JP2002053625A - Rubber-reinforced vinyl-based resin, method for producing the same and rubber-reinforced vinyl-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain (1) a rubber-reinforced vinyl-based resin which provides a molding excellent in impact resistance, weather resistance, gloss, etc., and has excellent moldability, to provide (2) a method for producing (1) the rubber- reinforced vinyl-based resin and to obtain (3) a rubber-reinforced vinyl-based resin composition composed of (1) the rubber-reinforced vinyl-based resin and another thermoplastic resin. SOLUTION: This rubber-reinforced vinyl-based resin is characterized in that the resin is obtained by polymerizing 95-20 wt.% of a vinyl-based monomer in the presence of 5-80 wt.% of a rubber-like copolymer (A) having 10-30 Mooney viscosity (ML 1+4 at 125 deg.C) obtained by polymerizing a monomer having a compounding ratio of ethylene/a 3-30C α-olefin/a nonconjugated diene of 45-60/35-55/0-20 (wt.%) by using a metallocene catalyst and has 5-200% graft ratio and 0.1-1.0 dl/g intrinsic viscosity [η] of methyl ethyl ketone-soluble part. This method for producing the rubber-reinforced vinyl-based resin is provided. This resin composition is obtained by compounding the rubber-reinforced vinyl- based resin with another thermoplastic resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a rubber-reinforced vinyl resin, a method for producing the same, and a rubber-reinforced vinyl resin composition. More specifically, excellent moldability, impact resistance,
The present invention relates to a rubber-reinforced vinyl resin capable of obtaining a molded article having excellent weather resistance, gloss, and the like, a method for producing the rubber-reinforced vinyl resin, and a rubber-reinforced vinyl resin composition.

[0002]

2. Description of the Related Art An E which does not substantially contain an unsaturated bond in its main chain.
The graft copolymer (AES resin) obtained by copolymerizing styrene, acrylonitrile, and the like with PM and EPDM as the rubber component of the base is more ultraviolet-ray than the ABS resin using the conjugated diene rubber as the base rubber component. It is known that the resistance to oxygen, ozone and ozone is great and the weather resistance is remarkably good. However, a molded article obtained from a conventional AES resin has a poor appearance and has a low-temperature property. Therefore, various improvements have been made,
Since propylene is used as the α-olefin in the rubber component, it has been difficult to improve the appearance and low-temperature characteristics of the molded product to levels higher than those of the conventional products.

[0003] On the other hand, AES having better impact resistance than the conventional ones
Resins are desired. In order to enhance the impact resistance, a method of increasing the amount of the rubber component of the substrate contained in the product or increasing the molecular weight of the hard resin component (matrix component) is considered. However, increasing the amount of the rubber component of the substrate contained in the product is not preferable because the rigidity is reduced and the appearance of the molded product is deteriorated. Also, in the method of increasing the molecular weight of the hard resin component, the fluidity is reduced and the appearance of a molded product is deteriorated. As described above, conventionally, it has been difficult to achieve a good balance between the impact resistance of a product and other physical properties.

[0004]

In view of such circumstances, the present inventors have conducted intensive studies with the aim of improving the above-mentioned drawbacks. As a result, a rubber-like copolymer having a specific viscosity polymerized with a specific catalyst has been obtained. A rubber-reinforced vinyl resin with specific physical properties obtained by polymerizing a specific amount of vinyl monomer in the presence of a polymer has excellent moldability, resulting in molded products with excellent impact resistance, weather resistance, gloss, etc. The inventors have found that the present invention can be obtained, and have completed the present invention.

[0005]

In order to solve the above-mentioned problems, a first invention of the present invention provides an ethylene / carbon number of 3 to 20.
Α-olefin / non-conjugated diene = 45-60 / 35-
A monomer having a mixing ratio of 55/0 to 20 (% by weight) is polymerized using a metallocene-based catalyst, and has a Mooney viscosity (ML).
_{1 + 4 (} 125 ° C.) 10-30 rubbery copolymer (A) 5
It is obtained by polymerizing 95 to 20% by weight of a vinyl monomer in the presence of 80% by weight, has a graft ratio of 5 to 200%, and has an intrinsic viscosity [η] of a methyl ethyl ketone-soluble component.
Is 0.1 to 1.0 dl / g.

Further, according to a second aspect of the present invention, there is provided a method for producing a rubber-reinforced vinyl resin, comprising:
Α-olefin / non-conjugated diene of 0 = 45-60 / 35
A monomer having a mixing ratio of from 55 to 0 to 20 (% by weight) is polymerized using a metallocene catalyst, and has a Mooney viscosity (M
L _{1 + 4 (} 125 ° C.) 10-30 rubbery copolymer (A) 5
In the presence of about 80 to 80% by weight, 95 to 20% by weight of a vinyl monomer is polymerized to have a graft ratio of 5 to 200% and an intrinsic viscosity [η] of 0.1 to 1.
Provided is a method for producing 0 dl / g of a rubber-reinforced vinyl resin.

In the third invention, the first invention or the second invention
A rubber-reinforced vinyl resin composition comprising the rubber-reinforced vinyl resin of the invention and another thermoplastic resin, wherein the ratio of the rubbery copolymer (A) in the rubber-reinforced vinyl resin composition is 5%. To 70% by weight.
Provided is a rubber-reinforced vinyl resin composition.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In the present invention, the rubbery copolymer (A) is ethylene, α-
Consists of olefins and non-conjugated dienes. In the present invention, the α-olefin refers to an α-olefin having 3 to 20 carbon atoms. α-olefin having 20 carbon atoms
If it exceeds, the copolymerizability is extremely reduced, and the surface appearance of a molded article obtained from the resin of the product is remarkably deteriorated. The preferred range of the carbon number of the α-olefin is from 3 to 16, and particularly preferred is from 3 to 12. Specific examples of the α-olefin include propylene,
Examples thereof include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, and 1-eicosene. These α-olefins may be used alone or as a mixture of two or more.

The ratio of ethylene to α-olefin is 45-60 / 35-55 by weight. Note that “/” means “pair”, and the same applies below. If the weight ratio value of the α-olefin exceeds 55, the weather resistance is inferior, and if it is less than 35, the rubbery copolymer has insufficient rubber elasticity and does not exhibit impact resistance. The ratio of ethylene to α-olefin is preferably 45-55 / 45-55. In addition, the amount of unsaturated groups of the α-olefin is preferably in the range of 4 to 40 in terms of iodine value.

The non-conjugated diene used for producing the rubbery copolymer (A) includes alkenyl norbornenes, cyclic dienes, and aliphatic dienes.
-Ethylidene-2-norbornene and dicyclopentadiene. These non-conjugated dienes can be used alone or in combination of two or more. The content of the non-conjugated diene in the rubbery copolymer (A) is 0 to 20% by weight. If the content of the non-conjugated diene exceeds 20% by weight, gelation proceeds, and impact resistance and gloss decrease. The preferred range of the content of the non-conjugated diene is 0 to 15% by weight.

The polymerization reaction for producing the rubbery copolymer (A) is usually carried out in an inert hydrocarbon solvent. Specific examples of such inert hydrocarbon solvents include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane and dodecane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; benzene; Examples thereof include aromatic hydrocarbons such as toluene and xylene. Solvents for these hydrocarbons
They can be used alone or in combination of two or more. In addition, the above-mentioned monomer, which is a raw material for producing the rubbery copolymer (A), can also be used as a solvent for hydrocarbons.

Hereinafter, the metallocene catalyst used in producing the rubbery copolymer (A) will be specifically described with reference to examples, but the invention is not limited to these examples. Examples of the metallocene-based catalyst that can be used include a catalyst composed of the following components (a) and (b), or a catalyst composed of the following components (c) and (d). The component (a) is a transition metal compound represented by the following general formula [I].

[0013]

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In the general formula [I], M is the periodic table IV
A group B metal, (C ₅ R _m ) is a cyclopentadienyl group or a substituted cyclopentadienyl group, and each R may be the same or different;
An alkyl group having 0 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkaryl group having 7 to 40 carbon atoms, or an aralkyl group having 7 to 40 carbon atoms, or 4 to 4 It forms an eight-membered carbon ring.
E is an atom having a non-bonded electron pair, and R 'is a group having 1 carbon atom.
-20 alkyl groups, C6-C40 aryl groups, C7-C40 alkaryl groups, or C7-C40
And R ″ is an alkylene group having 1 to 20 carbon atoms, dialkylsilicon or dialkylgermanium, which is a group connecting two ligands, and s is 1
Or 0, and when s is 1, m is 4 and n is 2 less than the valence of E; when s is 0, m is 5 and n is 1 less than the valence of E; When ≧ 2, each R ′ may be the same or different, and each R ′ may be bonded to form a ring. Q is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkaryl group having 7 to 40 carbon atoms, or
40 aralkyl groups, p and q are integers of 0 to 4, and satisfy the relationship of 0 <p + q ≦ 4.

Specific examples of component (a) include bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) ) Zirconium diphenyl, dimethylsilylbis (cyclopentadienyl) zirconium dichloride, dimethylsilylbis (cyclopentadienyl) zirconium dimethyl, methylenebis (cyclopentadienyl) zirconium dichloride, ethylenebis (cyclopentadienyl) zirconium dichloride, bis (Indenyl) zirconium dichloride, bis (indenyl) zirconium dimethyl, dimethylsilylbis (indenyl) zirconium dichloride, methylenebis (indenyl) zircon Umujikurorido, bis (4,
Examples thereof include 5,6,7-tetrahydroindenyl) zirconium dichloride and bis (4,5,6,7-tetrahydroindenyl) zirconium dimethyl, and compounds obtained by substituting zirconium in these compounds with titanium or hafnium. The component (a) is not limited to those exemplified above. These transition metal compounds can be used alone or in combination of two or more.

The component (b) is a linear aluminoxane compound represented by the following general formula [II] and / or a cyclic aluminoxane compound represented by the following general formula [III].

[0017]

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[0018]

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In the general formulas [II] and [III],
Each R may be the same or different, and includes an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a
An aralkyl group having 40 carbon atoms or an aralkyl group having 7 to 40 carbon atoms, preferably a methyl group, an ethyl group, particularly preferably a methyl group, and n is 2 to 50, preferably 4
Is an integer of up to 30. These aluminoxane compounds can be used alone or in combination of two or more.

The proportion of the component (a) to the component (b) is usually the molar ratio of the transition metal to the aluminum atom,
1: 1 to 1: 100,000, preferably 1: 5 to 1: 5
0000.

The component (c) is a transition metal alkyl compound represented by the following general formula [IV].

[0022]

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In the general formula [IV], M is a metal of Group 4 of the periodic table, (C ₅ R _m ) is a cyclopentadienyl group or a substituted cyclopentadienyl group, and each R is the same. Or a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, and 7 to 40 carbon atoms.
Is an alkaryl group or an aralkyl group having 7 to 40 carbon atoms, or two adjacent carbon atoms are bonded to each other to form a 4- to 8-membered carbon ring, and E is an atom having a non-bonded electron pair. R ′ is an alkyl group having 1 to 20 carbon atoms,
An aryl group having 6 to 40 carbon atoms, an alkaryl group having 7 to 40 carbon atoms, or an aralkyl group having 7 to 40 carbon atoms, wherein R ″ is an alkylene group having 1 to 20 carbon atoms, dialkylsilicon, or dialkylgermanium; Is a group linking two ligands, s is 1 or 0,
When s is 1, m is 4, n is 2 less than the valence of E, when s is 0, m is 5, and n is 1 less than the valence of E, and when n ≧ 2, R's may be the same or different, each R 'may combine to form a ring, R''' is an alkyl group having 1 to 20 carbon atoms, 6 to 6 carbon atoms.
40 aryl groups, alkaryl groups having 7 to 40 carbon atoms,
Or, it is an aralkyl group having 7 to 40 carbon atoms, p and q are integers of 0 to 3, and satisfies the relationship of 0 <p + q <4.

Specific examples of component (c) include bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium diethyl, bis (cyclopentadienyl) zirconium diisobutyl, and bis (cyclopentadienyl) Zirconium diphenyl, bis (cyclopentadienyl) zirconium di {bis (trimethylsilyl) methyl}, dimethylsilylbis (cyclopentadienyl) zirconium dimethyl, dimethylsilylbis (cyclopentadienyl) zirconium diisobutyl, methylenebis (cyclopentadienyl) ) Zirconium dimethyl, ethylene bis (cyclopentadienyl) zirconium dimethyl, bis (indenyl) zirconium dimethyl, bis (indenyl) zirconium diisobutyl, etc. Zirconium compounds in,
Compounds substituted with titanium or hafnium are mentioned. The component (c) is not limited to those exemplified above. These transition metal alkyl compounds can be used alone or in combination of two or more.

The above-mentioned transition metal alkyl compound may be used after being synthesized in advance, or may be a transition metal halide in which R ″ in the above general formula [IV] is substituted with a halogen atom, and trimethylaluminum, triethylaluminum, diethylaluminum. It may be formed by bringing an organometallic compound such as monochloride, triisobutylaluminum, methyllithium, and butyllithium into contact in a reaction system.

The component (d) is an ionic compound represented by the following general formula [V].

[0027]

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In the general formula [V], [L] k + is a Bronsted acid or a Lewis acid, and M ′ is the first in the periodic table.
A1 to An are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a dialkylamino group having 1 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon atom having 6 carbon atoms. ~ 40 aryl groups, 6 to 6 carbon atoms
40 aryloxy groups, alkaryl groups having 7 to 40 carbon atoms, aralkyl groups having 7 to 40 carbon atoms, 1 to 40 carbon atoms
Is a halogen-substituted hydrocarbon group, an acyloxy group having 1 to 20 carbon atoms, or an organic metalloid group, k is an ionic value of L, is an integer of 1 to 3, p is an integer of 1 or more,
q = (k × p).

Specific examples of component (d) include trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, methyl (di-n-butyl) ammonium tetraphenylborate, tetraphenylborate Dimethylanilinium borate, methylpyridinium tetraphenylborate, methyl tetraphenylborate (2-
Cyanopyridinium), methyl tetraphenylborate (4-cyanopyridinium), trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, and the like. Component (d) is not limited to those exemplified above. These ionic compounds can be used alone or in combination of two or more.

The use ratio of component (c) to component (d) is generally 1: 0.5 to 1:20, preferably 1: 0.8 to 1:10, in molar ratio.

In producing the rubbery copolymer (A), at least one of the catalyst components can be used by being supported on a suitable carrier. The type of the carrier is not particularly limited, and any of inorganic oxide carriers, other inorganic carriers, and organic carriers can be used without limitation.
There is no particular limitation on the method of supporting the carrier,
Conventionally known methods can be used.

The rubbery copolymer (A) has a Mooney viscosity (ML _{1 + 4 at} 125 ° C.) of 10 to 30. If the Mooney viscosity exceeds 30, a rubber-reinforced vinyl resin product having excellent fluidity cannot be obtained, and if the Mooney viscosity is less than 10, the impact resistance of the resin product becomes poor, and neither is preferable. The Mooney viscosity is particularly preferably in the range of 15 to 30 in the above range. The rubbery copolymer (A) whose Mooney viscosity is controlled as described above can be easily produced by using the above-mentioned metallocene catalyst and selecting conditions.

Molecular weight distribution of rubbery copolymer (A) (Mw / Mn)
Is 1.2 to 3 depending on the use of the rubber-reinforced vinyl resin.
Can be selected within the range. That is, when the molecular weight distribution of the rubbery copolymer (A) is within the above range,
A resin product with excellent impact resistance can be obtained. The molecular weight distribution is
Among the above ranges, a range of 1.5 to 3 is particularly preferable. Rubbery copolymer whose molecular weight distribution is controlled as above (A)
Can be easily produced by using the above metallocene catalyst and selecting conditions.

The glass transition temperature (Tg) of the rubbery copolymer (A) is preferably in the range of -110 to + 20 ° C, particularly preferably in the range of -70 to -30 ° C. Further, the melting point (Tm) of the rubbery copolymer (A) is from 0 to 1
Those having a temperature range of 00 ° C are preferable, and those having a temperature range of 40 to 70 ° C are particularly preferable because a rubber-reinforced vinyl resin having an excellent balance between impact resistance and workability can be obtained. Rubber-like copolymer (A) whose glass transition temperature (Tg) is controlled as above
Can be easily produced by using a metallocene catalyst and selecting conditions.

The rubber-reinforced vinyl resin according to the present invention is obtained by polymerizing 95 to 20% by weight of a vinyl monomer in the presence of 5 to 80% by weight of the rubbery copolymer (A). It is. When the amount of the rubber-like copolymer (A) is less than 5% by weight, the impact resistance of the rubber-reinforced vinyl resin is insufficient. Since the surface hardness of a molded article made of a vinyl resin decreases, none of them is preferable. The preferred range of the amount of the rubbery copolymer (A) is 5 to 60% by weight, and particularly preferred is 1 to 60% by weight.
0 to 40% by weight.

In the present invention, the vinyl monomer includes
Examples include aromatic vinyl, (meth) acrylate, vinyl cyanide, unsaturated carboxylic acid, and imide compounds of α, β-unsaturated dicarboxylic acid. Specific examples of the aromatic vinyl monomer include styrene, α-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, p-tert-butylstyrene, ethylstyrene, There are vinyl naphthalene and the like, preferably styrene or α-methylstyrene, and particularly preferably styrene.

As the (meth) acrylate, methyl acrylate, ethyl acrylate, propylene acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate,
Alkyl acrylates such as ethylhexyl acrylate and cyclohexyl acrylate; and alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propylene methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, and cyclohexyl methacrylate. Can be Particularly, methyl methacrylate is preferred.

Examples of vinyl cyanide include acrylonitrile and methacrylonitrile, and acrylonitrile is particularly preferred. As the unsaturated carboxylic acid, unsaturated acids such as acrylic acid and methacrylic acid, and unsaturated acid anhydrides such as maleic anhydride, itaconic anhydride and citraconic anhydride can be used.

Examples of the imide compound of an α, β-unsaturated dicarboxylic acid include maleimide, N-alkylmaleimides such as N-methylmaleimide, N-butylmaleimide and N-cyclohexylmaleimide, and N- (p-methylphenyl) And N-aromatic maleimides such as maleimide and N-phenylmaleimide. The above maleimides may all be used from the corresponding α, β-unsaturated dicarboxylic acid as the imide compound, or the corresponding α, β-
A method of imidizing after copolymerizing the unsaturated dicarboxylic acid may be used. Of these, N-
Cyclohexylmaleimide and N-phenylmaleimide.

It is preferable to use two or more of these vinyl monomers in combination. Examples of particularly preferred combinations of monomers include (1) styrene-acrylonitrile, (2) styrene-methyl methacrylate, and (3) styrene-acrylonitrile-methyl methacrylate. Part or all of the above styrene is α-
By substituting with methylstyrene, the heat resistance of the rubber-reinforced vinyl resin can be improved. Further, by substituting part or all of styrene with halogenated styrene, flame retardancy can be exhibited. Further, by using methyl methacrylate in combination with the above monomers, the rubber-reinforced vinyl-based resin is improved in transparency and exhibits excellent coloring properties.

The graft ratio of the rubber-reinforced vinyl resin according to the present invention is in the range of 5 to 200%. If the graft ratio is less than 5%, the amount of the vinyl monomer grafted to the rubber-like copolymer (A) is small, so that the interfacial adhesion between the rubber phase and the matrix phase is reduced and the impact resistance is reduced. When the graft ratio exceeds 200%, the moldability deteriorates. The preferred range of the graft ratio is from 20 to 140%, particularly preferably from 30 to 80%.

The rubber-reinforced vinyl resin has an intrinsic viscosity [η] (measured at 30 ° C.) of methyl ethyl ketone-soluble component in the range of 0.1 to 1.0 dl / g. If the intrinsic viscosity [η] is less than 0.1 dl / g, the impact resistance becomes insufficient. If the intrinsic viscosity [η] exceeds 1.0 dl / g, the moldability deteriorates due to a decrease in fluidity, and neither is preferable. Among the intrinsic viscosities [η] in the above range, preferred values are 0.2 to 0.7.
dl / g, and particularly preferably 0.24 to 0.6.
dl / g.

The rubber-reinforced vinyl resin according to the present invention can be produced by polymerizing the above-mentioned vinyl monomer on the rubbery copolymer (A). The production method can be a conventionally known radical polymerization method, for example, a solution polymerization method or a bulk polymerization method. Further, when the rubbery copolymer (A) is a bulk, various homomixers, emulsified and dispersed using an emulsifying and dispersing equipment such as a homogenizer, the emulsified and dispersed rubber component. It can be used by an emulsion polymerization method, an emulsion / suspension polymerization method, a suspension polymerization method, or the like. In order to obtain a resin product having excellent coloring properties and a molded article excellent in gloss, it is preferably produced by a solution polymerization method or a bulk polymerization method, and particularly preferably a solution polymerization method.

Hereinafter, an example in which the rubber-reinforced vinyl resin according to the present invention is produced by a solution polymerization method will be described in detail. In the solution polymerization method, a solvent is used. Solvents are inert solvents used in ordinary radical polymerization, for example, ethylbenzene, aromatic hydrocarbons such as toluene, methyl ethyl ketone, ketones such as acetone, dichloromethylene, halogenated hydrocarbons such as carbon tetrachloride, Acetonitrile, dimethylformamide, N-methylpyrrolidone and the like can be mentioned. The amount of solvent used is rubbery copolymer
20 to 200 parts by weight based on 100 parts by weight of the sum of (A) and all monomers
It is selected in the range of parts by weight, preferably in the range of 50 to 150 parts by weight.

The polymerization temperature varies depending on whether or not a polymerization initiator is used and, if used, the type and amount of the polymerization initiator.
The temperature is preferably in the range of 0 to 140 ° C. Polymerization temperature is 8
If the temperature is lower than 0 ° C., the viscosity of the polymerization system becomes high in the latter half of the polymerization, so that it is difficult to perform stable operation.
If the temperature exceeds ℃, the amount of low molecular weight components caused by the polymerization reaction due to heat increases, so neither is preferable. Within the above temperature range, the temperature is preferably from 85 to 130 ° C, particularly preferably 9 to 130 ° C.
0-120 ° C.

In the above polymerization, a polymerization initiator, a chain transfer agent, an oxidation stabilizer and the like can be added or mixed. Examples of the polymerization initiator that can be added include, for example, ketone peroxides, dialkyl peroxides, diacyl peroxides, peroxyesters, and organic peroxides such as hydroperoxides. Mercaptans, α-methylstyrene dimer and the like can be mentioned. In addition, other additives such as phenol-based or phosphorus-based oxidation stabilizers, benzotriazole-based or hindered amine-based light stabilizers, and lubricants such as stearyl alcohol and ethylenebisstearamide can be mixed.

When the rubber-reinforced vinyl resin is produced by a solution polymerization method, any of a batch system and a continuous system may be used. Further, the method of maintaining the mixed state so that the reaction system is substantially uniform is not particularly limited.
Usually, a stirring and mixing method using a ribbon-type stirring blade, a turbine-type stirring blade, a screw-type stirring blade, an anchor-type stirring blade, or a circulating mixing method using a pump or the like provided outside the reaction system is adopted. A combination method may be used.

Next, as a method for recovering a copolymer by devolatilizing a solvent, unreacted monomers and the like from a reaction product obtained by the polymerization reaction, a method of suspending and dispersing in water and performing steam stripping is used. An optimal method can be selected according to the polymerization method employed, such as a method of preheating the copolymer solution and flushing under reduced pressure, or a method of directly dissolving with an extruder equipped with a vent.

The rubber-reinforced vinyl resin according to the present invention can be blended with other thermoplastic resins or melt-kneaded to form a rubber-reinforced vinyl resin composition according to the purpose of use. Other thermoplastic resins that can be blended include, for example, polyethylene, polypropylene, polyvinyl chloride, chlorinated polyethylene, BR, NBR, SB
R, S-B-S block copolymer, hydrogenated S-B-
S, polystyrene, HIPS, styrene-acrylonitrile copolymer, ABS resin, AES resin, 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, Examples include polyimide, PPS, polyetheretherketone, vinylidene fluoride polymer, polycarbonate, polyacetal, polyamide, polyamide-based elastomer, polyester-based elastomer, and PPE resin.

The other thermoplastic resins exemplified above may be one kind or a mixture of two or more kinds. Among the other thermoplastic resins exemplified above, preferred are styrene-acrylonitrile copolymer, ABS resin, AES resin, AS
A resin, N-cyclohexylmaleimide copolymer styrene resin, N-phenylmaleimide copolymer styrene resin, MBS resin, methyl methacrylate-styrene copolymer, polycarbonate, polyamide, polyamide elastomer and the like.

The ratio when blending another thermoplastic resin with the rubber reinforced vinyl resin according to the present invention depends on the content of the rubbery copolymer (A) in the rubber reinforced vinyl resin composition (hereinafter referred to as rubber). Content) can be arbitrarily selected according to the purpose, but in order to satisfy impact resistance, moldability and transparency, it can be selected to be in the range of 5 to 70% by weight. The rubber content in the rubber-reinforced vinyl resin composition is 5
If it is less than 10% by weight, the impact resistance is insufficient, and
If it exceeds 0% by weight, the surface hardness decreases, and both are not preferred. The preferred range of the rubber content is 10 to 65% by weight.
And a particularly preferable range is 10 to 40% by weight.

The method for obtaining the rubber-reinforced vinyl resin composition can be appropriately selected according to the form of the rubber-reinforced vinyl resin according to the present invention and the form of another thermoplastic resin. For example, when the rubber-reinforced vinyl-based resin is a solution, a method of mixing another thermoplastic resin in the form of a solution or a latex is preferable.
Mixing, dry blending, or melt kneading can be performed in the form of powder-powder, powder-pellet, pellet-pellet, or the like. Melt kneading can be performed by a method using a Banbury mixer, a kneader, a roll, an extruder, or the like, and a kneading method using an extruder is particularly preferable.

The rubber-reinforced vinyl-based resin and the rubber-reinforced vinyl-based resin composition of the present invention include antioxidants such as hindered phenols, phosphorus and sulfur, light stabilizers, ultraviolet absorbers, lubricants, Agents, flame retardants, flame retardant aids,
Various commonly used resin additives such as a filler and a foaming agent can be added and blended.

The rubber-reinforced vinyl resin and the rubber-reinforced vinyl resin composition of the present invention can be produced by various conventionally known molding methods, such as automobile parts, OA equipment housings, television front frames, and various home electric appliances. It can be a target product such as a product part. As the molding method,
There are an injection molding method, a compression molding method, an extrusion molding method and the like. Among them, the injection molding method is effective because the productivity of a target product is high. Conditions for manufacturing a product by the injection molding method include setting the cylinder temperature of the injection molding machine to 1
It is molded at a temperature of 80 to 280 ° C, preferably 200 to 240 ° C, and a mold temperature of 40 to 100 ° C, preferably 50 to 80 ° C.

[0055]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples described below unless departing from the gist of the present invention. In the examples described below, “parts” and “%” in the text all mean “parts by weight” and “% by weight”, and various physical property tests were measured according to the following procedures.

(A) Ethylene content in ethylene-α-olefin copolymer: The ethylene / α-olefin copolymer was subjected to ethylene / α-olefin copolymer analysis using ¹ H-NMR and ¹³ C-NMR.
An α-olefin composition ratio was determined, and a calibration curve showing the relationship between the α-olefin composition ratio and a previously determined result of infrared analysis was prepared. Based on this calibration curve, the composition of the ethylene-α-olefin copolymer obtained in each example was determined. (b) Mooney viscosity (ML _{1 + 4} @ 125 ° C): JIS K6300
It measured according to. (c) Molecular weight distribution (Mw / Mn): Measured at 120 ° C. using o-dichlorobenzene as a solvent using a 150C gel permeation chromatography (GPC) apparatus manufactured by WATERS.

(D) Glass transition temperature (Tg): Measured by a DSC (differential scanning calorimeter) measuring method. (e) Measurement of graft ratio and intrinsic viscosity [η]: A fixed amount (x) of the graft polymer is put into acetone and shaken for 2 hours with a shaker to dissolve the free copolymer. This solution is centrifuged at 23000 rpm for 30 minutes using a centrifuge to obtain an insoluble content. Next, by vacuum drying, 1
Dry at 20 ° C. for 1 hour to obtain an insoluble matter (y). The graft ratio was calculated from the following equation. Graft ratio (%) = {(y) −
(X) × Rubber fraction in graft polymer} / {(x) × Rubber fraction in graft polymer｝ × 100. The intrinsic viscosity [η] is
Methyl ethyl ketone (MEK) soluble in MEK at 30 ° C
Was measured.

(F) MFR: The melt flow rate (g / 10 min) measured under the conditions of a temperature of 220 ° C. and a load of 10 kg. (g) Izod impact strength: 1/4 inch x 1/2 inch, per notched test piece, ASTM D-256
It measured according to. (h) Weather resistance: A 1/8 inch × 1/2 inch Izod impact strength test specimen was used as a sunshine weatherometer using a carbon arc as a light source (manufactured by Suga Test Instruments Co., Ltd .: Model: WEL-6XS-). After exposure for 1000 hours under DC), the Izod impact strength was measured, and the retention was calculated. The weatherometer test conditions were: black panel temperature: 63 ± 3 ° C., tank temperature: 60 ± 5% RH, rain cycle: 18 minutes every 2 hours, carbon exchange cycle:
60 Hr.

(I) Flow mark: mold clamping pressure 120 to
n using an injection molding machine, the molding temperature was set to 220 ° C., a flat plate having a thickness of 2.5 mm and a length and width of 150 × 150 mm was formed, and the occurrence of flow marks on the surface of the flat plate was visually observed. Judged. Observation results were indicated by “○” when no flow mark was observed, “×” when observed over the entire surface, and “△” when intermediate between the two. (j) Surface gloss: measured in accordance with ASTM D-523 (θ = 45 °).

Example 1 A rubber-like copolymer 1 shown in Table 1 was placed in a 20-liter stainless steel autoclave equipped with a ribbon-type stirring blade, an auxiliary agent continuous addition device, and a thermometer.
22 parts, 55 parts of styrene, 23 parts of acrylonitrile,
Charge 110 parts of toluene, raise the internal temperature to 75 ° C,
The contents of the autoclave were stirred for 1 hour to form a homogeneous solution. Thereafter, 0.45 part of t-butyl peroxyisopropyl carbonate was added, and the internal temperature was further raised.
After the temperature reaches 0 ° C, the stirring speed is maintained at 1
The polymerization reaction was performed at 00 rpm. From the fourth hour after the initiation of the polymerization reaction, the internal temperature was raised to 120 ° C., and the reaction was continued for another 2 hours while maintaining this temperature to complete the reaction. After cooling the internal temperature to 100 ° C, octadecyl-3- (3,3
After adding 0.2 part of 5-di-t-butyl-4-hydroxyphenol) -propionate and 0.02 part of silicone oil, the reaction mixture was extracted from the autoclave,
Unreacted substances and the solvent were distilled off by steam distillation, and the cylinder temperature was 220 ° C. and the degree of vacuum was 7 with an extruder equipped with a 40 mmφ vent.
The volatile content was substantially devolatilized at a pressure of 00 mmHg, and the rubber-reinforced vinyl resin was pelletized. Table 2 shows the results of evaluating various physical properties of the obtained pellets.

[Examples 2 to 3, Comparative Examples 1 to 3] In the example described in Example 1, the rubbery copolymer shown in Table 2 was used in place of the rubbery copolymer 1. A rubber-reinforced vinyl-based resin was obtained in the same procedure as in Example 1 except that the resin was used. Table 2 shows the results of evaluating various physical properties of the obtained pellets.

Example 4 70% of the rubber-reinforced vinyl resin obtained in the example described in Example 1 was replaced with 30% of an AS resin of styrene / acrylonitrile = 74/26 and [η] = 0.30.
Various physical properties were evaluated for the pellets obtained by blending. Table 2 shows the evaluation results.

[0063]

[Table 1]

[0064]

[Table 2]

From Tables 1 and 2, the following becomes clear. (1) Mooney viscosity (ML1 + 4 at 125 ° C.) of 10 to 30 as a rubbery copolymer for producing a rubber-reinforced vinyl resin.
The rubber-reinforced vinyl resin obtained from the above is excellent in fluidity, impact resistance, weather resistance, appearance of a molded product and the like (see Examples 1 to 3). (2) The rubber-reinforced vinyl resin composition obtained by blending another thermoplastic resin with the rubber-like copolymer for the production of the rubber-reinforced vinyl resin also has fluidity, weather resistance,
Excellent in appearance and the like of molded articles (see Example 4). (3) On the other hand, when a rubbery copolymer having a Mooney viscosity (ML _{1 + 4} @ 125 ° C.) of 40 is used, the fluidity and the appearance of the molded article are inferior (see Comparative Example 1). ). (4) The rubbery copolymer has an ethylene content of 6
Those using more than 0% by weight and having a propylene content of less than 35% by weight are inferior in fluidity, weather resistance, appearance of molded articles and the like (see Comparative Example 2). (5) A rubbery copolymer using a vanadium catalyst and having a large molecular weight distribution (Mw / Mn) of 5.4 has poor fluidity and impact resistance (Comparative Example 3). reference).

[0066]

The rubber-reinforced vinyl resin and the rubber-reinforced vinyl resin composition according to the present invention are as described in detail above, exhibit the following particularly advantageous effects, and are useful in industrial applications. The value is extremely large. 1. The rubber-reinforced vinyl resin according to the present invention is produced using a metallocene catalyst as a rubbery copolymer, and each component of ethylene / α-olefin having 2 to 20 carbon atoms / non-conjugated diene is in a specific range. And the Mooney viscosity (ML
_{1 + 4 (} 125 ° C.) in the range of 10 to 30; therefore, the rubber-reinforced vinyl resin has fluidity, impact resistance,
Excellent in weather resistance, appearance of molded products, etc., and these properties are balanced. 2. The rubber-reinforced vinyl-based resin composition according to the present invention is excellent in fluidity, weather resistance, appearance of a molded product, and the like, like the original rubber-reinforced vinyl-based resin.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yuji Nakagawa 1-1-18 Kyobashi, Chuo-ku, Tokyo Inside Techno Polymer Co., Ltd. (72) Inventor Hironari Muraki 1-1-18 Kyobashi, Chuo-ku, Tokyo Techno Polymer Co., Ltd. F-term (reference) 4J002 AC03W AC07W AC08W BB03W BB12W BC03W BD04W BD14W BH02W BN06X BN15W BP01W CG00W CH07W CL00W CM04W CN03W 4J026 AC02 BA05 BA06 BA26 BA27 AC01 AC01 GA01 AC01 GA01 AC28A AC39A BA00A BA01B BB00A BB01B BC25B CB94C EB02 EB03 EB04 EB05 EB08 EB09 EB16 EB17 EB18 EC03 EC05 ED06 GA01 GA06 4J100 AA02P AA03Q AA04Q AA07Q AA16Q AA19A AA04 DA22A

Claims (4)

[Claims] 1. Ethylene / α-olefin having 3 to 20 carbon atoms / non-conjugated diene = 45 to 60/35 to 55/0 to 2
A monomer having a mixing ratio of 0 (% by weight) is polymerized using a metallocene catalyst, and has a Mooney viscosity (ML _{1 + 4} ＠ 125
C) is 10 to 30 and the rubbery copolymer (A) is 5 to 80% by weight.
Is obtained by polymerizing 95 to 20% by weight of a vinyl monomer in the presence of a compound, having a graft ratio of 5 to 200% and an intrinsic viscosity [η] of methyl ethyl ketone-soluble component of 0.1 to
A rubber-reinforced vinyl-based resin having a weight ratio of 1.0 dl / g. 2. A method for producing a rubber-reinforced vinyl resin, comprising: ethylene / α-olefin having 3 to 20 carbon atoms.
A monomer having a mixing ratio of non-conjugated diene = 45 to 60/35 to 55/0 to 20 (% by weight) is polymerized using a metallocene catalyst, and has a Mooney viscosity (ML _{1 + 4} @ 125 ° C.) of 10 In the presence of 5 to 80% by weight of a rubber-like copolymer (A) of 30 to 30%, 95 to 20% by weight of a vinyl monomer is polymerized,
A method for producing a rubber-reinforced vinyl resin having a graft ratio of 5 to 200% and an intrinsic viscosity [η] of methyl ethyl ketone-soluble component of 0.1 to 1.0 dl / g. 3. The rubber-like copolymer (A) has a molecular weight distribution.
(Mw / Mn) is in the range of 1.2 to 3, glass transition temperature (Tg) is-
The rubber-reinforced vinyl resin according to claim 1 or 2, wherein the melting point (Tm) is in a range from 110 to + 20 ° C and from 0 to 100 ° C. 4. A rubber-reinforced vinyl resin composition comprising the rubber-reinforced vinyl resin according to claim 1 and another thermoplastic resin, wherein the rubber-reinforced vinyl resin composition comprises The ratio of the rubbery copolymer (A) occupying is 5 to 7
A rubber-reinforced vinyl-based resin composition characterized by being 0% by weight.