JPH06136231A - Polymer composition - Google Patents

Abstract

PURPOSE:To improve compatibility between a halogen-containing polymer, a (meth) acrylic acid ester-containing polymer or a (meth) acrylonitrile-containing polymer and a styrenic elastomer or an olefinic nolymer. CONSTITUTION:An aqueous dispersion comprising (a) an olefinic polymer, (b) a polymer selected from among a halogen-containing polymer, a (meth)acrylic acid ester-containing polymer and a (meth)acrylonitrile-containing polymer and (c) a styrenic elastomer and a free radical generator is heated to a temperature not substantially cause the decomposition of the free radical generator and the alkyl acrylate monomer is impregnated into the styrenic elastomer. Then the aqueous dispersion is further heated and graft reaction is completed to give a polymer composition comprising a modified styrenic polymer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polymer composition comprising a specific modified polymer.

[0002]

2. Description of the Related Art Styrene-based elastomers or modified polymers obtained by grafting vinyl monomers onto the styrene-based elastomers are highly flexible and have good rubber elasticity at room temperature. Since it has a polyisoprene block or a hydrogenated product thereof, it has good compatibility with polyolefins and is widely used in the field of improving impact resistance of polyolefins (for example, JP-A-61-31452, Kaihei 4-132752, etc.). However, the elastomer is a halogen-containing polymer typified by vinyl chloride, a (meth) acrylic acid ester-containing polymer typified by polymethyl methacrylate, and a (meth) acrylonitrile typified by an acrylonitrile-butadiene-styrene copolymer. Since the compatibility with the vinyl polymer such as the content polymer is not sufficient, sufficient effect cannot be exhibited in the field of improving physical properties such as impact resistance of the vinyl polymer.

If a styrene-based elastomer and a polyolefin can be blended with the vinyl polymer, it is possible to impart the good molding processability of the polyolefin to the effect of improving the physical properties of the styrene-based elastomer, thereby creating a more preferable material. It is possible. However, it is known that the compatibility between polyolefin and the vinyl polymer is extremely poor, and not only the mixing of the both results in poor moldability but also the incompatibility makes the molded product inferior in appearance. Can't get Also,
The mechanical properties of the molded body of such a simple mixture are significantly lowered, and it is impossible to obtain a practically usable one.

[0004]

The present invention aims to improve the above-mentioned drawbacks in the mixing of the styrene elastomer and the vinyl polymer and the drawbacks in the mixing of the polyolefin and the vinyl polymer. The present invention has been completed based on the finding that compatibility is remarkably improved when a modified styrene-based polymer is used and this object is achieved. That is, the present invention relates to a vinyl polymer selected from (a) 0 to 95% by weight of olefin polymer, (b) halogen-containing polymer, (meth) acrylic acid ester-containing polymer or (meth) acrylonitrile-containing polymer. Coalescing 10
0-5% by weight, and (c) styrene elastomer 10
0 parts by weight, alkyl acrylate monomer 10-200
Parts by weight and an aqueous suspension containing 0.01 to 10 parts by weight of the radical generator with respect to 100 parts by weight of the alkyl acrylate monomer are heated to a temperature at which decomposition of the radical generator does not substantially occur, Modified styrene obtained by a method in which the styrene elastomer is impregnated with an alkyl acrylate monomer and then the aqueous suspension is further heated to complete the graft reaction. MFR is 0.1 to 20 g / 10 min. It is an object of the present invention to provide a polymer composition containing 2 to 200 parts by weight of a system polymer based on 100 parts by weight of the total amount of (a) and (b).

[0005]

[Detailed Description of the Invention]

(1) Modified Styrene Polymer A modified styrene polymer that constitutes one component of the polymer composition of the present invention (hereinafter sometimes abbreviated as “modified polymer”).
Is a modified polymer obtained by subjecting a styrene elastomer to an alkyl acrylate monomer under a graft reaction condition, and is 100 parts by weight of a styrene elastomer, 10 to 200 parts by weight of an alkyl acrylate monomer, and 100 parts by weight of an alkyl acrylate monomer. In contrast, an aqueous suspension containing 0.01 to 10 parts by weight of a radical generator is heated to a temperature at which decomposition of the radical generator does not substantially occur, and the alkyl acrylate monomer is added to the styrene elastomer. After impregnation, the aqueous suspension is further heated to complete the graft reaction and has an MFR (melt flow rate) of 0.1 to 20 g / 10 minutes, preferably 0.5. -10g /
It's 10 minutes. In addition, MFR is JIS K721
It is a value measured at 230 ° C. under a load of 2.16 kg in accordance with 0, and the following is also the same. Such a modified polymer is preferably produced by the following method.

1) Raw Materials (a) Styrenic Elastomer A styrenic elastomer is an elastomeric random or block copolymer of a styrene compound such as styrene and α-methylstyrene and a conjugated diene such as 1,3-butadiene and isobrene. Mention may be made of hydrogenated products of polymers. Among these styrene elastomers, block copolymers of styrene compounds and conjugated dienes are preferable, and those block copolymers having a general formula represented by the following formula are preferable. General formula: (AB) _{n + 1} , or A- (BA) _n , or B
-(AB) _{n + 1} (A in the above formula is a polymer block composed of a styrene compound, B is a conjugated diene polymer block, and n is 1 to 1).
An integer of 20, the ratio of A block to the whole numerator is 1
~ 50% by weight. ) The average molecular weight of these copolymers is
It is 10,000 to 1,000,000, preferably 50,000 to 250,000. If it is less than the above range, the copolymer does not become elastomeric, and if it exceeds the above range, the processability is deteriorated, which is not preferable.

Specific examples of these styrenic elastomers include styrene / butadiene random copolymers, styrene / isoprene random copolymers, styrene / butadiene diblock copolymers, styrene / isobrene block copolymers, styrene. Butadiene / styrene triblock copolymer, styrene / isoprene / styrene triblock copolymer, polystyrene block terminated styrene / butadiene radial block copolymer, polystyrene block terminated styrene / isoprene radial block copolymer, Examples thereof include styrene / conjugated diene block copolymers such as styrene / butadiene multiblock copolymers and styrene / isobutylene multiblock copolymers, and hydrogenated products thereof. Among these styrene-based elastomers, a particularly preferable one is a hydrogenated styrene / conjugated diene block copolymer because it can be easily modified with an alkyl acrylate monomer. These styrene-based elastomers may be used as a mixture of two or more.

(B) Alkyl acrylate monomer As the alkyl acrylate monomer used for producing the modified polymer, a commercially available one can be used. Specific examples include acrylic acid esters such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, hexyl acrylate and octyl acrylate; methyl methacrylate, ethyl methacrylate, Methacrylic acid esters such as n-butyl methacrylate, sec-butyl methacrylate, decyl methacrylate, 2-ethylhexyl methacrylate and glycidyl methacrylate can be mentioned. Of these, methyl methacrylate is preferable in terms of compatibility with the polymer.

A mixture of a majority weight of the alkyl acrylate monomer with another vinyl monomer copolymerizable with the alkyl acrylate monomer may be used. Examples of the other vinyl monomer include unsaturated aromatic monomers such as styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, dimethylstyrene and chlorostyrene; vinyl acetate and vinyl propionate. Vinyl esters such as acrylic acid,
Methacrylic acid, maleic anhydride, dimethyl maleate,
Unsaturated organic acids such as di (2-ethylhexyl) maleate; unsaturated nitriles such as acrylonitrile and methacrylonitrile; unsaturated mono- or dihalides such as vinyl chloride and vinylidene chloride.

The alkyl acrylate monomer is usually used in an amount of 10 parts by weight based on 100 parts by weight of the styrene elastomer.
To 200 parts by weight, preferably 20 to 100 parts by weight. If the amount is less than the above amount, the effect cannot be sufficiently exerted in terms of compatibility, and if the amount exceeds the above amount, the effect cannot be sufficiently exerted in imparting the properties of the styrene-based elastomer, which is not preferable. The addition can be done all at once or in portions. In subjecting the styrene elastomer and the alkyl acrylate monomer as described above to the graft reaction condition, a radical generator is usually used except for the reaction by radiation.

(C) Radical Generator As the radical generator used in the production of the modified polymer, a general-purpose radical generator can be used, but in view of the preferred graft reaction method described later. Those having a decomposition temperature of 50 ° C. or higher and being oil-soluble in terms of reaction efficiency are preferable. Here, the "decomposition temperature" is the temperature at which the decomposition rate of the radical generator reaches 50% when 0.1 mol of the radical generator is added to 1 liter of benzene and the mixture is left standing for 10 hours. . So-called "1
"Decomposition temperature to obtain a half-life of 0 hours". If this decomposition temperature is low, the polymerization of the alkyl acrylate monomer may progress abnormally,
There is a drawback that a homogeneous modified polymer cannot be obtained. However, conversely, it is also possible to combine the one having a high decomposition temperature and the one having a low decomposition temperature appropriately to cause the decomposition to be carried out stepwise or continuously to efficiently perform the graft reaction.

Examples of such a radical generator include 2,4-dichlorobenzoyl peroxide, t-butylperoxypivalate, o-methylbenzoyl peroxide, bis-3,5,5-trimethylhexanoyl peroxide. , Octanoyl peroxide, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, cyclohexanone peroxide, 2,5-dimethyl-2,5-dibenzoylperoxyhexane, t-butylperoxybenzoate, The-
t-butyl-diperoxyphthalate, methyl ethyl ketone peroxide, dicumyl peroxide, di-t
-Organic peroxides such as butyl peroxide; azo compounds such as azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile). The amount of the radical generator used is within a range of about 0.01 to 10% by weight with respect to the amount of the alkyl acrylate monomer used, and is appropriately adjusted depending on the type of the radical generator and reaction conditions. If the amount used is less than this amount, the reaction does not proceed smoothly. On the other hand, if the amount used exceeds this amount, a gel is likely to be formed in the modified polymer and the effect of the present invention is difficult to be exhibited.

2) Manufacture of modified polymer Although a modified polymer is manufactured by subjecting each of these raw material components to a graft polymerization reaction, various graft reactions have been conventionally proposed. One of them is a method of graft-polymerizing a styrene elastomer in a molten state in the presence of a radical initiator. However, these methods do not always provide the desired properties because they cause decomposition or crosslinking reaction of the styrene elastomer in the molten state, and the amount of the alkyl acrylate monomer that can be introduced is limited. It is also known to perform graft polymerization in a solution using an aromatic hydrocarbon solvent such as xylene. However, since the styrene elastomer has poor solubility in the solvent, the polymerization reaction can be performed only in a dilute solution, and it is not easy to introduce a large amount of the alkyl acrylate monomer, and the polymerization of the alkyl acrylate monomer is difficult. It has the disadvantage that it does not increase in frequency.

Therefore, the production by the aqueous suspension grafting method described below is a particularly preferable method because it is easy to control the gel content due to the intermolecular crosslinking reaction during the polymerization. That is, an aqueous suspension containing styrene-based elastomer particles, an alkyl acrylate monomer and a radical generator is heated to a temperature at which decomposition of the initiator does not substantially occur, and the styrene-based elastomer particles are impregnated with the monomer. After that, a method of further heating the aqueous suspension to complete the polymerization of the monomer is preferable, and this method will be described.

Alkyl Act on Styrenic Elastomer
Relate Impregnation : As a typical preferable method for impregnating the styrene-based elastomer particles with the alkyl acrylate monomer in an aqueous medium, an aqueous suspension of the styrene-based elastomer particles preferably contains a radical generator (and other optional additives). The method is started by adding an alkyl acrylate monomer in which an additive) is dissolved and stirring, or by adding styrene elastomer particles to an aqueous dispersion of an alkyl acrylate monomer in which a radical generator is dissolved and stirring. In the impregnation step, industrially the temperature is raised to a temperature at which the radical generator does not substantially decompose,
Impregnation should be carried out efficiently, and it is generally preferable to operate from room temperature to 100 ° C, particularly 60 to 90 ° C. In this step, the alkyl acrylate is impregnated so that the amount of free alkyl acrylate is 80% by weight or less of the amount of the alkyl acrylate used. Since the styrene elastomer is relatively compatible with the alkyl acrylate, even if 80% by weight or less of the alkyl acrylate is liberated before the initiation of the polymerization, these alkyl acrylate impregnate the styrene elastomer particles during the polymerization. The polymer particles obtained by polymerizing the acrylate do not precipitate independently of the modified styrenic polymer particles. The impregnation time is usually about 2 to 8 hours.

The content of the styrene elastomer and the alkyl acrylate in the aqueous dispersion is usually about 5 to 100 parts by weight with respect to 100 parts by weight of water. Such an aqueous dispersion can be stably maintained in a dispersed state by simply performing sufficient stirring, but if an appropriate suspension stabilizer is used, a suspension dispersion can be prepared more easily and stably. be able to. In this case, examples of the suspension stabilizer include water-soluble polymers such as polyvinyl alcohol, methyl cellulose, and hydroxy cellulose; anionic surfactants such as alkylbenzene sulfonate; nonionic surfactants such as polyoxyethylene alkyl ether. An agent; or a water-insoluble inorganic salt such as magnesium oxide or calcium phosphate, or a mixture thereof, is used in an amount of about 0.01 to 10% by weight with respect to water.

When the styrene elastomer particles are impregnated with the alkyl acrylate monomer (and the radical generator etc.), auxiliary materials such as a plasticizer, a lubricant and an antioxidant can be simultaneously impregnated (these auxiliary materials are styrene). In some cases, it has already been added to the system elastomer,
It can also be added after the graft polymerization reaction).

Polymerization : When the temperature of the aqueous suspension thus prepared is raised to a temperature above the temperature at which the radical generator used decomposes at an appropriate rate, the impregnated alkyl acrylate monomer undergoes graft polymerization. Modified polymer particles are produced. It is preferable to appropriately stir the aqueous suspension during the graft polymerization. The polymerization temperature is generally 50-150.
The temperature should be appropriately selected within the range of ° C, but need not be constant throughout the graft polymerization process. The polymerization is usually about 2 to 10 hours. Polymerization pressure is normal pressure to 10 kg / cm ²
The degree is normal. Further, in order to control the molecular weight of the polymer resulting from the polymerization of the alkyl acrylate monomer, n-
Butyl mercaptan, n-dodecyl mercaptan, t-
A chain transfer agent such as dodecyl mercaptan may be added.

After the polymerization, if the same post-treatment as the usual post-treatment of aqueous suspension polymerization of vinyl monomer (for example, styrene) is carried out, the shape of the styrene-based elastomer used is maintained almost as it is, and immediately after molding A modified polymer particle is obtained which can be used as a material. Therefore, the styrene-based elastomer used before the modification may be in the form of powder, but it is more convenient to be in the form of particles in consideration of handling during the subsequent molding process. That is, the particle size is preferably one that is generally used as a molding material because the modified polymer produced can be directly used as a molding material, and generally, the average particle diameter is 1 to 8 mm, preferably 3 It is about 7 mm. There is no significant change in its size before and after the modification treatment.

(2) Olefin-based polymer The olefin-based polymer which may constitute one component of the polymer composition of the present invention includes ethylene, propylene, butene-1, hexene-1, heptene-1, and octene. −
A homopolymer or a copolymer of two or more α-olefins having 2 to 12 carbon atoms, preferably about 2 to 8 carbon atoms such as 1,4-methylpentene-1, or these olefins and vinyl esters, unsaturated organic acids or the like. Examples thereof include copolymers composed of derivatives and vinylorganosilane.
The copolymer may be random, block or graft, and may have any bonding mode. These olefin polymers may be used as a mixture of two or more.

Specific examples include high, medium and low density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer (random, block),
Propylene-butene-1 random copolymer, propylene-ethylene-butene-1 random copolymer, copolymer of propylene and α-olefin having 5 to 12 carbon atoms and optionally ethylene or butene-1, ethylene- Typical examples are vinyl acetate copolymer, ethylene-vinyltrimethoxysilane copolymer, maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, ethylene-methyl acrylate copolymer, ethylene-methacrylic acid copolymer and the like. Is. Among them, polyethylene, polypropylene, ethylene-propylene copolymer,
And the like are preferable in terms of thermal stability and moldability.

(3) A vinyl polymer selected from a halogen-containing polymer, a (meth) acrylic acid ester-containing polymer or a (meth) acrylonitrile-containing polymer, which constitutes one component of the polymer composition of the present invention. The polymer is a halogen-containing polymer, a (meth) acrylic acid ester-containing polymer, or a (meth) acrylonitrile-containing polymer described below.

1) Halogen-containing polymer Examples of the halogen-containing polymer include polyvinyl chloride, polyvinylidene chloride, vinyl chloride / vinylidene chloride copolymer, vinyl chloride / vinyl acetate copolymer, vinyl chloride / ethylene copolymer. Polymers, vinyl chloride / acrylonitrile copolymer, vinyl chloride / methyl acrylate copolymer, chlorine-containing polymers such as chlorinated polyethylene, polyvinyl fluoride, polyvinylidene fluoride, polychlorotrifluoroethylene, ethylene-tetrafluoroethylene copolymer Polymer,
Commercially available fluorine-containing polymers such as ethylene-chlorotrifluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-propylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer Although those used are appropriately used, polyvinyl chloride and polyvinylidene fluoride are particularly preferable in terms of moldability. Further, the halogen-containing polymer may be blended with another polymer as long as the effect of the present invention is not impaired. For example, polyvinyl chloride and acrylonitrile-butadiene copolymer rubber are compatible with each other and can be mixed in a larger amount, which is preferable.

2) (Meth) acrylic acid ester-containing polymer Examples of the (meth) acrylic acid ester-containing polymer include methyl polyacrylate and ethyl polyacrylate.
Commercially available products such as polybutyl acrylate, polymethyl methacrylate, methyl methacrylate / methyl acrylate copolymer, methyl methacrylate / acrylonitrile copolymer, and methacrylic acid / α-methylstyrene copolymer can be appropriately used. is there. Among these, it is preferable to use polymethyl methacrylate in terms of moldability.

3) (Meth) acrylonitrile-containing polymer As the (meth) acrylonitrile-containing polymer, for example, acrylonitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer, acrylonitrile / styrene / ethylene / propylene copolymer, A commercially available product such as a methyl methacrylate / styrene / butadiene copolymer can be appropriately used. Among these, it is preferable to use an acrylonitrile / butadiene / styrene copolymer in terms of good physical properties such as mechanical properties.

Of course, various additives such as stabilizers, colorants, fillers, nucleating agents, softening agents, plasticizers, antistatic agents and the like have been added to these vinyl polymers within a range that does not impair the effects of the present invention. It may be one.

(4) Composition ratio of the composition The composition ratio of the composition of the present invention is (a) olefin polymer 0 to 95% by weight, preferably 0 to 80% by weight, and (b) (meth) acrylic acid. Ester-containing polymer or (meth) acrylonitrile-containing polymer 100 to 5% by weight, preferably 100 to 20% by weight, (c) modified polymer per 100 parts by weight of total use of (a) and (b) 2 to 200 parts by weight, preferably 5 to 150 parts by weight. If the amount of the modified polymer used is less than this amount, it is difficult to achieve a sufficient effect in terms of obtaining a homogeneous composition, while if it exceeds this amount, physical properties such as mechanical properties deteriorate. In addition to these essential components, additional components can be added to the composition of the present invention in an amount within a range that does not impair the effects of the invention. Examples of the additional component include other thermoplastic resins, rubber substances, inorganic fillers, pigments, plasticizers, various stabilizers (antioxidants, antistatic agents, light stabilizers, antiblocking agents, lubricants), etc. .

(5) Manufacture of composition Although it can be obtained by dry blending the above-mentioned various components and directly molding, generally, a roll, Banbury mixer,
The composition is kneaded with an ordinary kneading machine such as an extruder and then used for molding. For molding, any method such as injection molding, hollow molding, extrusion molding, compression molding and the like can be adopted.

[0029]

EXAMPLES Next, the present invention will be described more specifically by way of examples. Example 1 Preparation of modified polymer : 20 kg of water and 50 kL of tricalcium phosphate as a suspending agent in an autoclave having a volume of 50 liters.
g, and sodium dodecylbenzene sulfonate.
6 g was mixed to make an aqueous medium, and styrene elastomer particles having a particle diameter of 3 to 4 mm (made by Shell Chemical Co., Ltd., Kr
6 kg of atonG 1657 (trade name)) was added and stirred to suspend. Separately, t-butyl peroxypivalate 130.2
g and 40.2 g of benzoyl peroxide were dissolved in 6 kg of methyl methacrylate monomer, added to the above suspension system, and nitrogen was introduced into the autoclave to pressurize the system to 0.5 kg / cm ² . . 6 inside the autoclave
The temperature was raised to 0 ° C., and the mixture was allowed to stand for 3 hours while stirring at this temperature to impregnate the entire amount of methyl methacrylate monomer containing a polymerization initiator into the styrene elastomer particles. Next, this suspension was heated to 75 ° C., and allowed to stand for 3 hours while stirring at this temperature for polymerization, and further heated to 90 ° C. and maintained for 3 hours to complete the polymerization. After cooling, the solid contents were taken out and washed with water to obtain 12 kg of modified polymer particles. The modified polymer particles obtained were sufficiently extracted with acetone to remove the ungrafted methyl methacrylate polymer, and the graft ratio was determined from the infrared absorption spectrum. The graft ratio was 12% by weight. It was Here, the graft ratio is: graft ratio = (amount of grafted monomer / amount of polymerized monomer) × 100 (%). The oil resistance of the modified polymer was 55% according to JIS-K6301 when using JIS No. 1 oil and measuring the volume change rate at 100 ° C. for 70 hours. On the other hand, when unmodified styrene elastomer particles (Kraton G 1657 manufactured by Shell Chemical Co., Ltd.) were subjected to the same evaluation, it was completely dissolved in JIS No. 1 oil.
The MFR of the polymer was 1.5 g / 10 minutes.

Production of polymer composition : Using the modified polymer particles obtained above, polyvinyl chloride (Binica compound D7210 (trade name) manufactured by Mitsubishi Kasei Polytech Co., Ltd.) in a ratio shown in Table 1, Toyo Seiki Co., Ltd. A 1 mm thick sheet was obtained by kneading at 180 ° C. with a Brabender Plastograph manufactured by Co., Ltd. and then by compression molding. Various evaluations were performed on these sheets. The results are shown in Table 1.

Comparative Example 1 Instead of the modified polymer particles of Example 1, unmodified styrenic elastomer particles (Kraton G 16 manufactured by Shell Chemical Co., Ltd.)
A sheet was obtained and evaluated in the same manner as in Example 1 except that 57) was used. The results are shown in Table 1.

Example 2 Modified polymer particles obtained in Example 1, polymethylmethacrylate (Acrypet (trade name) manufactured by Mitsubishi Rayon Co., Ltd.)
Was used at a ratio shown in Table 2 and was kneaded at 180 ° C. with a Brabender Plastograph manufactured by Toyo Seiki Co., Ltd., and then a 1 mm thick sheet was obtained by a compression molding method. Various evaluations were performed on these sheets. The results are shown in Table 2.

Comparative Example 2 Instead of the modified polymer particles of Example 2, unmodified styrene elastomer particles (Kraton G 16 manufactured by Shell Chemical Co., Ltd.)
A sheet was obtained and evaluated in the same manner as in Example 2 except that 57) was used. The results are shown in Table 2.

Example 3 Using the modified polymer particles obtained in Example 1 and an acrylonitrile-butadiene-styrene copolymer (Taflex YT410 (trade name) manufactured by Mitsubishi Kasei Polytech Co., Ltd.) in the proportions shown in Table 3 , Toyo Seiki Co., Ltd. Brabender Plastograph, kneading at 230 ℃, then 1m by compression molding method
An m-thick sheet was obtained. Various evaluations were performed on these sheets. The results are shown in Table 3.

Comparative Example 3 Instead of the modified polymer particles of Example 3, unmodified styrenic elastomer particles (Kraton G 16 manufactured by Shell Chemical Co., Ltd.) were used.
A sheet was obtained and evaluated in the same manner as in Example 3 except that 57) was used. The results are shown in Table 3.

Example 4 Using the modified polymer particles obtained in Example 1, polyvinylidene fluoride (Kainer 460 (trade name) manufactured by Penwald Co., Ltd.) in a ratio shown in Table 4, manufactured by Toyo Seiki Co., Ltd. A 1 mm thick sheet was obtained by a compression molding method after kneading at 200 ° C. with a Brabender Plastograph. Various evaluations were performed on these sheets. The results are shown in Table 4.

Comparative Example 4 Instead of the modified polymer particles of Example 4, unmodified styrene elastomer particles (Kraton G 16 manufactured by Shell Chemical Co., Ltd.) were used.
A sheet was obtained and evaluated in the same manner as in Example 4 except that 57) was used. The results are shown in Table 4.

Example 5 The modified polymer particles obtained in Example 1, polypropylene (Mitsubishi Polychemical MA3 (trade name) manufactured by Mitsubishi Yuka: MFR1)
1.0 g / 10 minutes) and polyvinyl chloride (Vinica Compound D7210 (trade name) manufactured by Mitsubishi Kasei Polytech Co., Ltd.) at a ratio shown in Table 5 at 180 ° C. in a Brabender Plastograph manufactured by Toyo Seiki Co., Ltd. After kneading, the 1 mm thick sheet was obtained by the compression molding method. Various evaluations were performed on these sheets. The results are shown in Table 5.

Comparative Example 5 A sheet was obtained and evaluated in the same manner as in Example 5 except that unmodified styrene elastomer particles were used in place of the modified polymer particles in Example 5. The results are shown in Table 5.

Example 6 Modified polymer particles obtained in Example 1, polypropylene (Mitsubishi Polychemicals MA3 manufactured by Mitsubishi Petrochemical: MFR 11.0 g /
10 minutes), polymethylmethacrylate (Acrypet manufactured by Mitsubishi Rayon Co., Ltd.) was used at a ratio shown in Table 6, and was kneaded at 200 ° C. in a Brabender Plastograph manufactured by Toyo Seiki Co., Ltd., and then 1 mm thick by compression molding. Got the sheet.
Various evaluations were performed on these sheets. The results are shown in Table 6.
Shown in.

Comparative Example 6 A sheet was obtained and evaluated in the same manner as in Example 6 except that unmodified styrene elastomer particles were used in place of the modified polymer particles in Example 6. The results are shown in Table 6.

Example 7 Modified polymer particles obtained in the process of Example 1 above,
Polypropylene (Mitsubishi Yuka Mitsubishi Polypro MA3: MF
R11.0 g / 10 minutes), and acrylonitrile / butadiene / styrene copolymer (Taflex YT410 (trade name) manufactured by Mitsubishi Kasei Polytech) at a ratio shown in Table 3, and Brabender Plastograph manufactured by Toyo Seiki Co., Ltd. At 230 ° C., a 1 mm thick sheet was obtained by compression molding. Various evaluations were performed on these sheets. The results are shown in Table 7.

Comparative Example 7 A sheet was obtained and evaluated in the same manner as in Example 7 except that unmodified styrene elastomer particles were used in place of the modified polymer particles in Example 7. The results are shown in Table 7.

Example 8 Modified polymer particles obtained in the process of Example 1 above,
Polypropylene (Mitsubishi Yuka Mitsubishi Polypro MA3: MF
R11.0 g / 10 minutes) and polyvinylidene fluoride (Kainer 460 manufactured by Penwald Co., Ltd.) in the ratios shown in Table 8 were used and kneaded at 200 ° C. in a Brabender Plastograph manufactured by Toyo Seiki Co., Ltd. A 1 mm thick sheet was obtained by the method. Various evaluations were performed on these sheets. The results are shown in Table 8.

Comparative Example 8 A sheet was obtained and evaluated in the same manner as in Example 8 except that unmodified styrene-based elastomer particles were used in place of the modified polymer particles in Example 8. The results are shown in Table 8.

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

[Table 3]

[0049]

[Table 4]

[0050]

[Table 5]

[0051]

[Table 6]

[0052]

[Table 7]

[0053]

[Table 8]

[0054]

INDUSTRIAL APPLICABILITY The polymer composition of the present invention can improve the compatibility of the polyolefin and the polar polymer by using the specific modified polymer, and has the advantages of both. It can be expected to be applied to parts, packaging materials, automobile parts, electric / electronic parts, etc. Further, since the modified styrene-based polymer obtained in the present invention contains a large amount of alkyl acrylate polymer units in the styrene-based elastomer, it is possible to improve the oil resistance, which is a drawback of the styrene-based elastomer.

Claims (1)

[Claims] 1. A vinyl polymer selected from (a) 0 to 95% by weight of an olefin polymer, (b) a halogen-containing polymer, a (meth) acrylic acid ester-containing polymer or a (meth) acrylonitrile-containing polymer. 100 to 5% by weight, and (c) 0.01 to 100 parts by weight of styrene elastomer, 10 to 200 parts by weight of alkyl acrylate monomer, and 100 parts by weight of alkyl acrylate monomer.
An aqueous suspension containing 10 parts by weight of a radical generator is heated to a temperature at which decomposition of the radical generator does not substantially occur, and the alkyl acrylate monomer is impregnated into the styrene elastomer. A modified styrenic polymer having an MFR of 0.1 to 20 g / 10 min, which was obtained by a method of further raising the temperature of the aqueous suspension to complete the graft reaction, had a total amount of (a) and (b) of 100. 2 to parts by weight
A polymer composition containing 200 parts by weight.