JP2002308997A - Rubbery polymer-containing material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a rubbery-elastomer material which, when compounded with a thermoplastic resin, can give a compound capable of giving a molding improved in impact resistance, or the like, and being resistant to hydrolysis and suitable for recycling. SOLUTION: A rubbery polymer-containing material is obtained by spray- recovering a rubbery polymer based on a composite rubber composed of a polyorganosiloxane component and a polyalkyl (meth)acrylate component. A thermoplastic resin composition is obtained by compounding the rubbery- polymer-containing material with a thermoplastic resin such as a polycarbonate or a polyester resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a rubbery polymer-containing material which is useful in applications for improving the properties of a thermoplastic resin.

[0002]

2. Description of the Related Art Conventionally, a method of blending a rubber-like elastic material to impart impact resistance to a thermoplastic resin is known. For example, polycarbonate resin is used as an engineering plastic that provides a molded article having excellent mechanical properties such as impact strength and tensile strength, and further, excellent electrical properties and transparency. Widely used in various fields, when this polycarbonate resin is used for applications requiring solvent resistance and impact resistance, etc., it is necessary to compound the polyester resin alone or in combination with the rubber-like elastic body. It is known that

[0003]

A resin which is easily hydrolyzed,
In particular, when a molded article is manufactured by blending a conventional rubber-like elastic body with a polycarbonate resin or the like, the molded article contains a small amount of salts serving as decomposition factors, and hydrolysis is caused by moisture and heat. The problem that the physical properties of the molded product are impaired is likely to occur. In particular, in view of the recent social situation in which a product requiring recycling is required, a product having a higher level of wet heat properties than before and having a high level of various properties such as impact resistance is desired.

That is, an object of the present invention is to improve the properties such as impact resistance when blended with a thermoplastic resin such as a polycarbonate resin or a polyester resin, and to further improve the thermoplastic resin such as hydrolysis. It is an object of the present invention to provide a rubber-like elastic material which hardly deteriorates in physical properties, has high moisture-heat resistance and can provide a molded product suitable for recycling, and a resin composition containing the same.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have obtained a rubbery polymer-containing material obtained by spraying and recovering a rubbery polymer comprising a specific component.
In particular, it has been found that the powder, granule or pellet exhibits a very excellent effect, and the present invention has been completed.

That is, the present invention is characterized in that a rubbery polymer obtained by spraying and recovering a rubbery polymer mainly composed of a composite rubber composed of a polyorganosiloxane component and a polyalkyl (meth) acrylate component is obtained. It is a coalescence-containing material, and is particularly preferably in the form of powder, granules or pellets.

Further, the present invention is a thermoplastic resin composition obtained by blending the above-mentioned rubbery polymer-containing material with a thermoplastic resin.

In the present invention, “(meth) acrylate” means acrylate and / or methacrylate.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The rubbery polymer used in the present invention is:
The main component is a composite rubber composed of a polyorganosiloxane component and a polyalkyl (meth) acrylate component. Such a rubbery polymer is disclosed in, for example,
No. 79954. As a specific example,
Copolymers obtained by polymerizing one or more vinyl monomers onto a composite rubber composed mainly of a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component are listed. Can be Particularly, 0.01 to 99.99 parts by mass of a polyorganosiloxane rubber component and 0.01 to 9 parts by mass of a polyalkyl (meth) acrylate rubber component.
One or more vinyl monomers in the presence of a composite rubber having an average particle diameter of 0.03 to 5.0 µm composed of 9.99 parts by mass (total amount of both rubber components 100 parts by mass) Is preferably a copolymer obtained by graft polymerization. In this case, the content of each of the polyorganosiloxane rubber component and the polyalkyl (meth) acrylate rubber component is more preferably from 2 to 98 parts by mass, and particularly preferably from 5 to 95 parts by mass.

When extremely excellent impact strength is required at a low temperature, satisfactory performance cannot be obtained with a simple mixture of the above rubber components. Impact characteristics can be obtained.

The average particle size of the composite rubber is 0.1 as described above.
03 to 5.0 μm is preferred. Average particle size is 0.03 μm
If it is more than the above, the impact resistance of the molded article made of the resin composition containing the compound will be improved. Further, the average particle size is 5.0 μm.
When it is at most m, the impact resistance of the molded product will be improved, and the appearance of the molded surface will also be good. In order to produce a composite rubber having such an average particle diameter, an emulsion polymerization method is optimal.
For example, first, a latex of a polyorganosiloxane rubber is prepared, and then a monomer for synthesizing an alkyl (meth) acrylate rubber is impregnated into rubber particles of the polyorganosiloxane rubber latex, and thereafter, the monomer for polymerization is polymerized. Is preferred.

The polyorganosiloxane rubber component constituting the composite rubber can be prepared, for example, by emulsion polymerization using the following organosiloxane and crosslinking agent (I). The graft crosslinking agent (I) can be used in combination.

As the organosiloxane, various cyclic members having three or more member rings are preferable, and three to six-member ring members are more preferable. Specific examples thereof include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane,
Examples include decamethylcyclopentasiloxane, dodecamethylcyclohexanesiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, and octaphenylcyclotetrasiloxane. These can be used alone or in combination of two or more. The amount of the organosiloxane used is preferably at least 50% by mass, more preferably at least 70% by mass in the polyorganosiloxane rubber component.

As the crosslinking agent (I), trifunctional or 4-functional
Functional silane crosslinking agents are preferred. Specific examples thereof include trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetrabutoxysilane and the like. Particularly, a tetrafunctional silane crosslinking agent is preferable, and tetraethoxysilane is most preferable. The amount of the crosslinking agent (I) used is preferably 0.1 to 30% by mass in the polyorganosiloxane rubber component.

As the graft-linking agent (I), the following formula (I)
-1) to (I-3)

[0016]

Embedded image

(In each formula, R ¹ represents a methyl group, an ethyl group, a propyl group, or a phenyl group, R ² represents a hydrogen atom or a methyl group, n is an integer including 0, and p is an integer.) The compound capable of forming the polymer constituent unit represented by any of the above is more preferable, but the graft crosslinking agent to be used is not limited to the specific examples.

In particular, (meth) acryloyloxysiloxane capable of forming a unit of the formula (I-1) has a high grafting efficiency, so that an effective graft chain can be formed. It is advantageous. Among compounds capable of forming the unit of the formula (I-1), methacryloyloxysiloxane is preferred. Specific examples thereof include β-methacryloyloxyethyldimethoxymethylsilane, γ
-Methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane, γ-methacryloyloxybutyl Diethoxymethylsilane and the like can be mentioned. The use amount of the graft crossing agent is preferably 0 to 10% by mass in the polyorganosiloxane rubber component.

For the production of the latex of the polyorganosiloxane rubber component, for example, the methods described in US Pat. Nos. 2,891,920 and 3,294,725 can be used. For example, a mixed solution of an organosiloxane, a crosslinking agent (I) and, if desired, a graft crosslinking agent (I) is sheared with water using a homogenizer or the like in the presence of a sulfonic acid emulsifier such as alkylbenzenesulfonic acid or alkylsulfonic acid. It is preferable to produce by a mixing method. Alkylbenzene sulfonic acid is suitable because it acts as an emulsifier for the organosiloxane and also serves as a polymerization initiator. At this time, when a metal salt of an alkyl benzene sulfonic acid, a metal salt of an alkyl sulfonic acid, or the like is used in combination, it is effective in stably maintaining the polymer during graft polymerization.

As the polymerization initiator, acids such as hydrochloric acid and sulfuric acid may be used in addition to the above-mentioned acids having emulsifying ability. As the emulsifier to be used in combination, a general emulsifier can be used, but it is preferable to use an emulsifier containing an alkali metal as a main component of a counter ion. Alkali metals are sodium,
It is classified as an alkali metal in the periodic table of elements such as potassium and cesium. Further, a sulfuric acid and / or sulfonic acid ester emulsifier is also preferable. Specific examples include sodium alkyl benzene sulfonate, sodium diphenyl ether disulfonate, sodium alkyl sulfate, sodium polyoxyethylene alkyl sulfate, sodium polyoxyethylene nonyl phenyl ether sulfate, and the like.

In the present invention, the polyalkyl (meth) acrylate rubber component constituting the composite rubber includes, for example, an alkyl (meth) acrylate shown below and a crosslinking agent (II)
And a graft crossing agent (II).

As the alkyl (meth) acrylate,
For example, methyl acrylate, ethyl acrylate, n
-Propyl acrylate, n-butyl acrylate, 2
Alkyl acrylates such as -ethylhexyl acrylate; alkyl methacrylates such as hexyl methacrylate, 2-ethylhexyl methacrylate, and n-lauryl methacrylate; Particularly, n-butyl acrylate is preferred.

Examples of the crosslinking agent (II) include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and 1,4-butylene glycol dimethacrylate.

Examples of the graft crosslinking agent (II) include, for example,
Allyl methacrylate, triallyl cyanurate, triallyl isocyanurate and the like can be mentioned. In particular, allyl methacrylate can be used as a crosslinking agent.

These crosslinking agents (II) and graft crossing agents (II) can be used alone or in combination of two or more. The total amount of the crosslinking agent (II) and the grafting agent (II) used is preferably 0.1 to 2.0% by mass in the polyalkyl (meth) acrylate rubber component.

The polyalkyl (meth) acrylate rubber component is introduced into a latex of a polyorganosiloxane rubber component neutralized by the addition of an aqueous alkali solution such as sodium hydroxide, potassium hydroxide or sodium carbonate.
It is preferable to add an alkyl (meth) acrylate, a cross-linking agent (II) and a graft cross-linking agent (II), impregnate the polyorganosiloxane rubber particles, and polymerize using a radical polymerization initiator. According to such a method, the polyalkyl (meth) entangled with the crosslinked network of the polyorganosiloxane rubber as the polymerization proceeds.
A crosslinked network of acrylate rubber is formed, and a latex of a composite rubber of a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component, which cannot be separated substantially, is obtained. Examples of the composite rubber obtained here include a composite rubber in which a main skeleton of a polyorganosiloxane rubber component has a repeating unit of dimethylsiloxane and a main skeleton of a polyalkyl (meth) acrylate rubber component has a repeating unit of n-butyl acrylate. Is preferred.

In the composite rubber prepared by such emulsion polymerization, since the polyorganosiloxane rubber component and the polyalkyl (meth) acrylate rubber component are tightly entangled with each other, a common organic solvent such as acetone and toluene cannot be used. Extraction is not possible. For example, the gel content measured by extracting the composite rubber with toluene at 90 ° C. for 12 hours is usually 80% by mass or more.

Such a composite rubber can be graft-copolymerized with a vinyl monomer. For example, a graft copolymer (rubber-based polymer containing a composite rubber as a main component) can be obtained by subjecting a vinyl monomer to radical polymerization in one step or in multiple steps in the presence of a composite rubber latex.

Examples of the vinyl monomer to be graft-polymerized to the composite rubber include aromatic alkenyl compounds such as styrene, methylstyrene and vinyltoluene; methacrylic esters such as methyl methacrylate and 2-ethylhexyl methacrylate; methyl acrylate And vinyl acrylates such as ethyl acrylate and butyl acrylate; and vinyl cyanide compounds such as acrylonitrile and methacrylonitrile. These can be used alone or in combination of two or more. Of these, methacrylates are preferred, and methyl methacrylate is particularly preferred.

The ratio of the composite rubber to the vinyl monomer in the graft copolymer is 30 to 95% by mass of the composite rubber, 5 to 5% of the vinyl monomer, based on the mass of the graft copolymer.
70 mass% is preferable, and 40 to 90 mass% of a composite rubber and 10 to 60 mass% of a vinyl monomer are more preferable. When the proportion of the vinyl-based monomer is 5% by mass or more, the dispersion of the graft copolymer in the resin composition becomes sufficient, and 70% by mass.
If it is below, the impact strength is improved.

The latex of the rubbery polymer thus obtained is recovered by spraying, formed into powders and granules, and pelletized if necessary. As a method for recovering the powder of the emulsion polymerization latex, besides the spray recovery method, there is a method of coagulating or pouring into a poor solvent to recover the precipitate. In the present invention, the spray recovery method is particularly used.

In the coagulation method, an acid or a salt is generally used as a coagulant. However, it is usually difficult to apply an acid coagulation method to an emulsion polymerization latex using a sulfuric acid or a sulfonic acid emulsifier. General. In this case, as the coagulant, aluminum sulfate, calcium chloride, calcium acetate, magnesium sulfate or the like is used. However, if a small amount of metals and ions derived from these salts remain in the recovered rubbery polymer, the wet heat properties of the molded product obtained from the thermoplastic resin composition containing the rubbery polymer may be reduced. Adversely affect. However, an alkali metal which is a counter ion of the emulsifier has a small effect on the wet heat characteristics. Based on such knowledge, in the present invention, spray recovery is selected so that metal salts or metals that have an adverse effect are not left in the rubbery polymer. That is, since no coagulant is used in the spray recovery, the possibility of containing unnecessary metal salts is eliminated.

The thermoplastic resin composition of the present invention is obtained by blending the rubbery polymer-containing powder, granules or pellets of the present invention with various thermoplastic resins, for example, as an impact modifier. The compounding amount is preferably 0.1 to 80 parts by mass, more preferably 0.2 to 50 parts by mass with respect to 100 parts by mass of the thermoplastic resin. When the amount is 0.1 part by mass or more, the effect of improving the impact resistance of the thermoplastic resin is increased, and when the amount is 80 parts by mass or less, it is advantageous in terms of cost.

As the thermoplastic resin used in the present invention, for example, polypropylene (PP), polyethylene (PE)
Olefin resins such as polystyrene (PS), high impact polystyrene (HIPS), (meth) acrylate-styrene copolymer (MS), styrene-acrylonitrile copolymer (SAN), styrene-maleic anhydride copolymer Coalescing (SMA), ABS, ASA, AES
Such as styrene resin (St resin), acrylic resin such as polymethyl methacrylate (PMMA) (Ac resin), polycarbonate resin (PC resin), polyamide resin (PA resin), polyethylene terephthalate ( PET), polybutylene terephthalate (PBT)
Polyester resin (PEs resin), (modified) polyphenylene ether resin (PPE resin), polyoxymethylene resin (POM resin), polysulfone resin (PSO resin), polyarylate resin ( PA
r-based resin), polyphenylene-based resin (PPS-based resin),
Engineering plastics such as thermoplastic polyurethane resin (PU resin), styrene elastomer,
Thermoplastic elastomer (TPE) such as olefin elastomer, vinyl chloride elastomer, urethane elastomer, polyester elastomer, polyamide elastomer, fluorine elastomer, 1,2-polybutadiene, trans 1,4-polyisoprene, PC / A
PC resin such as BS / St resin alloy, PVC / A
PVC resin such as BS / St resin alloy, PA / AB
PA resin such as S / St resin alloy, PA resin / T
PA alloy such as PE alloy, PA / PP / Polyolefin resin alloy, PBT resin / TPE, PC / PBT
PC-based resin / PEs-based resin alloys, polyolefin-based resins / TPE, alloys of olefin-based resins such as PP / PE, PPE / HIPS, PPE / PBT, PPE
Polymer alloys such as PPE resin alloys such as / PA and PVC / PMMA such as PVC / PMMA;
Hard, semi-hard, soft vinyl chloride resins and the like can be mentioned.
In particular, a thermoplastic resin containing a polycarbonate resin and / or a polyester resin as a main component is preferable. This resin may be mixed with other resins such as ABS resin and polystyrene.

The mixing of the rubbery polymer-containing powder, granules or pellets of the present invention with a thermoplastic resin is carried out, for example, by a kneader. Specifically, mixing rolls, calender rolls, Banbury mixers, 1 shaft or 2 shafts
A screw extruder can be used. Also, if necessary,
Various additives such as dyes and pigments, stabilizers, reinforcing materials, fillers, and flame retardants may be blended.

By molding the thermoplastic resin composition of the present invention, a molded article having improved desired physical properties such as impact resistance can be obtained. For the molding, various molding machines such as an injection molding machine, a blow molding machine, and an inflation molding machine can be used.

[0037]

The present invention will be described below in detail with reference to examples. In the following description, "parts" all mean parts by mass.

<Production Example 1: Powdery rubbery polymer (S-
1)> 2 parts of tetraethoxysilane, 0.5 part of γ-methacryloyloxypropyldimethoxymethylsilane and 97.5 parts of octamethylcyclotetrasiloxane were mixed to obtain 100 parts of a siloxane mixture. To 100 parts of this siloxane mixture, 200 parts of distilled water in which 1 part of sodium dodecylbenzenesulfonate and 1 part of dodecylbenzenesulfonic acid were dissolved was added.
The mixture was preliminarily stirred at 00 rpm, and further emulsified and dispersed with a homogenizer at a pressure of 300 kg / cm ² to obtain an organosiloxane latex. This latex was transferred to a separable flask equipped with a condenser and a stirring blade, and heated at 80 ° C. for 5 hours while stirring and mixing.
The mixture was allowed to stand at 0 ° C., and after 48 hours, the pH of this latex was neutralized to 7.4 with an aqueous solution of sodium hydroxide, and the polymerization was completed to obtain a polyorganosiloxane rubber latex. The polymerization rate of this polyorganosiloxane rubber was 89.5%, and the average particle size of the rubber was 0.16 μm.

117 parts of this polyorganosiloxane rubber latex was placed in a separable flask equipped with a stirrer, 57.5 parts of distilled water was added, the atmosphere was replaced with nitrogen, and the temperature was raised to 50 ° C. Butyl acrylate 33.95
Part, allyl methacrylate 1.05 part and tert-
A mixture of 0.26 parts of butyl hydroperoxide was charged and stirred for 30 minutes to allow the mixture to permeate the polyorganosiloxane rubber particles. Then, ferrous sulfate 0.0
02 parts, ethylenediaminetetraacetic acid disodium salt 0.0
A mixture of 0.7 parts, 0.26 parts of Rongalite and 5 parts of distilled water was charged to start radical polymerization, and then the internal temperature was adjusted to 7
The mixture was kept at 0 ° C. for 2 hours to complete the polymerization to obtain a composite rubber latex. The average particle size of this composite rubber was 0.19 μm. Further, the solid content was obtained by drying the composite rubber latex, and the gel content measured by extracting with toluene at 90 ° C. for 12 hours was 97.3% by mass.

To this composite rubber latex, a mixture of 0.12 parts of tert-butyl hydroperoxide and 30 parts of methyl methacrylate was added dropwise at 70 ° C. for 15 minutes, and then kept at 70 ° C. for 4 hours to obtain a composite. The graft polymerization to rubber was completed to obtain a graft copolymer latex. The conversion of methyl methacrylate is 9
It was 6.4%.

Finally, the graft copolymer latex was spray-recovered to recover 99.8 parts of a powder composed of the graft copolymer (rubber polymer). This spray recovery is performed using an atomizer type spray device, and the inlet temperature 1
The reaction was performed at 04 ° C and an outlet temperature of 62 ° C. The water content of the obtained powder [rubber polymer (S-1)] was 0.5% or less.

<Production Example 2: Pellets of rubbery polymer (S
-1P)> The powdery rubbery polymer S-1 obtained in Production Example 1
Was further extruded with a single 25 mmφ extruder at a temperature of 120 ° C., and the strand obtained using a strand die was placed on a pelletizer, and was about 2 mm in diameter and about 5 mm in length.
To obtain a rubbery polymer (S-1P) in the form of pellets.

<Production Example 3: Granular rubbery polymer (S-1)
G)> The rubbery polymer (S-1) in the pellets obtained in Production Example 2
P) was cooled at −20 ° C. for 24 hours, and
L-volume Henschel mixer, 1500 rpm, 30
Crushed for 2 seconds and 75 to dry attached water
At 48 ° C. for 48 hours, and then pulverized material obtained is sieved, passed through a sieve having an opening of 3 mm, and opened at 0.8.
Those which did not pass through the sieve having a diameter of mm were recovered as a granular rubbery polymer (S-1G).

<Comparative Production Example 1: Rubbery polymer (S-2)
Spray recovery is not performed on the graft copolymer latex obtained in Production Example 1, but instead, it is dropped into 200 parts of hot water containing 2.0 parts of aluminum sulfate, coagulated, separated, washed, and then dried. Drying treatment at 48 ° C. for 48 hours to obtain a powder comprising a graft copolymer [rubber polymer (S-2)] 96.5
Got a part.

<Comparative Production Example 2: Rubbery polymer (S-3)
> The same procedure as in Comparative Production Example 1 was carried out except that 2.0 parts of calcium chloride was used instead of 2.0 parts of aluminum sulfate, to obtain a powder of the graft copolymer [rubber polymer (S- 3)] 96.5 parts were obtained.

<Examples 1 to 6 and Comparative Examples 1 to 8> Rubbery polymers (S-1), (S-1P), (S-1G),
(S-2) and (S-3) were blended with various resins at the ratios shown in Table 1 to prepare various thermoplastic resin compositions. These resin compositions using a 30 mm ² screw extruder 2
The pellet was pelletized at 60 ° C., then dried at 90 ° C. for 12 hours, and injection-molded at a molding temperature of 260 ° C. to obtain an ASTD638 type 1 dumbbell test piece. Each test piece was immersed in pure water maintained at 80 ° C. for 8 hours, and then the tensile rupture strength was measured. The tensile rupture strength before immersion was defined as 100%.
The ratio of the measured value after immersion for 8 hours to the ratio was determined as the retention. Table 2 shows the results.

[0047]

[Table 1]

The abbreviations in Table 1 indicate the following resins and additives. -"PC": polycarbonate resin (manufactured by Nippon GE Plastics Co., Ltd., trade name: Lexan 141)-"PBT": polyester resin (manufactured by Nippon GE Plastics Co., Ltd., trade name: Barox 325)-"HIPS": high-impact polystyrene (Manufactured by Idemitsu Petrochemical Co., Ltd., trade name IT42) "AS": styrene-acrylonitrile copolymer (manufactured by Technopolymer Co., Ltd., trade name: 290FF) "SAN": SAN resin (manufactured by Ube Saicon Co., Ltd.)
"ABS": ABS resin (manufactured by Ube Saicon Co., Ltd.)
"Stb1": Stabilizer (trade name, ADK STAB AO-60, manufactured by Asahi Denka Co., Ltd.) "stb2": Stabilizer (trade name, ADK STAB PEP-36, manufactured by Asahi Denka Co., Ltd.) "P- 1 ": Phosphate ester (manufactured by Daihachi Chemical Co., trade name: CR-733S)

[0049]

[Table 2]

As is clear from the results in Table 2, Example 1
In Nos. To 4, rubbery polymer (S-
1) Since the thermoplastic resin composition containing (S-1P) and (S-1G) is used, there is little decrease in physical properties such as breaking strength after a wet heat property test, and the composition has excellent wet heat properties. ing. On the other hand, in Comparative Examples 1 to 8, since the thermoplastic resin composition containing the rubbery polymer (S-2) (S-3) obtained by the salt coagulation method was used, the breaking strength after the wet heat property test was low. It will drop significantly.

[0051]

As described above, when the rubbery polymer-containing material of the present invention is blended with a thermoplastic resin such as a polycarbonate resin or a polyester resin, various properties such as impact resistance are improved. In addition, deterioration of the physical properties of the thermoplastic resin such as hydrolysis is less likely to occur, and a molded article having high wet heat resistance and suitable for recycling can be provided. Therefore, its environmental and industrial value is extremely large.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) C08L 101/00 C08L 101/00 F term (reference) 4F070 AA32 AA60 AB08 DA34 DC01 4J002 AC041 AC061 BB031 BB051 BB121 BC021 BC031 BC061 BC071 BD031 BD121 BG061 BH011 BN061 BN151 BN192 CB001 CF001 CF061 CF071 CF161 CG001 CH071 CK021 CL001 CN011 CN031

Claims (4)

[Claims] 1. A rubbery polymer-containing material obtained by spraying and recovering a rubbery polymer mainly composed of a composite rubber composed of a polyorganosiloxane component and a polyalkyl (meth) acrylate component. . 2. The rubbery polymer-containing material according to claim 1, wherein the shape of the rubbery polymer material is powder, granules or pellets. 3. A thermoplastic resin composition comprising the rubbery polymer-containing material according to claim 1 and a thermoplastic resin. 4. The thermoplastic resin composition according to claim 3, wherein the thermoplastic resin contains a polycarbonate resin and / or a polyester resin.