastic resin having excellent impact resistance, weather resistance, molded appearance, chemical resistance, scratch resistance and slidability.

[0002]

2. Description of the Related Art A rubber-modified thermoplastic resin (AES resin) obtained by graft-polymerizing styrene, acrylonitrile, or the like using ethylene-α-olefin having substantially no double bond in the main chain as a rubber component is known. It is known that compared to an ABS resin using a conjugated diene rubber, the resistance to ultraviolet rays, oxygen and ozone is large, and the weather resistance is remarkably good. For this reason, rubber-modified thermoplastic resins such as AES resin are used as automotive exterior parts, but due to poor chemical resistance, it is necessary to take measures such as reducing the amount of rubber. Inviting. Furthermore, since it is used without painting, good colorability and scratch resistance are required, but rubber-modified thermoplastic resins are generally inferior in colorability and scratchiness compared to homogeneous systems, May be restricted.

[0003]

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 specific ethylene-α-olefin rubbers having specific physical properties. Rubber with excellent physical properties such as impact resistance, weather resistance, molded appearance, chemical resistance, scratch resistance and slidability by obtaining a rubber-modified thermoplastic resin having specific physical properties obtained by polymerizing vinyl monomer components It is intended to provide a modified thermoplastic resin.

[0004]

According to the present invention, ethylene / α-olefin having 3 to 20 carbon atoms / non-conjugated diene = 5 to 9 is used.
Tm (melting point) consisting of 5/95 to 5/0 to 30% by weight
(A) and Tm (melting point)
Is less than 70 ° C. or in the presence of a rubbery polymer (B) having no Tm (provided that (A) / (B) = 10 to 90/90 to 10% by weight), an aromatic vinyl compound and a vinyl cyanide compound And at least one monomer component selected from the group of other copolymerizable vinyl monomers, and a graft ratio of 10 to 100%.
Wherein the intrinsic viscosity [η] of the methyl ethyl ketone-soluble component is 0.2 to 0.8 dl / g. Here, as the rubber-modified thermoplastic resin, a rubbery polymer (A) is used.
An ethylene-butene copolymer or an ethylene-octene copolymer having a Tm (melting point) of 0 ° C or more, wherein the rubbery polymer (B) has a Tm of 20 ° C or more and less than 70 ° C. It is preferably a (non-conjugated diene) copolymer. Further, as the rubber-modified thermoplastic resin, the rubbery polymer (A) is an ethylene-butene copolymer or an ethylene-octene copolymer having a Tm (melting point) of 70 ° C. or higher, and the rubbery polymer ( B) is Tm
Those which are ethylene-propylene- (non-conjugated diene) copolymers having no polymer are also preferable.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION As the rubbery polymer used in the present invention, two types of rubbery polymers having different Tm (melting points) are used in combination. As a result, a thermoplastic resin having an excellent balance of impact resistance, chemical resistance, scratch resistance, and slidability can be obtained. Here, as the two rubbery polymers, ethylene / α-olefin having 3 to 20 carbon atoms / non-conjugated diene =
A rubbery polymer (A) having a Tm (melting point) of 70 ° C. or more, and a Tm (melting point) of less than 70 ° C. or Tm (melting point) It is a rubbery polymer (B) without any. Here, the Tm (melting point) of the rubber polymer is measured by using a DSC (differential scanning calorimeter) to measure the endothermic change at a constant heating rate of 20 ° C. per minute, and determine the peak temperature of the obtained endothermic pattern. This is the read value. Further, "having no Tm (melting point)" means that the endothermic change peak is not shown in the DSC measurement, and the rubbery polymer has substantially no crystallinity.

The above-mentioned rubbery polymer has 3 to 2 carbon atoms.
Α-olefin of 0 (hereinafter referred to as “α-olefin”)
Specifically, propylene, 1-butene, 1-
Pentene, 1-hexene, 4-methyl-1-pentene,
Examples thereof include 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, and 1-eicosene. These α-olefins can be used alone or in combination of two or more. The α-olefin has 3 to 20 carbon atoms, preferably 3 to 16, more preferably 6 to 12 carbon atoms. When the carbon number exceeds 20,
Since the copolymerizability is extremely reduced, the surface appearance of the resin is significantly deteriorated. The weight ratio of ethylene / α-olefin is
5 to 95/95 to 5, preferably 50 to 90/5
0 to 10, more preferably 60 to 88/40 to 12,
Especially preferably, it is 70-85 / 30-15. If the weight ratio of the α-olefin exceeds 95, the weather resistance is poor, which is not preferable. On the other hand, if it is less than 5, the rubbery polymer has insufficient rubber elasticity, so that sufficient impact resistance is not exhibited. Non-conjugated dienes include alkenyl norbornenes, cyclic dienes, and aliphatic dienes, preferably 5-ethylidene-2-norbornene and dicyclopentadiene. These non-conjugated dienes can be used alone or in combination of two or more. The ratio of the non-conjugated diene to the total amount of the rubbery polymer is from 0 to 3
0% by weight, preferably 0 to 20% by weight, more preferably 0 to 10% by weight. If the proportion of the non-conjugated diene exceeds 30% by weight, the appearance of the molded article and the weather resistance are undesirably deteriorated. The rubbery polymers (A) and (B) of the present invention
Is preferably in the range of 4 to 40 in terms of iodine value.

The rubbery polymer (A) of the present invention has an ethylene-α-olefin having a Tm (melting point) of 70 ° C. or more.
(Non-conjugated diene) rubber having a Tm of 70 ° C.
As described above, ethylene-propylene rubber, ethylene-butene rubber, ethylene-hexene rubber, ethylene-octene rubber, ethylene-decene rubber, and the like having crystallinity can be mentioned, and ethylene-butene rubber and ethylene-octene rubber are preferable.

The rubbery polymer (B) of the present invention is an ethylene-α-olefin- (non-conjugated diene) rubber having a Tm (melting point) of less than 70 ° C. or having substantially no Tm.
For example, ethylene-propylene rubber, ethylene-butene rubber, ethylene-hexene rubber, ethylene-octene rubber, ethylene-decene rubber, etc., having a Tm of 70 ° C.
Less, preferably 40 ° C. or less, more preferably those having substantially no Tm. Preferred are ethylene-propylene rubber and ethylene-butene rubber.

Rubbery polymer (A) and rubbery polymer (B)
The following or are preferable as the combination of Rubbery polymer (A); ethylene-butene copolymer or ethylene-octene copolymer having a Tm (melting point) of 70 ° C. or more Rubbery polymer (B); ethylene having a Tm of 20 ° C. or more and less than 70 ° C. -Propylene- (non-conjugated diene) copolymer In the case of this combination, it is possible to obtain an effect that a weather-resistant resin excellent in gloss, scratch resistance and slidability can be obtained. Rubbery polymer (A); ethylene-butene copolymer or ethylene-octene copolymer having a Tm (melting point) of 70 ° C. or more Rubbery polymer (B); ethylene-propylene- (non-conjugated diene having no Tm) ) Copolymer In the case of this combination, the effect of being excellent in the balance between impact resistance, chemical resistance, scratch resistance and slidability is obtained.

The weight average molecular weight (Mw) of the rubbery polymers (A) and (B) is preferably from 60,000 to 300,000, and more preferably from 70,000 to 250,000. If it is less than 60,000, impact resistance will not be exhibited, while if it has a high molecular weight exceeding 300,000, the molded appearance will be poor, which is not preferable.

In order to exhibit the effects of the present invention, in addition to the rubber structure in which the rubbery polymers (A) and (B) used are easily compatible with each other, the graft reaction proceeds uniformly during graft polymerization. Selecting such organic peroxides and solvents,
The rubbery polymers (A) and (B) are dissolved in a uniform solution to initiate polymerization, or those previously melt-kneaded are dissolved in a solution, and solution polymerization or bulk polymerization is performed. The intended effect can be obtained by devising a polymerization method such as emulsion polymerization or suspension polymerization.

The monomer components used in the graft polymerization of the present invention include an aromatic vinyl compound, a vinyl cyanide compound,
And at least one selected from the group of other copolymerizable vinyl monomers.

Among them, aromatic vinyl compounds include:
Styrene, α-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene,
Monobromostyrene, dibromostyrene, fluorostyrene, pt-butylstyrene, ethylstyrene, vinylnaphthalene and the like can be mentioned, and these can be used alone or in combination of two or more. it can. 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 used is preferably from 10 to 80% by weight, more preferably from 20 to 70% by weight, based on the monomer component. If it is less than 10% by weight,
If the thermal stability of the resin decreases, on the other hand, if it exceeds 80% by weight, the toughness of the resin decreases, which is not preferable.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile.
Preferably it is acrylonitrile. The amount of the vinyl cyanide compound used is from 0 to 95% by weight, preferably from 5 to 50% by weight, more preferably from 10 to 35% by weight in the monomer component.
% By weight. If the content exceeds 95% by weight, the appearance of the molded product is reduced, and the gloss and the color tone are deteriorated.

Further, among the above monomer components, other copolymerizable vinyl monomers include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2- Ethyl hexyl acrylate, cyclohexyl acrylate, alkyl acrylate such as phenyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate , Phenyl methacrylate, benzyl methacrylate Methacrylic acid alkyl esters; unsaturated anhydrides such as maleic anhydride and itaconic anhydride; unsaturated acids such as acrylic acid and methacrylic acid; maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide , An imide compound of α, β-unsaturated dicarboxylic acid such as N-cyclohexylmaleimide, and the like, preferably methyl methacrylate,
N-phenylmaleimide and N-cyclohexylmaleimide are mentioned. These other copolymerizable vinyl monomers can be used alone or as a mixture of two or more. The amount of the other copolymerizable vinyl monomer to be used is such that the effect of the present invention is not impaired, and is 0 to 95% by weight, preferably 5 to 95% by weight in the monomer component. More preferably, the content is 15 to 90% by weight.

The ratio of the rubbery polymer to the monomer component is preferably 5 to 40% by weight, more preferably 10 to 3% by weight of the total amount of the rubbery polymers (A) and (B).
5% 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 decreases,
The scratch resistance and slidability are poor, which is not preferable. Also,
(A) / (B) is 90-
10/10 to 90% by weight, preferably 80 to 20/20
~ 80% by weight, more preferably 70 ~ 30/30 ~ 7
0% by weight. When the amount of the rubbery polymer (A) is less than 10% by weight, chemical resistance, scratch resistance and slidability are inferior. On the other hand, when the amount exceeds 90% by weight, impact resistance is inferior.

The graft ratio of the rubber-modified thermoplastic resin of the present invention is 10 to 100%, preferably 20 to 80%, more preferably 30 to 60%. Graft rate is 10%
If it is less than 100%, the impact strength is low. On the other hand, if it exceeds 100%, the balance between the impact resistance and the appearance of the molded product is unfavorably deteriorated. 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.

The intrinsic viscosity [η] of the methyl ethyl ketone soluble component, which is a matrix component of the rubber-modified thermoplastic resin of the present invention (measured in methyl ethyl ketone at 30 ° C.)
Is from 0.2 to 0.8 dl / g, preferably from 0.25 to
0.7 dl / g, more preferably 0.3 to 0.5 dl
/ G. If the intrinsic viscosity [η] is less than 0.2 dl / g, the impact strength becomes low, while 0.8 dl / g.
If the amount exceeds g, the gloss is reduced and flow marks are generated, which is not preferable. The intrinsic viscosity [η] can be easily controlled by changing the types and amounts of the polymerization initiator, the chain transfer agent, the solvent, and the like, and further, the polymerization temperature and the like.

The rubber-modified thermoplastic resin of the present invention is prepared by subjecting the above monomer components to emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, etc. in the presence of the specific rubbery polymers (A) and (B). To produce a radical graft polymerization. Preferred are emulsion polymerization and solution polymerization. For the radical graft polymerization, commonly used polymerization solvents (in the case of solution polymerization), polymerization initiators, chain transfer agents, emulsifiers (in the case of emulsion polymerization) and the like are used. Further, the rubbery polymer and the monomer component used to produce the rubber-modified thermoplastic resin may be polymerized by adding the monomer component at a time in the presence of the entire amount of the rubbery polymer, Alternatively, polymerization may be performed by continuous addition. 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 to be 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 monomer component.

As the above-mentioned polymerization initiator, a general initiator suitable for a polymerization method is used. In the case 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 monomer components.

In the emulsion polymerization, an organic hydroperoxide represented by cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide and the like, and a sugar-containing pyrophosphoric acid formulation, A redox system in combination with a reducing agent represented by a rate formulation or the like, or a peroxide such as persulfate, azobisisobutyronitrile, benzoyl peroxide or the like is used. Preferably, it is an oil-soluble initiator, represented by organic hydroperoxides represented by cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide and the like, sugar-containing pyrophosphoric acid formulation, sulfoxylate formulation and the like. A redox system based on a combination with a reducing agent to be used 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 or less of the total amount. Further, the polymerization initiator is
It 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, preferably 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 higher alcohol sulfate, an alkylbenzene sulfonate, a fatty acid sulfonate, a phosphoric acid salt, and a fatty acid salt. 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 amount of emulsifier used is
Usually, it is about 0.3 to 5.0% by weight. 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 of the present invention may be blended with the following other polymers according to the purpose. That is, as another polymer, for example, ethylene,
Propylene, butene-1,3-methylbutene-1,3-
Α such as methylpentene-1 and 4-methylpentene-1
-Homopolymers of olefins and copolymers thereof. Representative examples are high-density, medium-density, low-density polyethylene and linear low-density polyethylene, ultra-high-molecular-weight polyethylene, ethylene-vinyl acetate copolymer, polyethylene such as ethylene-ethyl acrylate copolymer,
Examples include polypropylene such as propylene homopolymer and propylene-ethylene-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 of the present invention. As the rubber-modified styrene resin, for example, high impact polystyrene, ABS resin,
AES resin, ACS resin, acrylic rubber reinforced AS resin, and the like can be given. 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, polybutylene terephthalate, polyacetal, polyamide, polyvinylidene fluoride, polystyrene, styrene-methyl methacrylate copolymer, styrene-maleic anhydride Copolymers, chlorinated polyethylene and the like can be mentioned. These other polymers can be used alone or
Mixtures of more than one species can be used.

The rubber-modified thermoplastic resin 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, an ultraviolet absorber, a lubricant, Usually used additives such as a coloring agent, a flame retardant, and an enhancer can be blended.

In order to mix the above-mentioned other polymer and additives with the rubber-modified thermoplastic resin of the present invention and the composition using the same, various extruders, Banbury mixers, kneaders,
It is obtained by kneading each component using a roll, a feeder ruder or 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 rubber-modified thermoplastic resin or the composition of the present invention thus obtained can be obtained by various methods such as injection molding, sheet extrusion, vacuum molding, heteroforming, foam molding, injection press, press molding, and blow molding. It can be molded into molded articles. The rubber-modified thermoplastic resin of the present invention and a composition using the same have excellent impact resistance, weather resistance, molded appearance, chemical resistance, scratch resistance and slidability. OA and home appliances,
It can be used for various parts, housings, chassis, trays, etc. in the fields of electricity / electronics, sundries, sanitary, and automobile.

[0031]

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.

The ethylene- containing ethylene-α-olefin copolymer is represented by 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. Melting point (Tm) Measured by a DSC (differential scanning calorimeter) measuring method manufactured by DuPont. Weight average molecular weight (Mw) (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.

Graft ratio A certain amount (x) of the graft copolymer (rubber-modified thermoplastic resin) 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 ° C.
For 1 hour to obtain an insoluble matter (y). The graft ratio is
It was calculated from the following equation. Graft ratio (%) = {[(y) − (x) × rubber fraction of graft copolymer] / [(x) × rubber fraction of graft copolymer]} × 100 intrinsic viscosity [η] rubber modification Methyl ethyl ketone (MEK) soluble matter, which is a matrix component of the thermoplastic resin, was measured in MEK at 30 ° C.

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.

The weathering test piece was measured by using a sunshine weather meter [WEL-6XS, manufactured by Suga Test Instruments Co., Ltd.] using a carbon arc as a light source.
-DC] for 1,000 hours, the Izod impact strength was measured, and the retention was calculated as compared to that before exposure. Test conditions; Black panel temperature 63 ± 3 ° C Humidity in the tank 60 ± 5% RH Rain cycle 18 minutes every 2 hours Carbon exchange cycle 60 hours

The surface gloss was measured according to the method of ASTM D523 (450). 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.

A molded article made of chemically resistant black blended pellets (blended resin 100 parts, carbon black 0.5 part, calcium stearate 0.3 part) 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. The surface of the scratch-resistant molded article was strongly wiped with gauze, and the degree of scratch on the surface was visually determined. ；: There is no scratch. Δ: Between ○ and ×. X: The scratch is markedly formed.

[0038] Using the slidability Suzuki type slide tester, as the mating member with steel (S45C). The test piece had an outer diameter of 25.6 mm,
A hollow cylindrical member having an inner diameter of 20.0 mm was used, and a mating member having the same shape was used. The measurement conditions for the dynamic friction coefficient are:
A load of 0.5 kg in an atmosphere at a room temperature of 23 ° C. and a humidity of 50%,
The measurement was performed at a running speed of 50 cm / sec and a running distance of 3 km, and the dynamic friction coefficient and the amount of wear were measured. The dynamic friction coefficient was calculated by the following equation. mu = ^{_{[3 × F × (r 2 2}} -r 1 2) ] / [P × (r ₂ ³ -
r ₁ ^3)] (wherein, mu is the dynamic friction coefficient, F is applied to the load cell force,
P represents a load, R represents an arm length to a load cell, r ₁ represents an inner diameter, and r ₂ represents an outer diameter. )

Reference Example 1 (Production of Rubbery Polymer) The rubbery polymers used in Examples and Comparative Examples were prepared as follows. Rubbery polymer (A) -1; 8 liters of purified toluene in a 20-liter autoclave purged with nitrogen;
60 mmol of methylaluminoxane in terms of aluminum atoms dissolved in 40 ml of purified toluene was added, and the temperature was raised to 40 ° C.
During the period, 1-butene was continuously supplied at 1.5 liter / hour. Then, 12 micromoles of dicyclopentadienyl zirconium dichloride dissolved in 12 ml 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 (A) -1 was recovered by steam distillation. Table 1 shows the melting point and weight average molecular weight of the obtained rubbery polymer (A) -1.

Rubbery polymers (A) -2 to 4 and (B)
-1 to -3; rubbery polymer (A) -1 except that the types and amounts of α-olefin and non-conjugated diene shown in Table 1 were used.
In the same manner as in the above, rubbery polymers (A) -2 to 4 and (B) -1 to 3 were obtained. The obtained rubbery polymer (A)-
Table 1 shows the melting points and weight average molecular weights of 2-4 and (B) -1-3.

[0041]

[Table 1]

Example 1 A 10-liter stainless steel autoclave equipped with a ribbon-type stirring blade was charged with 10 parts of the rubbery polymer (A) -1.
Parts, 10 parts of rubbery polymer (B) -3 and 55 parts of styrene.
Parts, 25 parts of acrylonitrile and 100 parts of toluene, and the temperature was increased while stirring 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. It takes 1 hour from the 6th hour after the start of the reaction,
The temperature was raised to 20 ° C., 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, a volatile substance was substantially distilled off using an extruder with a 40 mmφ vacuum vent (220 ° C., 700 mmHg vacuum), and pellets of a graft copolymer (rubber-modified thermoplastic resin) were obtained. The obtained pellets were used for the above evaluation. Table 2 shows the results.

Examples 2 to 5 Example 1 except that the kind and amount of the rubbery polymer used and the composition ratio of the monomer component used were changed as shown in Table 2.
In the same manner as in the above, a graft copolymer (rubber-modified thermoplastic resin) of each example was obtained. Table 2 shows the results.

Example 6 10 parts of the rubbery polymer (A) -2 and 10 parts of the rubbery polymer (B) -2 were dissolved in 1000 parts of cyclohexane, and 7 parts of oleic acid was added and heated. At 70 ° C. to prepare a rubbery polymer solution. 1.0 part of potassium hydroxide was dissolved in 300 parts of water and heated to obtain a 70 ° C. aqueous solution of potassium hydroxide. The rubbery polymer solution was gradually added to the aqueous solution while maintaining the temperature while using a homomixer at 3000 rpm to obtain an emulsified solution. Cyclohexane was removed from the obtained emulsified solution to obtain a latex. A mixed solution of 20 parts of latex, 180 parts of water and 10 parts of potassium oleate obtained in a reactor was taken, and 0.2 parts of sodium pyrophosphate, 0.2 parts of dextrose, 0.004 parts of ferrous sulfate and 0.005 parts of cumene were added. 0.4 parts of hydroperoxide was added and mixed with stirring. 11 parts of styrene, 60 parts of methyl methacrylate, 9 parts of acrylonitrile and t
A mixture of 0.3 parts of dodecyl mercaptan was added with stirring under a nitrogen stream to carry out a polymerization reaction. The addition time was 2 hours and the polymerization temperature was 60 ° C. The obtained resin latex was coagulated, dried and pelletized to obtain pellets of a graft copolymer (rubber-modified thermoplastic resin). Table 2 shows the results.

Comparative Example 1 Example 1 was repeated except that only the rubbery polymer (A) -1 was used.
A graft copolymer (rubber-modified thermoplastic resin) was obtained in the same manner as described above. Table 3 shows the results. Comparative Example 2 Example 1 except that only the rubbery polymer (B) -3 was used.
A graft copolymer (rubber-modified thermoplastic resin) was obtained in the same manner as described above. Table 3 shows the results. Comparative Examples 3 to 6 The type and amount of the rubbery polymer used and the composition ratio of the monomer component used were changed as shown in Table 3, and the amount of the organic peroxide, the amount of the molecular weight regulator, the polymerization temperature, etc. were adjusted. Except that the procedure was the same as in Example 1, to obtain each graft copolymer (rubber-modified thermoplastic resin). Table 3 shows the results.

[0046]

[Table 2]

[0047]

[Table 3]

The rubber-modified thermoplastic resin of the present invention (Example 1)
All 6) are excellent in impact resistance, weather resistance, molded appearance, chemical resistance, scratch resistance and slidability. On the other hand, Comparative Examples 1 and 2 are examples using only one type of rubbery polymer. Comparative Example 1 has low impact strength, and Comparative Example 2 has low surface gloss, chemical resistance, and scratch resistance. Poor performance and slidability. Comparative Example 3 is an example in which the graft ratio is low outside the range of the present invention, and is inferior to Example 2 in impact resistance, scratch resistance and slidability. Comparative Example 4 is an example in which the graft ratio is high outside the range of the present invention, and is inferior to Example 2 in surface gloss and molded appearance. Comparative Example 5 is an example in which the intrinsic viscosity [η] of the soluble portion of methyl ethyl ketone is low outside the range of the present invention, and is inferior in impact strength, chemical resistance, scratch resistance and slidability. Comparative Example 6 is an example in which the intrinsic viscosity [η] of the methyl ethyl ketone-soluble component is high outside the range of the present invention, and the impact strength and molded appearance are inferior.

[0049]

The rubber-modified thermoplastic resin of the present invention has specific physical properties obtained by graft-polymerizing a specific amount of a monomer component in the presence of two specific rubbery polymers having different melting points. Rubber-modified thermoplastic resin having excellent impact resistance, weather resistance, molded appearance, chemical resistance, scratch resistance and slidability.

Claims (3)

[Claims] 1. A rubbery polymer having a Tm (melting point) of 70 ° C. or more, comprising ethylene / α-olefin having 3 to 20 carbon atoms / non-conjugated diene = 5 to 95/95 to 5/0 to 30% by weight. (A) and a rubbery polymer (B) having a Tm (melting point) of less than 70 ° C. or no Tm (provided that (A) / (B) = 1)
0 to 90/90 to 10% by weight], and at least one monomer selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound and other copolymerizable other vinyl monomers. A rubber obtained by graft polymerization of a body component, having a graft ratio of 10 to 100%, and an intrinsic viscosity [η] of methyl ethyl ketone-soluble component of 0.2 to 0.8 dl / g. Modified thermoplastic resin. 2. The rubbery polymer (A) having a Tm of 70 ° C. or higher.
(Melting point) ethylene-butene copolymer or ethylene-octene copolymer, wherein the rubbery polymer (B) has an ethylene-propylene- (non-conjugated diene) copolymer having a Tm of 20 ° C. or more and less than 70 ° C. The rubber-modified thermoplastic resin according to claim 1, which is a union. 3. The rubbery polymer (A) having a Tm of 70 ° C. or higher.
2. An ethylene-butene copolymer or ethylene-octene copolymer having a (melting point), and the rubbery polymer (B) is an ethylene-propylene- (non-conjugated diene) copolymer having no Tm. Rubber-modified thermoplastic resin.