JP2002285009A - Thermoplastic polymer composition containing minerals - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic polymer composition containing minerals excellent in mechanical strengths, appearance, flame retardancy, abrasion resistance and oil resistance. SOLUTION: The thermoplastic polymer composition consists of (A) a branched inorganic compound and (B) a thermoplastic polymer. The average particle size of (A) ranges 1-100,000 nm, and (A) is silicon oxide and/or aluminum oxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inorganic-containing thermoplastic polymer composition. More specifically, the present invention relates to a thermoplastic polymer composition having excellent mechanical strength, appearance, abrasion resistance, flame retardancy, moldability, and oil resistance.

[0002]

2. Description of the Related Art Resins or elastomers containing filler-based inorganic compounds such as calcium carbonate, silica or talc are widely used for applications such as automobile parts.
However, since the inorganic compound and the organic resin or elastomer are incompatible with each other, a decrease in strength, a poor appearance, and a decrease in moldability due to poor dispersion cannot be avoided. For example, so-called dynamic crosslinking in which a rubber-like polymer such as a radical-crosslinkable olefin-based elastomer and an olefin-based resin such as PP that are not radically crosslinkable are crosslinked while being melt-kneaded in an extruder in the presence of a radical initiator. Dynamically crosslinked thermoplastic elastomer composition containing a filler-based inorganic compound such as calcium carbonate or talc in the thermoplastic elastomer composition according to JP-A-2000-53
816). However, the appearance and abrasion resistance are not sufficient due to the large dispersed particle diameter of the inorganic compound of the composition. Further, there is disclosed a crosslinked elastomer composition (US Pat. No. 5,929,156) obtained by blending a specific highly dispersible silica with an elastomer.
Although the dispersibility is improved by having a specific structure, there is a problem of moldability due to lack of thermoplasticity.

[0003]

SUMMARY OF THE INVENTION In view of such circumstances, the present invention has no such problems as described above, that is, a rubber excellent in mechanical strength, appearance, abrasion resistance, moldability and flame retardancy. It is intended to provide a composition.

[0004]

Means for Solving the Problems The present inventors diligently studied a thermoplastic polymer composition having excellent mechanical strength, and as a result, it was found that an inorganic compound having a specific structure has a specific particle size. It has been found that not only mechanical strength but also appearance, abrasion resistance, moldability and flame retardancy can be drastically improved, and the present invention has been completed. That is, the present invention relates to (A)
In a polymer composition comprising an inorganic compound having a branched structure (hereinafter, sometimes simply referred to as (A)) and (B) a thermoplastic polymer (hereinafter, sometimes simply referred to as (B)), (A) a thermoplastic polymer composition characterized by having an average particle size of 1 to 100,000 nm, especially a thermoplastic polymer composition characterized in that (A) is silicon oxide and / or aluminum oxide Is provided.

Hereinafter, the present invention will be described in detail. The composition of the present invention is a thermoplastic polymer composition comprising (A) a specific inorganic compound and (B) a thermoplastic polymer. Here, it is essential that the inorganic compound (A) has a branched structure. By having a branched structure, the entanglement with the polymer chain of (B) increases, and the mechanical strength is dramatically improved while maintaining the moldability. And the average particle size is 1
１００100,000 nm, preferably 1 to 50,000 nm, more preferably 1 to 1000 nm.
0 nm, most preferably 1 to 5000 nm, and very preferably 1 to 500 nm, improved mechanical strength, appearance, abrasion resistance, moldability and flame retardancy, and completed the present invention. .

Hereinafter, each component of the present invention will be described in detail. The inorganic compound (A) in the present invention is not particularly limited as long as it satisfies the requirements of the branched structure and the average particle size of the present invention. For example, silicon oxide or aluminum oxide is used. Among (A), silicon oxide is preferable, and there is no particular limitation as long as the silicon oxide has a branched structure as shown in the embodiment of FIG. Silicon oxide is also called synthetic silica,
Roughly speaking, there are two synthesis methods, a wet method and a dry method.
The former includes one synthesized by a reaction between sodium silicate and a mineral acid, and one obtained by hydrolysis of alkoxysilane. The latter include those synthesized by high-temperature hydrolysis of silicon halide in an oxyhydrogen flame. Such a synthetic silica is preferably amorphous. As one of particularly preferred synthetic silicas, US Pat. M. And amorphous silica such as Huberpol 135, Zeopol 8715, 8745, and 8755 manufactured by Huber. The manufacturing method is a wet method, and US Pat.
No. 929156.

The amorphous silica (A) is produced by adding an acid to a mixture of water and an alkali metal silicate at 60 to 90 ° C. The water and / or silicate may be heated separately, or may be mixed and heated simultaneously.
The alkali metal silicate is an alkali metal or alkaline earth metal salt of meta or disilicate, and is not particularly limited. It is preferable to use an electrolyte such as sodium sulfate as a reaction medium. Another preferred synthetic silica is hydrophilic or hydrophobic aerosil manufactured by Nippon Aerosil Co., Ltd., which is called fumed silica. For example, OX50.50,90G, 130,150,200,300,38
0, 380S, etc., and those obtained by treating the above grades with dimethyldichlorosilane, hexamethyldisilazane, octylsilane, dimethylsilicone oil, methacryloxysilane, aminosilane, and hexamethyldisilazane. Can be used. The production method is dry, silicon tetrachloride and hydrogen, oxygen,
High-temperature hydrolysis with water. The component (B) in the present invention is a thermoplastic resin and / or a thermoplastic elastomer.

The thermoplastic resins include, for example, polyaromatic vinyl, polycarbonate, polyphenylene ether, polyolefin, polyvinyl chloride, polyamide, polyester, polyphenylene sulfide, and the like.
Polymethacrylates or the like may be used alone or in combination of two or more. Particularly, thermoplastic resins of polyaromatic vinyl type, polycarbonate type and polyphenylene ether type are very preferable. As the combination of (A), aromatic polycarbonate and aromatic vinyl-based resin, or aromatic vinyl-based resin and polyphenylene ether, or aromatic polycarbonate, aromatic vinyl-based resin, and polyphenylene ether are most preferred.

The aromatic vinyl resin as one of the thermoplastic resins (B) in the present invention is a rubber-modified aromatic vinyl resin and / or a non-rubber-modified aromatic vinyl resin. The rubber-modified aromatic vinyl-based resin comprises an aromatic vinyl-based resin matrix and rubber particles dispersed therein, and the aromatic vinyl-based resin is an aromatic vinyl monomer in the presence of a rubber-like polymer. And, if desired, a vinyl monomer copolymerizable therewith is added, and the monomer (or a mixture thereof) is subjected to rubber polymerization by a known bulk polymerization method, bulk suspension polymerization method, solution polymerization method, or emulsion polymerization method. It can be obtained by graft-polymerizing a polymer in the form of a polymer.

Examples of such a polymer include impact-resistant polystyrene, ABS resin (acrylonitrile-butadiene-styrene copolymer), AAS resin (acrylonitrile-acryl rubber-styrene copolymer), and AES resin (acrylonitrile- Ethylene-propylene rubber-styrene copolymer). Here, the rubber-like polymer needs to have a glass transition temperature (Tg) of −30 ° C. or less, and if it exceeds −30 ° C., the impact resistance decreases. Examples of such rubbery polymers include diene rubbers such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), and saturated rubbers obtained by hydrogenating the diene rubbers, isoprene rubber, chloroprene rubber, and polyacrylic rubber. Examples include acrylic rubbers such as butyl acid and ethylene-propylene-diene monomer terpolymer (EPDM). Diene rubbers are particularly preferred.

The aromatic vinyl monomer as an essential component in the graft-polymerizable monomer mixture to be polymerized in the presence of the rubbery polymer is, for example, styrene, α-methylstyrene, paramethylstyrene or the like. Yes, styrene is most preferred, but other aromatic vinyl monomers described above may be copolymerized mainly with styrene. If necessary, one or more monomer components copolymerizable with the aromatic vinyl monomer can be introduced as components of the rubber-modified aromatic vinyl resin in (B). When it is necessary to increase oil resistance, unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile can be used. When it is necessary to lower the melt viscosity at the time of blending, the carbon number is 1 to 8
Acrylic ester consisting of the above alkyl group can be used. Further, when it is necessary to further increase the heat resistance of the resin composition, α-methylstyrene, acrylic acid,
Monomers such as methacrylic acid, maleic anhydride, and N-substituted maleimide may be copolymerized. The content of the vinyl monomer copolymerizable with the vinyl aromatic monomer in the monomer mixture is from 0 to 40% by weight.

The rubber-like polymer in the rubber-modified aromatic vinyl resin is preferably 5 to 80% by weight, particularly preferably 10 to 50% by weight, and the graft-polymerizable monomer mixture is preferably 95 to 20% by weight. %, More preferably 90
５０50% by weight. Within this range, the balance between impact resistance and rigidity of the target resin composition is improved.
Further, the rubber particle diameter of the styrene polymer is 0.1 to
5.0 μm is preferable, and 0.2 to 3.0 μm is particularly preferable. Within the above range, impact resistance is particularly improved. Reduced viscosity ηsp / c of resin portion, which is a measure of the molecular weight of rubber-modified aromatic vinyl resin (0.5 g / dl, measured at 30 ° C .: toluene solution when matrix resin is polystyrene, unsaturated nitrile-aromatic matrix resin) Methyl ethyl ketone in the case of an aromatic vinyl copolymer) is 0.30
０．８0.80 dl / g.
More preferably, it is in the range of 40 to 0.60 dl / g. Means for satisfying the above requirements regarding the reduced viscosity ηsp / c of the rubber-modified styrenic resin include adjustment of the polymerization initiator amount, polymerization temperature, and chain transfer agent amount.

As a method for producing a rubber-modified aromatic vinyl resin, in particular, a uniform polymerization stock solution comprising a rubbery polymer, a monomer (or a monomer mixture), and a polymerization solvent is continuously mixed with a stirrer. A bulk polymerization method in which the mixture is supplied to a multi-stage bulk polymerization reactor, and is continuously polymerized and devolatilized, is preferable. When a rubber-modified styrene polymer is produced by a bulk polymerization method, the reduced viscosity ηsp
The control of / c can be performed by the polymerization temperature, the type and amount of the initiator, the solvent, and the amount of the chain transfer agent. When a monomer mixture is used, the copolymer composition can be controlled by the charged monomer composition. The control of the rubber particle diameter can be performed by the stirring rotation speed. That is, the reduction in particle size can be achieved by increasing the rotation speed, and the increase in particle size can be achieved by reducing the rotation speed.

In the present invention, the aromatic polycarbonate as one of the thermoplastic resins of the component (B) can be selected from aromatic homopolycarbonates and aromatic copolycarbonates. As the production method, a phosgene method in which phosgene is blown into a bifunctional phenol compound in the presence of a caustic alkali and a solvent, or a transesterification method in which a bifunctional phenol compound is transesterified with diethyl carbonate in the presence of a catalyst Can be mentioned. The aromatic polycarbonate preferably has a viscosity average molecular weight of 10,000 to 100,000. Here, the bifunctional phenol compound is 2,2'-bis (4-hydroxyphenyl) propane, 2,2'-bis (4-hydroxy-3,5-dimethylphenyl) propane, bis (4-hydroxyphenyl) propane. Phenyl) methane, 1,1′-bis (4-hydroxyphenyl) ethane, 2,2′-bis (4-hydroxyphenyl) butane, 2,2′-bis (4-hydroxy-3,5
-Diphenyl) butane, 2,2'-bis (4-hydroxy-3,5-dipropylphenyl) propane, 1,1 '
-Bis (4-hydroxyphenyl) cyclohexane, 1
-Phenyl-1,1'-bis (4-hydroxyphenyl) ethane and the like, and 2,2'-bis (4-hydroxyphenyl) propane [bisphenol A] is particularly preferable. In the present invention, the bifunctional phenolic compounds may be used alone or in combination.

In the present invention, the polyphenylene ether as one of the thermoplastic resins of the component (B) is a homopolymer and / or a copolymer having an aromatic ring in the main chain and linked by an ether bond, Specifically, poly (2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, and the like are preferable. 6-dimethyl-1,4-phenylene ether) is preferred. The method for producing such a polyphenylene ether is not particularly limited. For example, a complex of a cuprous salt and an amine according to the method described in U.S. Pat. No. 3,306,874 is used as a catalyst. It can be easily produced by oxidative polymerization of 6-xylenol. In addition, US Pat. No. 3,306,875 and US Pat.
No. 257,357, U.S. Pat. No. 3,257,358.
It can be easily produced by the method described in Japanese Patent Publication No. Sho 52-17880 and Japanese Patent Laid-Open Publication No. Sho 50-51197. The reduced viscosity ηsp / c (0.5 g / dl, chloroform solution, measured at 30 ° C.) of the polyphenylene ether used in the present invention is preferably in the range of 0.20 to 0.70 dl / g. .30 to 0.60 dl /
More preferably, it is in the range g. As a means for satisfying the above requirement regarding the reduced viscosity ηsp / c of the polyphenylene ether, adjustment of the amount of a catalyst in the production of the polyphenylene ether can be exemplified.

The aromatic vinyl thermoplastic elastomer as one of the thermoplastic elastomers (B) used in the present invention is a block copolymer comprising an aromatic vinyl unit and a conjugated diene unit, or the above conjugated diene unit portion. It is a partially hydrogenated block copolymer. The aromatic vinyl monomer constituting the block copolymer,
For example, styrene, α-methylstyrene, paramethylstyrene, p-chlorostyrene, p-bromostyrene,
2,4,5-tribromostyrene and the like, and styrene is most preferred, but other aromatic vinyl monomers described above may be copolymerized mainly with styrene. Further, examples of the conjugated diene monomer constituting the block copolymer include 1,3-butadiene and isoprene.

In the block structure of the block copolymer, a polymer block composed of an aromatic vinyl unit is represented by S, and a polymer block composed of a conjugated diene and / or a partially hydrogenated unit thereof is represented by B. When displaying with,
SB, S (BS) n (where n is an integer of 1 to 3), S
(BSB) n, where n is an integer of 1 to 2
A block copolymer or (SB) nX (where n is 3 to 6)
Integer. X is a residue of a coupling agent such as silicon tetrachloride, tin tetrachloride, and a polyepoxy compound. ) Is preferably a star-shaped (star) block copolymer having a B-part as a bonding center. Above all, SB type 2 and SBS 3
And SBSB type 4 linear block copolymers are preferred.

In the present invention, another preferred thermoplastic elastomer as (B) is a crosslinked thermoplastic elastomer comprising (B-1) a crosslinkable rubbery polymer and (B-2) a thermoplastic resin. It is. The (B-1) crosslinkable rubbery polymer has a glass transition temperature (Tg) of -30.
C. or lower, and such rubbery polymers include, for example, diene rubbers such as polybutadiene, poly (styrene-butadiene), and poly (acrylonitrile-butadiene); saturated rubber obtained by hydrogenating the diene rubber; isoprene; Crosslinking of rubber, chloroprene rubber, acrylic rubber such as polybutyl acrylate, ethylene-propylene copolymer rubber, ethylene-propylene-diene monomer terpolymer rubber (EPDM), ethylene-octene copolymer rubber, etc. Examples thereof include rubber or non-crosslinked rubber, and a thermoplastic elastomer containing the above rubber component.

In the present invention, among the (B-1) crosslinkable rubbery polymers (hereinafter sometimes simply referred to as (B-1)), ethylene / α-olefin copolymers are particularly preferable, and ethylene and carbon number are preferred. Is more preferably an α-olefin having 3 to 20. For example, propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1,
Heptene-1, octene-1, nonene-1, decene-
1, undecene-1, dodecene-1 and the like. Among them, hexene-1, 4-methylpentene-1 and octene-1 are preferable, and α- having 3 to 12 carbon atoms is particularly preferable.
Olefins, especially propylene, butene-1,
Octene-1 is most preferred. (B-1) may contain a monomer having an unsaturated bond, if necessary, for example, conjugated diolefins such as butadiene and isoprene, and non-conjugated diolefins such as 1,4-hexadiene;
Cyclic diene compounds such as dicyclopentadiene and norbornene derivatives, and acetylenes are preferable, and ethylidene norbornene (ENB) and dicyclopentadiene (DCP) are particularly preferable.

In the present invention, ethylene-α of (B-1)
The olefin copolymer is preferably produced using a known metallocene catalyst. Generally, a metallocene-based catalyst is composed of a cyclopentadienyl derivative of a group IV metal such as titanium or zirconium and a co-catalyst, and is not only highly active as a polymerization catalyst, but also has a higher polymer yield than a Ziegler-based catalyst. Has a narrow molecular weight distribution, and the distribution of the comonomer α-olefin having 3 to 20 carbon atoms in the copolymer is uniform. (B-1) used in the present invention
The ethylene / α-olefin copolymer preferably has an α-olefin copolymerization ratio of 1 to 60% by weight,
More preferably 10 to 50% by weight, most preferably 20% by weight.
~ 45% by weight. When the copolymerization ratio of α-olefin is 6
If it exceeds 0% by weight, the hardness and tensile strength of the composition are greatly reduced, while if it is less than 1% by weight, flexibility and mechanical strength are reduced.

(B-1) The density of the ethylene / α-olefin copolymer is preferably in the range of 0.8 to 0.9 g / cm ³ . By using an olefin-based elastomer having a density in this range, an elastomer composition having excellent flexibility and low hardness can be obtained. The (B-1) ethylene / α-olefin copolymer used in the present invention preferably has a long-chain branch. The presence of the long-chain branch enables the density to be lower than the ratio (% by weight) of the copolymerized α-olefin without lowering the mechanical strength.
An elastomer having low hardness and high strength can be obtained. Examples of the olefin elastomer having a long chain branch include U
It is described in SP5278272 and the like. The (B-1) ethylene / α-olefin copolymer preferably has a DSC melting point peak at room temperature or higher. When it has a melting point peak, the form is stable in the temperature range below the melting point, the handleability is excellent, and the stickiness is small.

The melt index of (B-1) used in the present invention is preferably in the range of 0.01 to 100 g / 10 min (190 ° C., 2.16 kg load), more preferably. 0.2 to 10 g / 10 min. If it exceeds 100 g / 10 minutes, the crosslinkability of the composition will be insufficient, and if it is less than 0.01 g / 10 minutes, the fluidity will be poor and the processability will be undesirably reduced. (B-1) used in the present invention may be a mixture of plural kinds. In such a case, it is possible to further improve the workability. In the present invention, as one of the preferable crosslinkable rubbery polymers among (B-1), the above-mentioned polystyrene-based thermoplastic elastomer can also be suitably used.

In the present invention, the hydrogenated copolymer as another preferred crosslinkable rubbery polymer (B-1) is a polymer having a double bond in a main chain and a side chain and / or a random copolymer. A hydrogenated rubber in which 50% or more of the total double bonds of the unsaturated rubber composed of a copolymer is hydrogenated. The total double bonds in the hydrogenated rubber are 50% or more, preferably 90% or more, more preferably 95% or more, and the remaining double bonds in the main chain are 5% or less, and the side chains are Is preferably 5% or less. Specific examples of such a rubber include a rubbery polymer obtained by partially or completely hydrogenating a diene rubber such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), polyisoprene, and polychloroprene. Hydrogenated butadiene rubber or hydrogenated isoprene rubber is particularly preferable.

Such a hydrogenated rubber can be obtained by partially hydrogenating the above rubber by a known hydrogenation method. For example, FLRamp, etal, J.Amer.Chem.Soc., 83,46
72 (1961) .Method of hydrogenation using triisobutylborane catalyst described in Hung Yu Chen, J. Polym. Sci. Polym. Lette
r Ed., 15,271 (1977) Hydrogenation using toluenesulfonyl hydrazide, or hydrogenation using an organic cobalt-organoaluminum catalyst or an organic nickel-organoaluminum catalyst described in JP-B-42-8704. And the like. Here, a particularly preferred method of hydrogenation is disclosed in JP-A-59-133203, JP-A-60-220147, which uses a catalyst capable of hydrogenation under mild conditions of low temperature and low pressure, or in an inert organic solvent. JP-A-62-207303 in which hydrogen is brought into contact with a bis (cyclopentadienyl) titanium compound in the presence of a catalyst comprising a hydrocarbon compound having a sodium, potassium, rubidium or cesium atom. This is the method shown in FIG.

The Mooney viscosity (ML) of the hydrogenated rubber measured at 100.degree.
The weight% styrene solution viscosity (5% SV) is 20 to 300
It is preferably in the range of centipoise (cps).
A particularly preferred range is 25 to 150 cps. The endothermic peak calorie, which is an index of the crystallinity of the hydrogenated rubber, is controlled by adding a polar compound such as tetrahydrofuran or controlling the polymerization temperature. The reduction of the endothermic peak calorific value is achieved by increasing the amount of the polar compound or decreasing the polymerization temperature to increase the 1,2-vinyl bond. (B-1) used in the present invention may be a mixture of plural kinds. In such a case, it is possible to further improve the workability. (B-1) used in the present invention may be a mixture of plural kinds. In such a case, it is possible to further improve the workability.

In the present invention, the thermoplastic resin (B-2) (hereinafter sometimes simply referred to as (B-2)) is the thermoplastic resin described in the above (B), and among them, olefin A resin is preferable, and specific examples thereof include an ethylene resin and a propylene resin. Specific examples of the propylene-based resin (B-2) include homo-isotactic polypropylene, syndiotactic polypropylene, propylene and ethylene,
And isotactic copolymer resins (including block and random) with other α-olefins such as 1, pentene-1 and hexene-1. In the present invention, among (B-2), propylene-based random copolymer resins such as (B-2-a) homo isotactic polypropylene or (B-2-b) random copolymer resin of ethylene and propylene Alternatively, (B-2-c) a propylene-based block copolymer resin is preferable. The appearance and mechanical strength are further improved by combining such two types of olefin resins, such as a crosslinked olefin resin and a decomposed olefin resin.

As (B-2-b), for example, a random copolymer resin of ethylene and propylene can be mentioned.
When the ethylene component is present in the polymer main chain, it becomes a cross-linking point of the cross-linking reaction, and exhibits the properties of the cross-linked olefin resin. (B-2-c) is preferably composed mainly of an α-olefin and does not contain an ethylene unit in the polymer main chain. However, when an ethylene-α-olefin copolymer is present as a dispersed phase, such as a propylene-based block copolymer resin, it exhibits the properties of a decomposable olefin-based resin. (B-2) may be a combination of a plurality of (B-2-a), (B-2-b), and (B-2-c) components. The melt index of the olefin resin suitably used in the present invention is 0.1 to 100 g / 10 min (23
(0 ° C., 2.16 kg load) are preferably used. If it exceeds 100 g / 10 minutes, the heat resistance and mechanical strength of the thermoplastic elastomer composition will be insufficient, and if it is less than 0.1 g / 10 minutes, the fluidity will be poor and the moldability will be reduced, which is not desirable. .

Composition 1 comprising (B-1) and (B-2)
In 00 parts by weight, (A) is used in a composition ratio of 1 to 99 parts by weight. Preferably it is 1 to 90 parts by weight, more preferably 5 to 50 parts by weight. If it is less than 1 part by weight, the effect of improving the properties such as mechanical strength of the composition is small, and if it exceeds 99 parts by weight, the fluidity of the composition tends to decrease. It is preferable that the thermoplastic elastomer comprising the crosslinkable rubbery polymer (B-1) and the thermoplastic resin (B-2) in the present invention is dynamically crosslinked. , May be simply referred to as (C)). (C) contains (C-1) a crosslinking initiator as an essential component, and if necessary, (C-2) a polyfunctional monomer, and (C-3)
Contains a monofunctional monomer. The above (C) is used in an amount of 0.01 to 1 based on 100 parts by weight of the composition comprising (A) and (B).
It is used in an amount of 0 parts by weight, preferably 0.05 to 3 parts by weight. If the amount is less than 0.01 part by weight, crosslinking is insufficient, and 1
When the amount exceeds 0 parts by weight, the appearance and mechanical strength of the composition are reduced.

Here, (C-1) a crosslinking initiator (hereinafter sometimes simply referred to as (C-1)) is an organic peroxide,
Examples thereof include radical initiators such as organic azo compounds, and specific examples thereof include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane and 1,1
-Bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl-4,4-bis (t-butylperoxy) butane, n-butyl-4, 4
Peroxy ketals such as -bis (t-butylperoxy) valerate; di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, α, α'-bis (t-butylperoxy- m-isopropyl) benzene, α, α'-bis (t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-
Dialkyl peroxides such as 2,5-bis (t-butylperoxy) hexane and 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3;

Acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,
Diacyl peroxides such as 5,5-trimethylhexanoyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide and m-trioyl peroxide; t-butylperoxyacetate, t-butylperoxyisobuty Rate, t-butylperoxy-2-ethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate,
2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxymaleic acid, t-
Peroxyesters such as butylperoxyisopropyl carbonate and cumylperoxyoctate;
And t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,
5-dihydroperoxide and 1,1,3,3-
Hydroperoxides such as tetramethylbutyl peroxide can be exemplified.

Among these compounds, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl -2,5-bis (t-butylperoxy) hexane and 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 are preferred. The component (C-1) is preferably used in an amount of 1 to 80% by weight, more preferably 10 to 50% by weight in the component (C). If the amount is less than 1% by weight, crosslinking is insufficient, and if it exceeds 80% by weight, the mechanical strength decreases.

In the present invention, one of the crosslinking agents (C)
(C-2) a polyfunctional monomer (hereinafter simply referred to as (C-2)
Sometimes. ) Is a radical polymerizable functional group
Groups are preferred, especially vinyl groups. Functional group
Is 2 or more, but the (C-3) monofunctional monomer (hereinafter
Below, it may be simply referred to as (C-3). Combination with)
It is particularly effective when there are three or more functional groups.
You. Specific examples include divinylbenzene and triallylyl.
Socyanurate, triallyl cyanurate, diacetate
Diacrylamide, polyethylene glycol diacryl
Rate, polyethylene glycol dimethacrylate,
Limethylolpropane trimethacrylate, trimethylo
Propane triacrylate, ethylene glycol di
Methacrylate, triethylene glycol dimethacrylate
, Diethylene glycol dimethacrylate, diiso
Propenylbenzene, P-quinonedioxime, P, P^'
-Dibenzoylquinone dioxime, phenyl maleimi
Do, allyl methacrylate, N, N ^'-M-phenylene
Bismaleimide, diallyl phthalate, tetraallyl o
Xyethane, 1,2-polybutadiene and the like are preferably used.
Can be Particularly, triallyl isocyanurate is preferable.
These polyfunctional monomers may be used in combination of two or more.
Good.

The above (C-2) is preferably 1 to 80% by weight, more preferably 10 to 50% by weight in the component (C).
Is used. If the amount is less than 1% by weight, crosslinking is insufficient, and if it exceeds 80% by weight, the mechanical strength decreases. The (C-3) used in the present invention is a vinyl monomer added to control the rate of the crosslinking reaction, preferably a radical polymerizable vinyl monomer, and an aromatic vinyl monomer and acrylonitrile. , Unsaturated nitrile monomers such as methacrylonitrile, acrylic acid ester monomers, methacrylic acid ester monomers, acrylic acid monomers, methacrylic acid monomers, maleic anhydride monomers, N-substituted maleimides Monomers and the like can be mentioned. The above (C-3)
The component (C) is preferably used in an amount of 1 to 80% by weight, more preferably 10 to 50% by weight. If the amount is less than 1% by weight, crosslinking is insufficient, and if it exceeds 80% by weight, the mechanical strength decreases.

In the present invention, (B-1) and (B-2)
If necessary, (D) a softening agent can be added to the composition consisting of paraffinic or naphthenic process oils. These are compositions 10 comprising (B-1) and (B-2) for adjusting the hardness and flexibility of the composition.
5 to 500 parts by weight, preferably 10 parts by weight, per 0 parts by weight
Use up to 150 parts by weight. If the amount is less than 5 parts by weight, flexibility and workability are insufficient, and if it exceeds 500 parts by weight, oil bleeding becomes remarkable, which is not desirable. In the present invention, in order to impart a function to the thermoplastic polymer composition, an organic compound (E) (hereinafter sometimes simply referred to as (E)) may be supported on (A) as necessary. . Organic additives and polymerizable monomers. As a loading method, (A) is impregnated with (E) in advance and then loaded (B)
And (A) (B) (E)
May be simultaneously melt-mixed, and (E) may be supported on (A) during the mixing process.

The organic additives used as (E) include, for example, dispersants, plasticizers, heat stabilizers, light stabilizers, flame retardants, colorants, foaming agents, lubricants, fragrances, smoke suppressants, adhesives Imparting agents, preservatives, warming agents, impact resistance improvers, repellents, wetting agents, surfactants, emulsifiers, destabilizing agents, coagulants, defoamers, antifreeze agents, creaming agents, thickeners, It is an additive such as a heat sensitive agent and a foaming agent. Of these, dispersants, flame retardants, plasticizers, heat stabilizers, and light stabilizers are preferred. The amount of (E) in the composition of the present invention is preferably 0.01 to 10000 parts by weight, more preferably 0.1 to 1000 parts by weight, and still more preferably 0.1 to 100 parts by weight, per 100 parts by weight of (A). 1 to 10
0 parts by weight, most preferably 1 to 50 parts by weight. The dispersant mentioned as one of the above (E) is a component for improving the dispersibility of (A), and is, for example, an alkylalkoxysilane such as vinylmethoxysilane and an aryloxyalkoxysilane such as phenylmethoxysilane. Silane coupling agents or other organic silicon compounds. The flame retardant as (E) is an organic silicon-based, organic metal salt-based, organic halogen-based, organic phosphorus-based,
One or more flame retardants selected from organic nitrogen-based or organic fibrous flame retardants.

The organic silicon-based flame retardant is silicone,
Polyorgano represented by organic silicate or silica
It is a flame retardant containing a silicon element such as siloxane. Po
Liorganosiloxane is used for oil, resin, rubber
are categorized. Polyorganosiloxanes are monofunctional R
_ThreeSiO_1/2M unit represented by_TwoWith SiO
D unit represented, trifunctional R₁SiO_3/2T represented by
Unit, tetrafunctional SiO _TwoQ unit represented by the formula: alkoxy
Or R containing aryloxy_Five(R₆O) SiO
_2.0(X unit), (R₇O)_TwoSiO_3.0(Y unit)
A straight chain containing a branched structure made by combining structural units
Has a chain polyorganosiloxane or three-dimensional network structure
Silicone resin, and rubber is a high molecular weight type
Vulcanizates of rubber-like linear polydiorganosiloxanes
You. Other polyorganosiloxanes include Epoxy
Modified with amino, mercapto, methacrylic groups, etc.
Polyorganosiloxane or polycarbonate
(PC) -silicone copolymer, acrylic rubber-silico
Complex and the like.

The organic metal salt-based flame retardant as the flame retardant in the above (E) is, for example, an organic metal sulfonate such as potassium trichlorobenzenesulfonate, potassium perfluorobutanesulfonate, potassium diphenylsulfon-3-sulfonate. Metal sulfonate, metal sulfate, metal phosphate, metal phosphate, and metal borate are bonded to the aromatic ring of a salt, an aromatic sulfonimide metal salt, or an aromatic group-containing polymer such as a styrene-based polymer or polyphenylene ether. And metal salt-based flame retardants such as polystyrene sulfonic acid alkali metal salts. Such a metal salt-based flame retardant promotes a decarboxylation reaction at the time of combustion, particularly when polycarbonate is used as a polymer, to improve flame retardancy. Further, in the case of the alkali metal polystyrene sulfonate, the metal sulfonate itself becomes a cross-linking point during combustion and greatly contributes to the formation of a carbonized film.

The organic halogen-based flame retardant as the flame retardant in the above (E) includes a halogenated bisphenol, an aromatic halogen compound, a halogenated polycarbonate, a halogenated aromatic vinyl polymer, a halogenated cyanurate resin, Halogenated polyphenylene ether and the like,
Preferably, decabromodiphenyl oxide, tetrabromobisphenol A, tetrabromobisphenol A
Oligomer, brominated bisphenol-based phenoxy resin, brominated bisphenol-based polycarbonate, brominated polystyrene, brominated cross-linked polystyrene, brominated polyphenylene oxide, polydibromophenylene oxide, decabromodiphenyl oxide bisphenol condensate, halogen-containing phosphorus Acid esters and fluorine-based resins.

The organic phosphorus-based flame retardant as the flame retardant in the above (E) includes phosphine, phosphine oxide,
Biphosphine, phosphonium salts, phosphinates, phosphates, phosphites and the like. More specifically, triphenyl phosphate, methyl neopentyl phosphite, pentaerythritol diethyl diphosphite, methyl neopentyl phosphonate, phenyl neopentyl phosphate, pentaerythritol diphenyl diphosphate, dicyclopentyl hypophosphate , Dineopentyl hypophosphite, phenylpyrocatechol phosphite, ethyl pyrocatechol phosphate and dipyrocatechol hypopositive phosphate. Here, as the organic phosphorus compound, an aromatic phosphate ester monomer and an aromatic phosphate ester condensate are particularly preferred.

The organic nitrogen-based flame retardant as the flame retardant in the above (E) is typically a compound containing a triazine skeleton, and is used as a flame retardant auxiliary for a phosphorus-based flame retardant to further improve the flame retardancy. It is a component of. Specific examples thereof include melamine, melam, melem, melon (product of deammonification of three to three molecules of melem at a temperature of 600 ° C. or more), melamine cyanurate, melamine phosphate, succinoguanamine, adipoguanamine. And melamine resin, melamine resin and BT resin, and melamine cyanurate is particularly preferred from the viewpoint of low volatility. The organic fibrous flame retardant as the flame retardant in the above (E) is a flame retardant used for preventing dripping of fire,
It becomes fibrous at the time of addition or processing. Specific examples thereof include aramid fiber, polyacrylonitrile fiber, and fluororesin.

Examples of the plasticizers mentioned as one of the above (E) include phthalic acid esters such as dimethyl phthalate, diethyl phthalate and diisobutyl phthalate, and phthalic acid mixed ester such as butyl benzyl phthalate; Aliphatic dibasic esters such as diisodecyl succinate and dioctyl adipate; glycol esters such as diethylene glycol dibenzoate; aliphatic acid esters such as butyl oleate and methyl acetyl ricinoleate; epoxidized soybean oil; epoxidation An epoxy plasticizer such as linseed oil,
In addition, trioctyl trimellitate, ethyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate
G, tributyl acetyl citrate, chlorinated paraffin,
Polypropylene adipate, polyethylene sebacate,
Examples include triacetin, tributyrin, toluenesulfonamide, alkylbenzene, biphenyl, partially hydrogenated t-phenyl, camphor and the like.

Examples of the heat stabilizer (E) include metal soap, lead stabilizer, organotin stabilizer, composite stabilizer, epoxy compound and the like. The light stabilizer as (E) is a light stabilizer selected from an ultraviolet absorber, a hindered amine light stabilizer, an antioxidant, an active species trapping agent, a light-blocking agent, a metal deactivator, a quencher and the like. Agent. Examples of the foaming agent (E) include an azo foaming agent, an N-nitroso foaming agent, and a sulfonyl hydrazide. Examples of the lubricant as (E) include hydrocarbon lubricants such as liquid paraffin,
Fatty acid-based lubricants, fatty acid amide-based lubricants, alcohol-based lubricants, metal soaps and the like can be mentioned.

Further, the composition of the present invention can contain an inorganic filler and a plasticizer to such an extent that its characteristics are not impaired. Examples of the inorganic filler used here include calcium carbonate, magnesium carbonate, silica, carbon black, glass fiber, titanium oxide, clay, mica, talc, magnesium hydroxide, and aluminum hydroxide. As the plasticizer, for example, polyethylene glycol, dioctyl phthalate (DO)
And phthalic acid esters such as P). Also, other additives such as organic / inorganic pigments, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, flame retardants, silicone oils, antiblocking agents, foaming agents, antistatic agents, antibacterial agents, etc. Are also preferably used. In the production of the composition of the present invention, a general method such as a usual resin composition, a Banbury mixer, a kneader, a single-screw extruder, or a twin-screw extruder used for production of a rubber composition may be employed. It is possible,
A twin screw extruder is preferably used. The twin screw extruder
It is more suitable for dispersing (A) and (B) uniformly and finely and further adding other components to continuously produce the composition of the present invention.

The composition of the present invention may be prepared by previously preparing (A) dispersed in (B) the average particle size required for the present application in (B) and then melt-extruding using the same. A) While (A) and (B) are simultaneously melt-extruded, (A) may simultaneously be produced by reaching the average particle of the requirements of the present application, and the production method is not particularly limited. A particularly preferred melt extrusion method is a case where a twin-screw extruder having a length L in the die direction from the raw material addition portion and having an L / D of 5 to 100 (where D is a barrel diameter) is used. is there. The twin-screw extruder has a plurality of supply portions at a main feed portion and a side feed portion having different distances from the tip portion, and a plurality of supply portions are provided between the plurality of supply portions and the tip portion. A kneading portion is provided between the supply portion and a short distance from the distal end portion, and the length of the kneading portion is 3D to 3D, respectively.
It is preferably 10D.

One of the twin-screw extruders of the production apparatus used in the present invention may be a twin-screw co-rotating extruder or a twin-screw different-direction rotating extruder. For screw engagement, non-engagement type, partial engagement type,
There is a complete meshing type, and any type may be used. In order to obtain a uniform resin at a low temperature by applying a low shear force, a screw in a different direction / partial engagement type is preferably used. When slightly large kneading is required, a co-rotating / completely meshing screw is preferable. If even greater kneading is required, a co-rotating, fully meshing screw
Is preferred.

In the method for producing the composition of the present invention, it is more preferable to satisfy the following kneading degree. ^{M = (π 2/2)} (L / D) D 3 (N / Q) 10 × 10 6 ≦ M ≦ 1000 × 10 6 where, L: die direction of extrusion PIC material added section as a base point (mm), D: extruder barrel inner diameter (mm), Q: discharge amount (kg / h), N: screw rotation speed (rpm) kneading degree ^{M = (π 2/2)} (L / D) D 3 (N / Q) Is 1
It is preferable that 0 × 10 ⁶ ≦ M ≦ 1000 × 10 ⁶ . The composition thus obtained can be used to produce various molded articles by any molding method. Injection molding, extrusion molding, compression molding, blow molding, calender molding, foam molding and the like are preferably used. In the present invention, a function can be imparted to various materials such as flame retardancy, dispersibility, oil absorption and stability by molding or processing (A). The function imparting agent can impart a function such as a polymer material as a kind of master batch.

[0047]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In these examples and comparative examples, the test methods used for evaluating various physical properties are as follows. (1) Average Particle Diameter of Inorganic Compound The particle diameter of the inorganic compound was determined by dividing each particle of 500 rubber-like polymers in a transmission electron micrograph taken by an ultra-thin section method of the composition by the following method. It is obtained by calculating.
That is, the particle diameter of each particle is obtained by calculating the area S of each particle,
Using (4S / π) ^0.5 as the particle diameter of each particle, the average particle diameter was calculated by number average. (2) Flame retardancy VB (Vertical Bur) conforming to UL-94
The self-extinguishing property was evaluated by the ning method. (1
/ 8 inch thickness test specimen) ：: Self-extinguishing property in less than 20 seconds ○: Self-extinguishing property in 20 or more ×: Burnt

(3) Wear Resistance Evaluation was performed using a Gakushin type abrasion tester. The evaluation conditions are as follows. Temperature condition: 23 ° C atmosphere Stroke: 120 mm Frequency: 1 reciprocal / 2 seconds Load: 200 g Friction material: 100% cotton cloth Kanakin No. 3 (JIS L
0803) Trifolded and mounted Contact area: 1 cm 2 Evaluation was performed for the number of times of friction reciprocation until disappearance of the surface roughness of the molded product (4) Appearance The appearance of the injection molded article was evaluated according to the following criteria. ◎ Very good ○ Good △ Good, but some aggregates are observed. × Agglomerates overall, no gloss

(5) Oil resistance Weight W of a composition sheet having a thickness of 2 mm in advance₀Measure
After that, the composition sheet was placed in liquid paraffin at 80 ° C. for 2 hours.
After standing for 0 hours, the weight of the composition sheet (W ₁)
And calculate the weight change rate as follows. Where the number
The smaller the value, the better the oil resistance. Weight change rate = (W₁ー W₀) / W₀× 100 (%) (6) Analysis of conjugated diene rubber 1) Hydrogenation rate (%) It was measured by NMR according to the following procedure. First, before hydrogenation,
Dissolve butadiene rubber in heavy chloroform and use FT-N
Chemical shift 4.7 at MR (270 mega, manufactured by JEOL)
~ 5.2 ppm (referred to as signal C0) of 1,2-vinyl
And the chemical shift 5.2-
5.8 ppm (referred to as signal D0) vinyl proton
(= CH_Two) Was calculated by the following equation. (V) = [0.5C0 / ｛0.5C0 + 0.5 (D0−
0.5C0)｝] × 100

Next, the polybutadiene rubber after the partial hydrogenation was dissolved in deuterated chloroform, and similarly, by FT-NMR, the hydrogenated 1,1 with a chemical shift of 0.6 to 1.0 ppm (referred to as signal A1) was used. Methyl proton (—CH ₃ ) due to two bonds, chemical shift 4.7 to 5.2 ppm
1,2 not hydrogenated (referred to as signal C1)
-Proton (= CH ₂ ) by vinyl, chemical shift 5.
It was calculated from the integrated intensity of 2-5.8 ppm (referred to as signal D1) of the unhydrogenated vinyl proton (= CH-) by the following equation. First, p = 0.5C0 / (0.5C1 + A1 / 3) A11 = pA1, C11 = pC1, D11 = pD1, and the hydrogenation rate of the 1,2-vinyl bond (B) (B) = [(A11 / 3 ) / ｛A11 / 3 + C11 /
2｝] × 100 Hydrogenation rate of 1,4-double bond (C) (C) = [｛0.5 (D0-0.5C0) -0.5 (D
11-0.5C11)｝ / 0.5 (D0-0.5C
0)] × 100 Hydrogenation rate of whole butadiene part (A) (A) = (V) × (B) / 100 + [100− (V)]
× (C) × 100

2) Microstructure The symbols defined above are described below. 1,2-vinyl bond before hydrogenation = (V) × (B) / 100 (%) 1,4 bond before hydrogenation = {100− (V)} × (C) / 100 (%) After hydrogenation 1,2-vinyl bond = (V) × {100- (B)} / 100 (%) 1,4-bond after hydrogenation = {100- (V)} × {100- (B)} / 100 (%)

(7) Tensile breaking strength [MPa] The tensile breaking strength was evaluated at 23 ° C. according to JIS K6251. The following components were used for each component used in Examples and Comparative Examples. (A) Thermoplastic polymer 1) Copolymer of ethylene and octene-1 (TPE-
1) It was prepared by a method using a metallocene catalyst described in JP-A-3-1630088. The ethylene / octene-1 composition ratio of the copolymer is 72/28 (weight ratio).
(Referred to as TPE-1) 2) Copolymer of ethylene and octene-1 (TPE-
2) It was produced by a method using a usual Ziegler catalyst. The ethylene / octene-1 composition ratio of the copolymer was 72/2.
8 (weight ratio). (Referred to as TPE-2)

3) Ethylene / propylene / ethylidene norbornene (ENB) copolymer (TPE-3) Produced by a method using a metallocene catalyst described in JP-A-3-1630088. The composition ratio of ethylene / propylene / ENB in the copolymer is 72/24/4 (weight ratio). (Referred to as TPE-3) 4) Polypropylene (PP) Isotactic homopolypropylene manufactured by Japan Polyolefin Co., Ltd. [MFR (5 g / min) (230 according to ASTM D 1238)
° C, 2.16 kg load)] (referred to as PP) 5) Polystyrene (PS) manufactured by Asahi Kasei Corporation, referred to as PS

6) Rubber-modified polystyrene (HIPS) HISA manufactured by Asahi Kasei Corporation. 7) ABS resin (ABS) manufactured by Asahi Kasei Corporation, called ABS. 8) Polyphenylene ether (PPE) PPE manufactured by Asahi Kasei Corporation. 8) Aromatic polycarbonate (PC) PC manufactured by Sumitomo Dow Co., Ltd.

(C) Inorganic Compound Silica having a branched structure was produced by the method described in US Pat. No. 5,929,156. Specifically, 260
One liter of water and 200 liters of 24.7% sodium silicate were charged to the reactor, heated at 82 ° C., and 9.5 kg of anhydrous sodium sulfate was added to the reactor. Thereafter, sulfuric acid (7.4%) was fed at 33 ° C. at a rate of 4.5 liters / minute, and after the PH of the reactor contents reached 7.5, the sulfuric acid feed rate was increased to 1.81. liter/
And add 24.7% sodium silicate to 1.38
Feed was started at liter / min. The feed rate was adjusted so that the pH became 7.5 by simultaneous addition of the two. The sodium silicate addition was stopped after 30 minutes, the sulfuric acid feed was 1.81 l / min and the pH of the reactants was 5.1.
Continued until. The precipitated silica was filtered, washed with water, and dried. In Examples 1 to 32 and Comparative Examples 2 to 3, silica having different average particle diameters was produced by adjusting the discharge amount Q and the screw rotation speed N and controlling the shear rate. The melt-kneading conditions at that time were based on (reference melting conditions) in Example 1. As a commercially available silica satisfying the requirements of the present application, U.S. Pat. M. Huberp from Huber
There is ol 135. Commercially available granular silica was used for comparison. The silicas of Comparative Examples 4 and 5 were Nipsil (trade name) manufactured by Nippon Silica Industry Co., Ltd.

(D) Crosslinking agent 1) Crosslinking initiator (C-1) 2,5-dimethyl-2,5-bis (t-manufactured by NOF Corporation)
Butylperoxy) hexane (trade name Perhexa 25)
B) (referred to as POX-1) 2) Crosslinking initiator (C-1) 2,5-dimethyl-2,5-bis (t-manufactured by NOF Corporation)
(Butyl peroxy) hexin-3 (trade name perhexin 25B) (referred to as POX-2) 3) Polyfunctional monomer (C-2) divinylbenzene (referred to as DVB) manufactured by Wako Pure Chemical Industries, Ltd. 4) polyfunctional Monomer (C-2) Triallyl isocyanurate (TA) manufactured by Nippon Kasei Co., Ltd.
5) Multifunctional monomer (C-2) N, N ^, -m phenylenebismaleimide (PMI) manufactured by Ouchi Shinko Chemical Co., Ltd. 6) Monofunctional monomer (C-3) ) Methyl methacrylate (MMA) manufactured by Asahi Kasei Corporation

(E) Paraffin oil Diana Process Oil PW-9 manufactured by Idemitsu Kosan Co., Ltd.
0 (referred to as MO) (f) Organic compound to be supported on (A) 1) Triphenyl phosphate (TPP) manufactured by Daihachi Chemical Industry Co., Ltd., referred to as TPP. 2) Methyl phenyl silicone (MPS) manufactured by Shin-Etsu Chemical Co., Ltd., referred to as MPS. 3) Vinylalkoxysilane (VS) manufactured by Shin-Etsu Chemical Co., Ltd., is referred to as VS. 4) Dimethyl silicone (DMS) DMS manufactured by Shin-Etsu Chemical Co., Ltd.

(Examples 1 to 4), (Comparative Examples 1 to 5) Table 1 was obtained by using a twin-screw extruder (25 mmφ, L / D = 47) consisting of 11 blocks having an inlet at the center of the barrel.
Each component described was used as (B-1) TPE-1 / (B-2) PP / (A) silica / (C-1) POX-1 / (C-2) TAIC /
(D) A composition comprising MO = 70/30/5 / 0.5 / 1.0 / 40 (weight ratio) was melt-kneaded in the following manner on the basis of the following melting conditions.

(Reference melting conditions) 1) Melt extrusion temperature 250 ° C. constant 2) Discharge rate Q = 12 kg / h 3) Extruder barrel inner diameter D = 25 mm 4) L / L when extruder length is L (mm) D = 475 5) Screw rotation speed N = 280 rpm From the elastomer composition thus obtained, 200
A sheet having a thickness of 2 mm was prepared by injection molding at ℃, and each characteristic was evaluated. The results are shown in Table 1. According to Table 1, when the (A) inorganic compound (silica) that satisfies the requirements of the present invention is used, tensile strength at break, appearance, flame retardancy,
It can be seen that the abrasion resistance and the oil resistance are improved.

(Examples 5 to 17) In Example 2, (B
Example except that the weight ratio of (-1) / (B-2) was changed from 70/30 to 50/50, and (B-1) was changed to hydrogenated rubber, TPE-2, TPE-3 The experiment similar to 2 was repeated.
Note that in Example 17, PP was set to PS as (B-2).
Changed to The results are shown in Table 2. According to Table 2, as (A), an ethylene / α-olefin copolymer composed of ethylene and an α-olefin having 3 to 20 carbon atoms produced using a metallocene catalyst and / or a double bond in the main chain and the side chain. 50% of the total double bonds of the unsaturated rubber comprising a homopolymer and / or a random copolymer having
It can be seen that the use of hydrogenated hydrogenated rubber improves the tensile rupture strength, appearance, flame retardancy, abrasion resistance, and oil resistance.

(Embodiments 18 to 23)
(C-1) and (C-2) were converted to (C-1) (C-
2) Change to (C-3) and (B-1) / (B-2)
The experiment similar to that of Example 2 was repeated, except that the weight ratio of was changed from 70/30 to 50/50. Table 3 shows the results. When (C-2) and (C-3) are used together,
Both were used in equal amounts. Table 3 shows that when TAIC is used as (C-2), the oil resistance is particularly excellent. (Examples 24 to 32), (Comparative Example 6) MPS or TPP was supported on silica (A) shown in Table 4 and mechanically mixed at a weight ratio shown in Table 4 to obtain a Labo Plastomill manufactured by Toyo Seiki Seisaku-sho, Ltd. Using, the melting temperature of 250 ℃,
Melting was performed at a rotation speed of 50 rpm for 5 minutes. From the resin composition thus obtained, a test piece having a thickness of 1/8 inch was prepared by a compression molding method, and the flame retardancy was evaluated. Table 4 shows the results.

(Examples 33 to 38) and (Comparative Example 7) In Example 2, the weight ratio of (B-1) / (B-2) was changed to 70/3.
0 to 60/40, and U.S. Pat. M. Huber
The same experiment as in Example 2 was repeated, except that Huberpol 135 manufactured by the company was used, and the organic compounds shown in Table 5 were further supported.
However, the average particle diameter of (A) silica was controlled by changing the kneading degree M by changing Q and N specified below. The results are shown in Table 5 (provided that the number of added parts is based on 100 parts by weight in total of (B-1) / (B-2)). ^{M = (π 2/2)} (L / D) D 3 (N / Q) 10 × 10 6 ≦ M ≦ 1000 × 10 6 where, L: die direction of extrusion PIC material added section as a base point (mm), D: extruder barrel inner diameter (mm), Q: discharge rate (kg / h), N: screw rotation speed (rpm)

[0063]

[Table 1]

[0064]

[Table 2]

[0065]

[Table 3]

[0066]

[Table 4]

[0067]

[Table 5]

[0068]

The composition of the present invention has mechanical strength, appearance,
Excellent flame retardancy, abrasion resistance and oil resistance. The composition of the present invention can be used for automotive parts, automotive interior materials, airbag covers, mechanical parts, electrical parts, cables, hoses, belts, toys, miscellaneous goods, daily necessities, building materials, sheets, films, and other applications. It can be used widely and plays a large role in the industrial world.

[Brief description of the drawings]

FIG. 1 is a diagram showing typical shapes of branched silica used in Examples and granular silica used in Comparative Examples.

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Claims (12)

[Claims] 1. A polymer composition comprising (A) an inorganic compound having a branched structure and (B) a thermoplastic polymer, wherein the average particle size of (A) is from 1 to 100,000 nm. Thermoplastic polymer composition. 2. The thermoplastic polymer composition according to claim 1, wherein (A) is silicon oxide and / or aluminum oxide. 3. The thermoplastic polymer according to claim 1, wherein (A) is amorphous silicon oxide produced by a wet method and / or amorphous fumed silicon oxide produced by a dry method. Coalescing composition. 4. The thermoplastic polymer composition according to claim 1, wherein (B) is a thermoplastic resin. 5. The method according to claim 1, wherein (B) is selected from the group consisting of polyaromatic vinyl, polycarbonate, polyphenylene ether, polyolefin, polyvinyl chloride, polyamide, polyester, polyphenylene sulfide, and polymethacrylate thermoplastic resins. The thermoplastic polymer composition according to claim 4, wherein the thermoplastic polymer composition is at least one kind of thermoplastic resin. 6. The method according to claim 1, wherein (B) comprises (B-1) a crosslinkable rubber-like polymer and (B-2) a thermoplastic resin, and is crosslinked. The thermoplastic polymer composition according to any one of the preceding claims. 7. (B-1) is ethylene and having 3 to 20 carbon atoms.
50% of the total double bonds of an unsaturated rubber composed of an ethylene / α-olefin copolymer containing α-olefin or a homopolymer and / or a random copolymer having a double bond in a main chain and a side chain The thermoplastic polymer according to claim 6, wherein the above is at least one kind of a crosslinkable rubbery polymer selected from hydrogenated hydrogenated rubbers, and (B-2) is an olefin resin and / or a styrene resin. Composition. 8. The thermoplastic polymer composition according to claim 6, wherein (C) the thermoplastic polymer composition is crosslinked with a crosslinking agent, and further (D) a softening agent is added. 9. The thermoplastic polymer composition according to claim 1, wherein an organic compound is supported on (A). 10. A function-imparting agent obtained by processing (A). 11. A master batch obtained by processing (A). 12. The function-imparting agent according to claim 10, which is obtained by polymerizing a polymerizable monomer in the presence of (A).