JPH09132618A - Rubber-reinforced thermoplastic resin and thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rubber-reinforced thermoplastic resin which can give a molding excellent in impact resistance and weather resistance and reduced in a content of gel-like foreign matters and excellent in surface appearance and to provide a thermoplastic resin composition containing the same. SOLUTION: This rubber-reinforced thermoplastic resin is obtained by polymerizing at least two monomer components selected from among aromatic vinyl compounds, vinyl cyanide compounds and (meth)acrylic esters in the presence of an ethylene/α-olefin copolymer rubber, wherein the content of toluene- insolubles of the resin is 0.1wt.% or below, and a composition prepared by mixing this resin with another thermoplastic resin is provided.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a rubber-reinforced thermoplastic resin which is excellent in impact resistance and weather resistance, in particular has less gel foreign matter in a molded article, and has an excellent surface appearance of a molded article, and a heat-resistant thermoplastic resin using the same. It relates to a plastic resin composition.

[0002]

2. Description of the Related Art E having substantially no unsaturated bond in its main chain
A graft copolymer (AES resin) obtained by copolymerizing PM and EPDM with rubber components such as styrene and acrylonitrile is an ABS using a conjugated diene rubber.
It is known that it has greater resistance to ultraviolet rays, oxygen, and ozone than resins and has significantly better weather resistance. However, the conventional AES resin has a drawback that the molding appearance is inferior. Therefore, various improvements have been made,
Since there are many gel foreign matters in the obtained molded product, a satisfactory molding appearance has not been obtained yet. Therefore, A
Although the ES resin has excellent weather resistance, its use range is limited compared to ABS resin, ASA resin and the like.

[0003]

The present invention has been made against the background of the above-mentioned problems of the prior art. It is excellent in impact resistance and weather resistance, and in particular, there are few gel foreign matters in the molded product, and the surface of the molded product. An object of the present invention is to provide a rubber-reinforced thermoplastic resin having an excellent appearance and a thermoplastic resin composition using the same.

[0004]

SUMMARY OF THE INVENTION The present invention provides an ethylene-α
A resin obtained by polymerizing at least two monomer components selected from an aromatic vinyl compound, a vinyl cyanide compound and a (meth) acrylic acid ester in the presence of the olefin copolymer rubber (a) ( b) and resin (b)
And a toluene-insoluble content of 0.1% by weight or less, to provide a rubber-reinforced thermoplastic resin.

The present invention also provides a thermoplastic resin composition containing 1 to 99% by weight of the above-mentioned rubber-reinforced thermoplastic resin and 99 to 1% by weight of another thermoplastic resin as main components.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Ethylene-α used in the present invention
-The olefin copolymer rubber (a) is, for example, ethylene /
C3-C20 α-olefin / non-conjugated diene = 5
The copolymer rubber is obtained by polymerizing a monomer having a mixing ratio of 95/95 to 5/0 to 30 (% by weight), but is not limited thereto.

Here, as the α-olefin having 3 to 20 carbon atoms, propylene, 1-butene, 1-pentene, 1
-Hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene and the like can be mentioned, but preferably propylene, 1-butene, 1-
Octene, more preferably propylene. These α-olefins may be used alone or in combination of two or more. The carbon number of the α-olefin is 3 to 20, but preferably 3 to
12, more preferably 3-8. When the carbon number exceeds 20, the copolymerizability is extremely lowered, so that the surface appearance of the obtained resin is remarkably deteriorated.

The weight ratio of ethylene / α-olefin is 5
~ 95 / 95-5, preferably 50-90 / 50-1
0, more preferably 60 to 88/40 to 12, particularly preferably 70 to 85/30 to 15. If the weight ratio of the α-olefin exceeds 95, the weather resistance is deteriorated, which is not preferable. On the other hand, when it is less than 5, impact resistance is not exhibited because the rubber elasticity of the copolymer rubber is insufficient.

Further, as the non-conjugated diene used,
Examples thereof include alkenyl norbornenes, cyclic dienes, and aliphatic dienes, and 5-ethylidene-2-norbornene and dicyclopentadiene are preferable. These non-conjugated dienes can be used alone or in combination with
Mixtures of more than one species can be used. Ethylene-α-
The content of the non-conjugated diene in the olefin copolymer rubber (a) is 0 to 30% by weight, preferably 0 to 15% by weight. When the content of the non-conjugated diene exceeds 30% by weight, gelation progresses and impact resistance and gloss decrease. The amount of unsaturated groups in the copolymer rubber (a) is 0 to 4 in terms of iodine value.
A range of 0 is preferred.

The ethylene-α-olefin copolymer rubber (a) has a polystyrene-equivalent weight average molecular weight of 100.
The content of ten thousand or more components is preferably 10% by weight or less,
More preferably, it is 8% by weight or less. This content is 1
When it exceeds 0% by weight, gel foreign matter is generated in the obtained molded product, and the gel foreign matter in the film sheet of the rubber-reinforced thermoplastic resin (b) obtained exceeds 5/50 μm · cm ² , The molded appearance may deteriorate. In addition, the toluene insoluble content of the obtained resin (b) may exceed 0.1% by weight.

The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the ethylene-α-olefin copolymer rubber (a) is
It is preferably 40 or less, more preferably 25 to 35. If the Mooney viscosity exceeds 40, the reaction becomes non-uniform, and the gel foreign matter in the film sheet increases.

The polymerization reaction for producing the ethylene-α-olefin copolymer rubber (a) of the present invention is usually carried out in an inert hydrocarbon solvent. Examples of such an inert hydrocarbon solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane and dodecane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aromatics such as benzene, toluene and xylene. Group hydrocarbons and the like can be mentioned. These hydrocarbon solvents may be used alone or in combination of two or more. Further, the raw material monomer can also be used as a hydrocarbon solvent.

In order to produce the ethylene-α-olefin copolymer rubber (a) used in the present invention, either a heterogeneous catalyst or a homogeneous catalyst may be used. As a heterogeneous catalyst,
For example, a vanadium-based catalyst in which a vanadium compound and an organic aluminum compound are combined can be used.
Examples of the homogeneous catalyst include metallocene catalysts. In particular, a metallocene catalyst is effective for producing the above-mentioned copolymer rubber using an α-olefin having 6 to 20 carbon atoms.

The content of the component having a polystyrene-reduced weight average molecular weight of 1,000,000 or more in the copolymer rubber (a) is 10%.
The weight% or less can be achieved by changing the kind and amount of the molecular weight modifier and the kind and amount of the catalyst.

In order to reduce the Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the copolymer rubber (a) to 40 or less, the kind and amount of the molecular weight modifier, the monomer concentration and the reaction temperature are changed. Can be achieved by

The glass transition temperature (Tg) of the ethylene-α-olefin copolymer rubber (a) is preferably -10 to -40 ° C, more preferably -70 to -50.
When it is ℃, a rubber-reinforced thermoplastic resin excellent in impact resistance at low temperature can be obtained.

Next, as the monomer used in the monomer component used in the production of the rubber-reinforced thermoplastic resin of the present invention,
At least two kinds selected from aromatic vinyl compounds, vinyl cyanide compounds and (meth) acrylic acid esters.

Of these, aromatic vinyl compounds include styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, t-butylstyrene, α-methylstyrene, 1,1-diphenylstyrene, N, N-
Diethyl-p-aminostyrene, N, N-diethyl-p
-Aminomethylstyrene, vinylpyridine, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, tribromostyrene, fluorostyrene, ethylstyrene, vinylnaphthalene and the like, preferably styrene, α-methylstyrene, Particularly preferred is styrene.

Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile.
Acrylonitrile is particularly preferred. Further, as the meth (acrylic) acid ester, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate are used. ) Acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, lauryl Examples thereof include (meth) acrylate and stearyl (meth) acrylate, with methyl (meth) acrylate being particularly preferable.

In addition to these, other vinyl type monomers such as unsaturated carboxylic acids and imide compounds of α, β-unsaturated dicarboxylic acids can be used in combination with the above-mentioned monomer component. Among these, examples of the unsaturated carboxylic acid include unsaturated acids such as acrylic acid and methacrylic acid, and unsaturated acid anhydrides such as maleic anhydride, itaconic anhydride, and citraconic anhydride.

As the imide compound of α, β-unsaturated dicarboxylic acid, maleimide and N-alkylmaleimides such as N-methylmaleimide, N-butylmaleimide and N-cyclohexylmaleimide, and N- (p-
Examples include N-aromatic maleimides such as methylphenyl) maleimide and N-phenylmaleimide. All of the above maleimides may be prepared by using the corresponding α, β-unsaturated dicarboxylic acid as an imide compound.
A method of copolymerizing β-unsaturated dicarboxylic acid and then imidizing it may be used. Among these, N-cyclohexylmaleimide and N-phenylmaleimide are preferable.

These monomers are used in combination of two or more, and a particularly preferable combination of monomers is
Styrene / acrylonitrile, styrene / methyl methacrylate, styrene / acrylonitrile / methyl methacrylate. Further, heat resistance can be imparted by replacing part or all of the above styrene with α-methylstyrene. Further, flame retardancy can be imparted by replacing part or all of styrene with halogenated styrene. Furthermore, when methyl methacrylate is used in combination with the above monomer combination, a rubber-reinforced thermoplastic resin having excellent colorability can be obtained.

In the present invention, the ethylene-α-olefin copolymer rubber (a) / the above-mentioned monomer component is used in a ratio of 5
-80 / 95-20% by weight, preferably 5-60 / 95
-40% by weight, more preferably 10-40 / 90-6
0% by weight. When the usage ratio of the ethylene-α-olefin copolymer rubber (a) is less than 5% by weight, impact resistance is poor, while when it exceeds 80% by weight, the surface hardness of the resin is lowered, which is not preferable.

The rubber-reinforced thermoplastic resin of the present invention is a known method of radically polymerizing the above-mentioned monomer components in the presence of the above-mentioned ethylene-α-olefin copolymer rubber (a), for example, a solution polymerization method or a block method. Polymerization methods, and further, emulsification / dispersion of a rubber component by using various emulsification / dispersion equipment such as a homomixer and a homogenizer, and an emulsion polymerization method and a suspension polymerization method in which the rubber component is used. Among them, the solution polymerization method or the bulk polymerization method is preferable to obtain the target resin. The solution polymerization method is particularly preferable.

As a method for producing a rubber-reinforced thermoplastic resin,
Hereinafter, the solution polymerization method will be described in detail. That is, a solvent is used in the solution polymerization method. The solvent is an inert polymerization solvent used in ordinary radical polymerization, for example, ethylbenzene, aromatic hydrocarbons such as toluene, methyl ethyl ketone, ketones such as acetone, dichloromethylene, halogen hydrocarbons such as carbon tetrachloride, Acetonitrile, dimethylformamide, N-methylpyrrolidone and the like can be mentioned. The amount of the solvent used is the total amount 1 of the ethylene-α-olefin copolymer rubber (a) and the monomer component.
The amount is preferably 20 to 200 parts by weight, more preferably 50 to 150 parts by weight, based on 00 parts by weight.

The polymerization temperature is 80 to 140 ° C, preferably 85 to 130 ° C, more preferably 90 to 120 ° C. If the polymerization temperature is lower than 80 ° C., the viscosity of the polymer increases in the latter half of the polymerization, and stable operation is difficult. On the other hand, if the polymerization temperature exceeds 140 ° C., the low molecular weight component due to the initiation reaction by heat increases, which is not preferable.

In the polymerization in the present invention, an organic peroxide such as a ketone peroxide, a dialkyl peroxide, a diacyl peroxide, a peroxy ester or a hydroperoxide is used as a polymerization initiator.

As the chain transfer agent, for example, mercaptans, α-methylstyrene dimer, etc. can be used. Further, other additives such as a phenol-based or phosphorus-based oxidation stabilizer, a benzotriazole-based or hindered amine-based light stabilizer, and a lubricant such as stearyl alcohol or ethylenebisstearamide can be blended.

When carrying out the solution polymerization in the present invention, either batch polymerization or continuous polymerization may be performed, but continuous polymerization is preferred. In this continuous polymerization, for example,
As a step, after the total amount of the copolymer rubber (a) to be used is dissolved in 60 to 95% by weight of the total amount of the above monomer components and 60 to 100% by weight of the total amount of the solvent to obtain a uniform solution,
70 to 130 in the presence of a radical initiator (polymerization initiator)
After polymerizing at a temperature of ℃ until the polymerization conversion rate of the monomer becomes 80% or more, as the second step, the addition amount is adjusted so that the polymerization conversion rate of the monomer is always maintained at 80% or more. While adding the remaining monomer component and the solvent continuously or intermittently, in the presence of the radical initiator, 90 to 1
A method in which polymerization is carried out at a temperature of 80 ° C. until the reaction is substantially completed, and then the solvent is separated and removed is preferred (Japanese Patent Publication No. S58-58-
53007 publication). According to this continuous polymerization method, a weather resistant and impact resistant thermoplastic resin having an improved delamination phenomenon can be obtained.

The embodiment for maintaining the mixed state so that the reaction system becomes substantially uniform is not particularly limited, but usually, a ribbon type stirring blade, a turbine type stirring blade, a screw type stirring blade, Stirring and mixing with an anchor type stirring blade or circulation mixing with a pump or the like provided outside the reaction system is used, and a combination thereof is also preferable. Further, in the case of continuous polymerization, a tube-type polymerization machine, an extruder-type polymerization machine, a kneader-type polymerization machine or the like can be used as the polymerization machine after the second group.

Next, as a method of dissolving the solvent, unreacted monomers and the like from the reaction product obtained by the polymerization reaction and recovering the resin, a method of suspending and dispersing in water and steam stripping, a resin A general method such as a method of preheating the solution and flushing it under reduced pressure, or a method of directly removing the solution with a vented extruder can be selected. On the other hand, other polymerization methods can also be carried out according to ordinary methods.

The graft ratio of the rubber-reinforced thermoplastic resin of the present invention thus obtained is 5 to 200%, preferably 20 to 140%, more preferably 30 to 80%.
%. If the graft ratio is less than 5%, the grafting will be insufficient and the impact resistance will not be expressed due to the decrease in the interfacial adhesion between the rubber phase and the matrix phase. On the other hand, if it exceeds 200%, the moldability will deteriorate. . This graft ratio can be easily adjusted by the polymerization temperature, the type and concentration of the polymerization initiator.

The rubber-reinforced thermoplastic resin of the present invention is
The intrinsic viscosity [η] (measured at 30 ° C.) of the methyl ethyl ketone soluble component is 0.1 to 1.0 dl / g, preferably 0.2 to
0.7 dl / g, more preferably 0.24 to 0.6 d
1 / g. When the intrinsic viscosity [η] is less than 0.1 dl / g, the impact resistance becomes insufficient, while when it exceeds 1.0 dl / g, the moldability is deteriorated due to the decrease in fluidity.
This intrinsic viscosity can be easily adjusted by the concentration of the chain transfer agent, the concentration of the polymerization initiator, the amount of the solvent, and the like.

Further, in the rubber-reinforced thermoplastic resin (b) of the present invention, the gel foreign matter in the resin (b) film sheet is preferably 5 pieces / 50 μm · cm ² or less, more preferably 1 piece / 50 μm · cm. ² or less. Here, in the evaluation of gel foreign matter (gel butt evaluation), the rubber-reinforced thermoplastic resin (b) was processed into a film having a thickness of about 50 μm, and 4c was formed.
It is a value obtained by counting the gel lumps of 1 mm or more present in m ² (2 cm × 2 cm) and expressing it as the number per 1 cm ² . When the number of the gel foreign matters exceeds 5/50 μm · cm ² , fish eyes due to a large number of gel foreign matters are observed on the surface of the molded product, which greatly reduces the commercial value of the molded product.

The rubber-reinforced thermoplastic resin (b) of the present invention thus obtained has a toluene insoluble content of 0.1% by weight or less,
It is preferably 0.05% by weight or less, particularly preferably 0.0
Not more than 3% by weight. Here, the toluene insoluble content means the weight ratio of the gel-like substance in which the resin (b) is dissolved in toluene and is not dissolved. This toluene insoluble content is 0.1% by weight
If it exceeds the range, many irregularities due to gel foreign matter called fish eyes appear on the surface of the molded product and the appearance deteriorates. When toluene is continuously polymerized using a plurality of polymerization units, the toluene insoluble matter has a polymerization conversion rate of 45% in the first polymerization unit.
It can be adjusted by increasing it to -80%, preferably 50-70%, and more preferably 50-60%. Even when such a method is not used, it can be adjusted by adjusting the content of the component having a weight average molecular weight of 1,000,000 or more in the obtained rubber-reinforced thermoplastic resin to 10% by weight or less. Further, in some cases, it can be adjusted by cutting or reducing the non-conjugated diene component in the ethylene-α-olefin copolymer rubber (a).

The rubber-reinforced thermoplastic resin (b) of the present invention is
It can be blended with the following other thermoplastic resins depending on the purpose to obtain a thermoplastic resin composition. Other thermoplastic resins include polyethylene, polypropylene,
Polyvinyl chloride, chlorinated polyethylene, BR, NBR,
S-B-S block copolymer, hydrogenated S-B-S block copolymer, HIPS, styrene-acrylonitrile copolymer, ABS resin, AES resin other than the rubber-reinforced thermoplastic resin of the present invention, ASA resin, Polysulfone, polyether sulfone, N-cyclohexylmaleimide copolymer styrene resin, N-phenylmaleimide copolymer styrene resin, MBS resin, methyl methacrylate-styrene copolymer, S-I-S block copolymer, Polyimide,
Examples thereof include PPS, polyether ether ketone, vinylidene fluoride polymer, polycarbonate, polyacetal, polyamide, polyamide elastomer, polyester elastomer, PPE resin and the like. These blending ratios are rubber-reinforced thermoplastic resin / other thermoplastic resin of the present invention = 1 to 99/99 to 1 (% by weight). When the proportion of the rubber-reinforced thermoplastic resin is less than 1% by weight, impact resistance is lowered, while when it exceeds 99% by weight, moldability is lowered, which is not preferable.

The content of the ethylene-α-olefin copolymer rubber (a) in the thermoplastic resin composition (hereinafter also referred to as "rubber content") can be arbitrarily selected according to the purpose. However, in order to satisfy the impact resistance and moldability of the composition, the range is 5 to 70% by weight, preferably 10 to
65% by weight. If the rubber content is less than 5% by weight,
If the impact resistance becomes insufficient, and if it exceeds 70% by weight,
It is not preferable because the surface hardness decreases.

The method for obtaining the thermoplastic resin composition of the present invention will be described in detail. After the two are mixed in the state of solution-solution or solution-latex, which is the reaction mixture after the completion of the polymerization, they are mixed, The resin composition may be recovered, or the powder after the resin recovery operation may be a powder.
The thermoplastic resin composition may be produced by mixing the two in the form of powder-pellet or pellet-pellet. The kneading method of the rubber-reinforced thermoplastic resin and other thermoplastic resin, various extruders, Banbury mixer,
Kneaders, rolls, etc. are used. A preferable kneading method is a method using an extruder.

The rubber-reinforced thermoplastic resin of the present invention and the composition using the same are prepared by adding an antioxidant such as a hindered phenol type, a phosphorus type and a sulfur type, a light stabilizer, an ultraviolet absorber, It is also possible to add commonly used additives such as lubricants, colorants, flame retardants, and enhancers.

The molding method of the rubber-reinforced thermoplastic resin of the present invention and the composition using the same include injection molding, blow molding, compression molding and extrusion molding.
It is molded by the injection molding method. In the case of the injection molding method, the cylinder temperature of the injection molding machine is usually 180 to 280.
℃, preferably 200 ~ 240 ℃, the mold temperature 40 ~
Molding is performed under the temperature condition of 100 ° C., preferably 50 to 80 ° C.

The rubber-reinforced thermoplastic resin of the present invention thus obtained and the composition using the same are excellent in impact resistance and weather resistance, and in particular, there are few gel foreign matters in the molded product and the surface appearance of the molded product is excellent. Therefore, it can be widely used for various applications utilizing these characteristics, for example, exterior parts of automobiles including two-wheeled vehicles, air conditioner outdoor units, and the like.

The preferred embodiment of the present invention is as follows. The α-olefin constituting the copolymer rubber (a) is propylene, 1-butene or 1-octene, and the combination of the monomer components is styrene / acrylonitrile, styrene / methyl methacrylate, or styrene / acrylonitrile / methyl methacrylate. , Rubber reinforced thermoplastics. A rubber-reinforced thermoplastic resin obtained by polymerizing a monomer component by a solution polymerization method in the presence of an ethylene-α-olefin copolymer rubber (a). A thermoplastic resin composition in which the other thermoplastic resin blended with the rubber-reinforced thermoplastic resin (b) is a styrene-acrylonitrile copolymer.

[0043]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the examples, parts and% are based on weight. In addition, various physical properties were measured according to the following procedures.

[0044] The ethylene content ethylene -α- olefin copolymer rubber, ¹ H-NM
The ethylene / α-olefin composition ratio was determined by using R and ¹³ C-NMR, and a calibration curve showing the relationship between this and the previously determined infrared analysis result was prepared. Based on this calibration curve, The composition of the copolymer rubber obtained in the examples was determined. Mooney viscosity According to JIS K6300, measurement temperature 100 ℃, preheat 1
Minutes, measurement 4 minutes. Weight average molecular weight and molecular weight distribution The product was measured at 120 ° C. using o-dichlorobenzene as a solvent using a 150 type gel permeation chromatography (GPC) device manufactured by WATERS.

Polymerization conversion rate of the first group From the solid content (%) in the polymer solution collected from the polymerization reactor of the first group, the polymerization conversion rate (%) of the monomer excluding the charged solid content was calculated. Grafting ratio A certain amount (x) of the rubber-reinforced thermoplastic resin was added to acetone, and shaken for 2 hours with a shaker to dissolve the free copolymer, and this solution was added with a centrifuge to obtain 23, 000r
After centrifugation at pm for 30 minutes to obtain an insoluble content, the product was dried at 120 ° C. for 1 hour using a vacuum drier to obtain an insoluble content (y).
A free copolymer was obtained and the graft ratio was calculated from the following formula. Graft ratio (%) = [(yx × Rubber fraction in rubber-reinforced thermoplastic resin) / (xx × Rubber fraction in rubber-reinforced thermoplastic resin)] × 100

Intrinsic viscosity [η] A free rubber-reinforced thermoplastic resin was isolated, dissolved in methyl ethyl ketone, and measured with an Ubbelohde viscometer at a temperature of 30 ° C. In a separable flask with a stirrer and a toluene insoluble content of 2 liters,
Polymer (rubber reinforced thermoplastic resin) 50g and toluene 1
Charge liter, heat and stir at 70 ° C. for 5 hours to dissolve the polymer, filter the polymer solution with a 400 mesh wire net, and filter out the gel-like substance (toluene-insoluble matter). It was dried for 2 hours, weighed, and expressed as% of the charged polymer amount.

Izod impact strength Measured according to ASTM D256 (section ¼ × 1
/ 2 inch, notched). Weather resistance (impact strength retention rate) Using a sunshine weatherometer [Suga Test Instruments Co., Ltd., WEL-6XL-DC] having a carbon arc as a light source, and exposing for 1,000 hours under the following test conditions,
The Izod impact strength was measured and the retention rate was calculated. Black panel temperature: 63 ± 3 ℃ Temperature in the tank: 60 ± 5% RH Rain cycle: Every 2 hours 18 minutes Carbon exchange cycle: 60 hours Izod impact strength; ASTM D256 (1/8 x 1/2 inch cross section)

Rockwell Hardness Measured according to ASTM D785 (R scale). Heat distortion temperature ASTM D648 (bending stress 18.5 kgf / cm
² ) was measured. Surface gloss Measured according to ASTM D523 (θ = 45 °). The number of gel lumps The number of gel lumps ( number of gel lumps) was evaluated by processing the rubber-reinforced thermoplastic resin (b) into a film having a thickness of about 50 μm,
The gel lumps of 1 mm or more present in 4 cm ² (2 cm × 2 cm) were counted and expressed as the number per 1 cm ² .

Reference Example (Preparation of Copolymer Rubbers a-1 to 6) Copolymer rubbers a-1 to 3 and a-5 to 6 are manufactured by Nippon Synthetic Rubber Co., Ltd., and their composition and physical properties are It shows in Table 1. The copolymer rubber a-4 is manufactured by Dow, ENGAG
It is E # 8200. Table 1 also shows the composition and physical properties of the copolymer rubber a-4.

Example 1 Into a stainless steel autoclave with an internal volume of 10 L equipped with a three-stage paddle type stirring blade, a thermometer, a pressure gauge, and an addition port at the top, 30 parts of the copolymer rubber a-1 previously made into a uniform solution was added. Parts, styrene 50 parts, toluene 150 parts,
While stirring, raise the temperature to 65 ° C, and add acrylonitrile 20
Parts, t-dodecyl mercaptan (0.1 part) and dibenzoyl peroxide (0.5 part) were added, and the atmosphere was replaced with nitrogen.
The polymerization reaction was carried out while controlling at 0 ° C. A phase transition occurred in about 2 hours. The polymerization conversion rate at that time was 60%.

The polymerization reaction was continued under the same conditions, and the temperature was raised to 120 ° C. 4 hours after the start of the polymerization reaction. Furthermore, after holding at 120 ° C. for 2 hours, cooling was started.
The polymerization conversion rate at the end was 98%. After cooling to about 90 ° C., 2,2′-methylene-bis (4
-Methyl-6-t-butylphenol) was added and mixed well, and then the reaction mixture was extracted by an autoclave. Next, by steam distillation, volatile components such as residual monomers and solvents are substantially distilled off, and after finely pulverizing, a 40 mmφ vented extruder (220 ° C.,
The rubber-reinforced thermoplastic resin was pelletized while the volatile components were substantially distilled off at 700 mmHg vacuum). Table 2 shows the physical properties of the obtained rubber-reinforced thermoplastic resin.

Examples 2 to 6 and Comparative Examples 1 to 4 A rubber-reinforced thermoplastic resin was prepared in the same manner as in Example 1 except that the type of copolymer rubber, the type and amount of monomers to be copolymerized were changed. A resin was obtained. The compositions and physical properties of the obtained rubber-reinforced thermoplastic resin are shown in Tables 2 and 3.

Examples 7 to 9 and Comparative Examples 5 to 7 A rubber-reinforced thermoplastic resin was obtained in the same manner as in Example 1 except that the type and amount of the copolymer rubber or the monomer to be copolymerized were changed. Then, this rubber-reinforced thermoplastic resin was blended with another thermoplastic resin, and the mixture was kneaded with an extruder having a 40 mmφ vent to obtain a thermoplastic resin composition. The composition and physical properties of the obtained composition are shown in Tables 4-5.
Shown in

[0054]

[Table 1]

[0055]

[Table 2]

[0056]

[Table 3]

[0057]

[Table 4]

[0058]

[Table 5]

Details of the copolymers * 1 to 3 in Tables 2 to 5 are as follows. * 1) Styrene-acrylonitrile copolymer * 2) Styrene-N-phenylmaleimide copolymer * 3) N-cyclohexylmaleimide-styrene-methylmethacrylate copolymer

[0060]

EFFECTS OF THE INVENTION According to the present invention, a rubber-reinforced thermoplastic resin having excellent impact resistance and weather resistance, in particular, a small amount of gel foreign matter in the molded product, and an excellent surface appearance of the molded product, and a thermosetting resin using the same A plastic resin composition is obtained.

Claims (2)

[Claims] 1. At least two monomer components selected from an aromatic vinyl compound, a vinyl cyanide compound and a (meth) acrylic acid ester in the presence of an ethylene-α-olefin copolymer rubber (a). A resin (b) obtained by polymerizing
A rubber-reinforced thermoplastic resin characterized by being less than or equal to wt%. 2. A rubber-reinforced thermoplastic resin 1 according to claim 1.
A thermoplastic resin composition containing 99% by weight to 99% by weight of another thermoplastic resin as a main component.