JP2009067969A - Thermoplastic polymer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic polymer composition having remarkable flame retardance and mechanical strength. <P>SOLUTION: The dynamically crosslinked thermoplastic polymer composition comprises an aromatic vinyl thermoplastic polymer rubber (A), a thermoplastic resin (B), and a flame-retardant (C). The thermoplastic polymer composition preferably comprises an aromatic vinyl random copolymer rubber as (A). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

   The present invention relates to a thermoplastic polymer composition. More particularly, it relates to a thermoplastic polymer composition having excellent flame retardancy and mechanical strength.

Thermoplastic polymers are not only excellent in moldability, but also in impact resistance and flexibility, so they are used in a wide range of material fields including automotive materials and electrical / electronic materials. Its use is limited because of its flammability.
As a method for making a thermoplastic polymer flame retardant, it is known to add a halogen-based, phosphorus-based, or inorganic flame retardant to the thermoplastic polymer, thereby achieving some degree of flame retardant. . However, in recent years, safety requirements for fires have been highlighted, and further development of advanced flame retardant technologies, as well as development of flame retardant technologies that do not degrade mechanical properties and are free from environmental problems, are strongly desired. Yes.

As a technique for making a thermoplastic polymer flame retardant, a coating material (see Patent Document 1) in which ammonium polyphosphate and a metal hydrate are blended with polypropylene and a styrene thermoplastic elastomer is disclosed. Although the coating material is excellent in moldability and flexibility, it is not cross-linked and therefore inferior in wear resistance or durability.
On the other hand, as a crosslinking material, a specific halogen-based flame retardant and antimony trioxide are blended with a thermoplastic resin, an electron beam crosslinked tube or a heat-shrinkable tube (see Patent Document 2), a mechanical material after crosslinking with respect to the initial stage. A flame retardant electric wire having a specific value as a characteristic (see Patent Document 3) is disclosed. Although the two cross-linked materials are excellent in durability, they are inferior in moldability due to lack of thermoplasticity.
Thus, development of the flame-retardant polymer composition which was excellent in the flame retardance and satisfy | filled mechanical strength is calculated | required.
JP-A-9-31267 Japanese Patent No. 2765361 Japanese Patent Laid-Open No. 10-168248

  In view of such a current situation, the present invention aims to provide a thermoplastic polymer composition which does not have the above-described problems, that is, has excellent flame retardancy and mechanical strength.

As a result of intensive investigation of a thermoplastic polymer rubber composition excellent in flame retardancy and mechanical strength, the present inventors have surprisingly achieved a dramatic increase in flame retardancy and mechanical strength by combining specific polymers. As a result, the present invention has been completed.
That is, the present invention provides the following composition.
(1) A dynamically crosslinked thermoplastic polymer composition comprising an aromatic vinyl-based thermoplastic polymer rubber (A), a thermoplastic resin (B), and a flame retardant (C).
(2) The thermoplastic polymer composition according to (1), wherein (A) is an aromatic vinyl-based thermoplastic random copolymer rubber (A-1).
(3) (A) is a thermoplastic copolymer rubber mainly composed of random bonds composed of 10 to 49% by weight of conjugated diene monomer units and 51 to 90% by weight of aromatic vinyl monomer units. The thermoplastic polymer composition according to (1) or (2), wherein the hydrogenation rate of the olefinic double bond is 50% or more.
(4) The thermoplastic polymer composition according to any one of (1) to (3), wherein (B) is an aromatic vinyl resin and / or a polyphenylene ether resin.
(5) The thermoplastic polymer composition according to any one of (1) to (4), wherein (C) is a non-halogen flame retardant.

(6) The thermoplastic polymer composition according to (5), wherein (C) is a phosphorus-based flame retardant.
(7) The thermoplastic polymer composition according to any one of (1) to (6), further comprising an ethylene / α-olefin copolymer (D).
(8) The thermoplastic polymer according to (7), wherein (D) is an ethylene / α-olefin copolymer containing ethylene and an α-olefin having 3 to 20 carbon atoms, produced using a metallocene catalyst. Composition.
(9) The thermoplastic polymer composition according to any one of (1) to (8), which is crosslinked with a crosslinking agent (E).
(10) A thermoplastic polymer composition comprising an aromatic vinyl-based thermoplastic polymer rubber (A) and a thermoplastic resin (B), wherein (A) is a conjugated diene monomer unit and an aromatic vinyl A copolymer rubber comprising monomer units and having a hydrogenation rate of olefinic double bonds of 50% or more, and after hydrogenation, the aromatic vinyl monomer unit block and ethylene / α-olefin unit Aromatic vinyl-based thermoplastic random copolymer rubber (A-2) formed from random blocks of monomer units and random blocks of ethylene / α-olefin / aromatic vinyl monomer units, which are thermoplastic. The thermoplastic polymer composition, wherein the resin (B) is an olefin resin or a thermoplastic resin containing an olefin resin.

  The thermoplastic polymer composition of the present invention is excellent in flame retardancy and mechanical strength.

The present invention will be specifically described below.
The composition of the present invention is a thermoplastic polymer composition comprising an aromatic vinyl-based thermoplastic polymer rubber (A), a thermoplastic resin (B), and a flame retardant (C). Here, it is important that (A) be crosslinked while maintaining thermoplasticity. Since the thermal decomposition is suppressed by crosslinking the above components, the flame retardancy is excellent. And when (C) was added with respect to (A) and (B), it discovered that a higher flame retardance was expressed, and completed this invention.
Hereinafter, each component of the present invention will be described in detail.

(A) Component The aromatic vinyl-based thermoplastic polymer rubber of the component (A) in the present invention is a thermoplastic rubber-like polymer containing an aromatic vinyl monomer unit, such as a conjugated diene monomer. A copolymer rubber comprising an aromatic vinyl monomer. Further, the stereoregularity is not limited by random or block, but aromatic vinyl random copolymer rubber (A-1) is preferable from the viewpoint of compatibility with the component (B).
The copolymer rubber of the component (A) has an olefinic double bond hydrogenation rate of 50% or more, and a conjugated diene monomer unit of 10 to 49% by weight, preferably 20 to 49% by weight. %, More preferably 25 to 45% by weight, and a random bond consisting mainly of aromatic vinyl monomer units of 51 to 90% by weight, preferably 51 to 80% by weight, more preferably 55 to 75% by weight. Preferred is a copolymer.
In the component (A), if necessary, for example, a monomer copolymerizable with a conjugated diene such as an olefin, methacrylic ester, acrylic ester, unsaturated nitrile, or vinyl chloride monomer. (Hereinafter referred to as a copolymerizable monomer) can be copolymerized.

Examples of the conjugated diene monomer include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3- Hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene and the like can be mentioned, and 1,3-butadiene, isoprene and 1,3-pentadiene are preferable, Most preferred are 3-butadiene and isoprene.
Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, t-butylstyrene, divinylbenzene, N, N-dimethyl-p-aminoethylstyrene, and vinylpyridine. Styrene and α-methylstyrene are preferable. The aromatic monomers can be used alone or in combination of two or more.

  In the preferred component (A) of the present invention, the vinyl bond in the conjugated diene monomer portion before hydrogenation may be present uniformly in the molecule, or may be increased or decreased or decreased along the molecular chain. Moreover, you may include the some block from which vinyl bond content differs. When the aromatic vinyl monomer and / or copolymerizable monomer is included, the conjugated diene monomer and the aromatic vinyl monomer and / or copolymerizable monomer are randomly bonded. However, it may contain a block-like aromatic vinyl monomer and / or a block-like copolymerizable monomer. The content of the block-like aromatic vinyl polymer is preferably 20% by weight or less, more preferably 10% by weight or less, based on the total aromatic vinyl monomer.

The total olefinic double bonds in the component (A) are 50% or more, preferably 90% or more, more preferably 95% or more, and the remaining double bonds of the main chain are 5% or less, side The residual double bond of the chain is 5% or less. Here, the hydrogenation rate is measured by a known NMR method, and the details are described in WO01 / 48079. Specific examples of such copolymer rubber include rubbery polymers obtained by partially or completely hydrogenating styrene-diene rubbers such as poly (styrene-butadiene) and poly (styrene-isoprene). it can.
Such a component (A) can be obtained by partially hydrogenating the above styrene / diene rubber by a known hydrogenation method. For example, F.A. l. Ramp, etal, j. Amer. Chem. Soc. 83, 4672 (1961), hydrogenation using a triisobutylborane catalyst, Hung Yu Chen, j. Polym. Sci. Polym. Letter Ed. , 15, 271 (1977), or hydrogenation using a toluenesulfonyl hydrazide or an organic cobalt-organic aluminum catalyst or an organic nickel-organic aluminum catalyst described in Japanese Patent Publication No. 42-8704 And the like.

Here, particularly preferred hydrogenation methods are disclosed in JP-A-59-133203 and JP-A-60-220147 using inert catalysts that can be hydrogenated under mild conditions of low temperature and low pressure, or inert organic compounds. Contacting with hydrogen in a solvent in the presence of a catalyst comprising a bis (cyclopentadienyl) titanium compound and a hydrocarbon compound having a sodium atom, a potassium atom, a rubidium atom or a cesium atom This is the method shown in the gazette.
Moreover, it is preferable that the 5 weight% styrene solution viscosity (5% SV) in 25 degreeC of (A) component exists in the range of 20-300 centipoise (cps). A particularly preferred range is 25 to 150 cps.

The component (A) used in the present invention may be a mixture of a plurality of types. In such a case, the workability can be further improved.
In the present invention, from the viewpoint of improving the crosslinking level of the component (A), the proportion of the polymer having a polystyrene equivalent molecular weight of 150,000 or less in the component (A) is preferably 30% or less. As a method of controlling the ratio, a method of increasing the total molecular weight so that a portion having a molecular weight of 150,000 or less is 30% or less, a method of removing a portion having a molecular weight of 150,000 or less by an operation such as extraction, or a polymerization catalyst And a polymerization method in which a molecular weight of 150,000 or less is not selectively generated.

  In the present invention, when the component (B) is an olefin resin or a thermoplastic resin (B-1) containing an olefin resin, in particular, the component (A) includes a conjugated diene monomer unit and an aromatic vinyl. A copolymer rubber comprising a monomer unit and having a hydrogenation rate of olefinic double bonds of 50% or more, and an aromatic vinyl monomer unit block (A-2-1) after hydrogenation; Thermoplastic weight formed from a random block of ethylene / α-olefin monomer units (A-2-2) and a random block of ethylene / α-olefin / aromatic vinyl monomer units (A-2-3) The combined rubber (A-2) is preferable. Here, containing (A-2-2) mainly comprising (A-2-3) is compatible with an olefin resin or a thermoplastic resin (B-1) containing an olefin resin. It is important for that. Specific examples of such (A-2) include copolymer rubber in which the conjugated diene monomer is 1,3-butadiene and the aromatic vinyl monomer is styrene. By hydrogenation of the copolymer rubber, a polystyrene block is formed from the aromatic vinyl monomer unit block (A-2-1), and a random block (A-2-R) of ethylene / α-olefin monomer unit is formed. From 2), an ethylene / butylene random copolymer block is formed, and from an ethylene / α-olefin / aromatic vinyl monomer unit random block (A-2-3), an ethylene / butylene / styrene random copolymer block is formed. A coalesced block is formed.

  The vinyl bond in the conjugated diene monomer portion before hydrogenation may be present uniformly in the molecule, or may increase or decrease or decrease along the molecular chain, and the vinyl bond content may be different. A plurality of blocks may be included. When the aromatic vinyl monomer and / or copolymerizable monomer is included, the conjugated diene monomer and the aromatic vinyl monomer and / or copolymerizable monomer are randomly bonded. However, it may contain a block-like aromatic vinyl monomer and / or a block-like copolymerizable monomer. The content of the block-like aromatic vinyl polymer is preferably 20% by weight or less, more preferably 10% by weight or less, based on the total aromatic vinyl monomer.

In addition, to the (A-1) and (A-2), the hydrogenation method described in (A), the copolymerizable monomer, the solution viscosity of styrene, the molecular weight, and the like are applied.
The component (A) in the present invention is preferably an aromatic vinyl random copolymer rubber (A-1), but if necessary, contains an aromatic vinyl block copolymer rubber (A-3). May be. One representative example of such a copolymer rubber is a copolymer having an aromatic vinyl block and a conjugated diene block or a hydrogenated product thereof, specifically a hydrogenated styrene-butadiene block copolymer. It is.
Such a block copolymer (A-3) is a block copolymer comprising an aromatic vinyl unit and a conjugated diene unit, or the conjugated diene unit part is partially hydrogenated or unsaturated as necessary. It is a block copolymer modified with a carboxylic acid group or its anhydride or epoxy group.

  When the polymer block composed of aromatic vinyl units is represented by S and the polymer block composed of conjugated dienes and / or partially hydrogenated units thereof is represented by B, the above block structure is SB, S ( BS) n, where n is an integer from 1 to 3, S (BSB) n (where n is an integer from 1 to 2), (SB) n X (where n Is an integer of 3 to 6. X is a coupling agent residue of silicon tetrachloride, tin tetrachloride, polyepoxy compound, etc.), and a star-shaped (star) block copolymer having a B moiety as a bond center It is preferable that Of these, SB type 2, SBS type 3 and SBSB type 4 linear block copolymers are preferred.

(B) Component In the present invention, the thermoplastic resin (B) is not particularly limited as long as it is compatible or uniformly dispersible with (A). For example, aromatic vinyl, polyphenylene ether, polyolefin, polyvinyl chloride, polyamide, polyester, polyphenylene sulfide, polycarbonate, polyoxyalkylene, polymethacrylate, etc., alone or in combination Can be used. In particular, an aromatic vinyl resin, a polyphenylene ether resin, an olefin resin, or the like is preferable as the thermoplastic resin.
The aromatic vinyl resin is mainly composed of an aromatic vinyl monomer such as a homopolymer of an aromatic vinyl monomer or a polymer comprising an unsaturated nitrile monomer unit and an aromatic vinyl monomer unit. It is a polymer, and it is not limited whether it is a rubber-modified product or a rubber non-modified product. Specifically, aromatic vinyl monomers such as styrene, α-methylstyrene, paramethylstyrene, and halogenated styrene are essential components, and unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile, carbon A copolymer containing monomers such as acrylic acid ester or methacrylic acid ester having 1 to 8 alkyl groups, or acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimide and the like is preferable. Further, if necessary, it can be rubber-modified, and a rubber-modified polymer in which the rubber-like polymer is dispersed in the form of particles in the polymer matrix is preferred.

Examples of such rubber-modified polymers include HIPS resin (rubber-modified polystyrene), ABS resin (acrylonitrile-butadiene-styrene copolymer), AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), AES resin ( Acrylonitrile-ethylene propylene rubber-styrene copolymer) and the like.
Preferred polyphenylene ether resins (referred to as PPE) as (B) in the present invention are, for example, poly (2,6-dimethyl-1,4-phenylene ether), 2,6-dimethylphenol and 2,3,6- A copolymer with trimethylphenol or the like is preferable, and poly (2,6-dimethyl-1,4-phenylene ether) is particularly preferable. Further, the production method of PPE is not particularly limited. For example, a complex of cuprous salt and amine according to the method described in US Pat. No. 3,306,874 is used as a catalyst, for example, 2,6 xylenol is used. In addition, it can be easily produced by oxidative polymerization. In addition, US Pat. No. 3,306,075, US Pat. No. 3,257,357, US Pat. No. 3,257,358, and JP-B-52 It can be easily produced by the methods described in JP-A-17880 and JP-A-50-51197. The reduced viscosity ηsp / C (0.5 g / dl, chloroform solution, measured at 30 ° C.) of the PPE used in the present invention is preferably in the range of 0.20 to 0.70 dl / g. More preferably, it is in the range of 0.60 dl / g.

The olefin resin as the preferred (B) in the present invention is, for example, a copolymer resin containing ethylene or / and α-olefin, which is 2 to 20 carbon atoms, such as ethylene or propylene resin. In particular, a propylene resin is more preferable.
Specific examples of the propylene-based resin most preferably used in the present invention include homoisotactic polypropylene, propylene, and other α-olefins such as ethylene, butene-1, pentene-1, and hexene-1. And isotactic copolymer resins (including blocks and random).
Random copolymer resin with α-olefin mainly composed of propylene in (B) can be produced by high pressure method, slurry method, gas phase method, bulk method, solution method, etc. The polymerization catalyst is preferably a Ziegler-Natta catalyst, a single site, or a metallocene catalyst. In particular, when a narrow composition distribution and molecular weight distribution are required, a random copolymerization method using a metallocene catalyst is preferable.

Moreover, the thing of the range of 0.1-100 g / 10min (230 degreeC, 2.16kg load (0.212Pa)) is preferably used for the melt index of the olefin resin used suitably by this invention. From the viewpoint of heat resistance and mechanical strength of the thermoplastic elastomer composition, it is preferably 100 g / 10 min or less, and from the viewpoint of fluidity and moldability, 0.1 g / 10 min or more is preferable.
Regarding the amount ratio in 100 parts by weight of the polymer component consisting of (A) and (B) in the present invention, (A) is preferably 1 to 99 parts by weight, more preferably 20 to 80 parts by weight, most preferably, 30 to 70 parts by weight.

Component (C) The flame retardant used as (C) in the present invention is one or more flame retardants selected from halogen-based, phosphorus-based, nitrogen-based, silicon-based, inorganic-based, char-forming agents, anti-drip agents and the like. is there. Non-halogen type is preferable, and among them, a phosphorus-based flame retardant is most preferable.
Examples of the halogen flame retardant as (C) include halogenated bisphenol, aromatic halogen compounds, halogenated polycarbonates, halogenated aromatic vinyl polymers, halogenated cyanurate resins, halogenated polyphenylene ethers, and the like. Preferably, decabromodiphenyl oxide, tetrabromobisphenol A, oligomer of tetrabromobisphenol A, brominated bisphenol phenoxy resin, brominated bisphenol polycarbonate, brominated polystyrene, brominated crosslinked polystyrene, brominated polyphenylene oxide, Examples thereof include polydibromophenylene oxide, decabromodiphenyl oxide bisphenol condensate, halogen-containing phosphate ester, and fluorine-based resin.
Among them, as the anti-drip agent, a fluorine-based resin that is a resin containing a fluorine atom in the resin is effective, and specific examples thereof include polymonofluoroethylene, polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene, Examples thereof include a tetrafluoroethylene / hexafluoropropylene copolymer. Further, if necessary, the above fluorine-containing monomer and a copolymerizable monomer may be used in combination.

Examples of the phosphorus-based flame retardant as the (C) include organic phosphorus compounds, red phosphorus, and inorganic phosphates.
Examples of the organic phosphorus compound include phosphine, phosphine oxide, biphosphine, phosphonium salt, phosphinate, phosphate ester, phosphite ester and the like. More specifically, triphenyl phosphate, methyl neobentyl phosphite, gentaerythritol diethyl diphosphite, methyl neopentyl phosphate, phenyl neopentyl phosphate, pentaerythritol diphenyl diphosphate, dicyclopentyl high positive phosphate Dineopentyl hypophosphite, phenyl pyrocatechol phosphite, ethyl pyrocatechol phosphate, dipyrocatechol high positive phosphate.
Here, especially as an organic phosphorus compound, an aromatic phosphate ester monomer (chemical formula (1)) and an aromatic phosphate ester condensate (chemical formula (2)) are preferable.

(However, Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ , Ar ₇ , Ar ₈ are each independently a phenyl group that is unsubstituted or substituted with at least one hydrocarbon group having 1 to 10 carbon atoms. Ar ₆ is a divalent aromatic group having 6 to 20 carbon atoms, and m is an integer of 1 or more.
In the above (C), one of the phosphorus-based flame retardant red phosphorus is a metal water whose surface is previously selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide and titanium hydroxide in addition to general red phosphorus. Coated with oxide film, coated with metal hydroxide selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide, titanium hydroxide and thermosetting resin, hydroxylated For example, a metal hydroxide film selected from aluminum, magnesium hydroxide, zinc hydroxide, and titanium hydroxide is double coated with a thermosetting resin film.

In (C), one inorganic phosphate of the phosphorus-based flame retardant is typically ammonium polyphosphate.
The nitrogen-based flame retardant as (C) in the present invention is one or more flame retardants selected from a triazine skeleton-containing compound, an aramid fiber, a polyacrylonitrile fiber, and the like.
The triazine skeleton-containing compound is a component for further improving flame retardancy as a flame retardant aid for phosphorus-based flame retardants. Specific examples include melamine, melam, melem, melon (product of deammonation of 3 to 3 melem molecules above 600 ° C), melamine cyanurate, melamine phosphate, succinoguanamine, adipoguanamine , Methylglutalogamine, melamine resin, and BT resin, melamine cyanurate is particularly preferable from the viewpoint of low volatility.

The aramid fiber as a nitrogen-based flame retardant preferably has an average diameter of 1 to 500 μm and an average fiber length of 0.1 to 10 mm. Isophthalamide or polyparaphenylene terephthalamide is dissolved in an amide polar solvent or sulfuric acid. However, it can be produced by solution spinning by a wet or dry method.
The polyacrylonitrile fiber as the nitrogen-based flame retardant preferably has an average diameter of 1 to 500 μm and an average fiber length of 0.1 to 10 mm. The polymer is dissolved in a solvent such as dimethylformamide and air at 400 ° C. It can be produced by dry spinning in a stream or by a wet spinning method in which a polymer is dissolved in a solvent such as nitric acid and wet spinning in water.

The silicon-based flame retardant as the (C) in the present invention is one or more flame retardants selected from silicone resin, silicone oil, polyorganosilicate, and silica.
The silicone resin is a silicone resin having a three-dimensional network structure formed by combining structural units of SiO ₂ , RSiO _3/2 , R ₂ SiO, and R ₃ SiO _1/2 . Here, R represents an alkyl group such as a methyl group, an ethyl group or a propyl group, an aromatic group such as a phenyl group or a benzyl group, or a substituent containing a vinyl group in the above substituent. Here, a silicone resin containing a vinyl group is particularly preferable. Such a silicone resin can be obtained by cohydrolyzing and polymerizing an organohalosilane corresponding to the above structural unit.
Silicone oil or polyorganosilicate as a silicon-based flame retardant is represented by, for example, chemical formula (3).

(However, p and q are 0 or 1, n is an integer greater than or equal to 1. R1-R4 is a C1-C20 hydrocarbon, especially a methyl group, a phenyl group, an alkyl group substituted phenyl group, It preferably has a substituent selected from alkenyl groups, and R1 to R4 may be the same or different.
The viscosity of the silicone oil or polyorganosilicate is preferably 600 to 1000000 centistokes (25 ° C.), more preferably 90000 to 150,000 centistokes (25 ° C.).

Silica as a silicon-based flame retardant is amorphous silicon dioxide. In particular, silica-coated silica treated with a hydrocarbon-based silane coupling agent on the silica surface is preferable, and further contains a vinyl group. Hydrocarbon compound-coated silica is preferred.
The silane coupling agent includes vinyl group-containing silanes such as p-styryltrimethoxysilane, vinyltrichlorosilane, vinyltris (βmethoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. , Β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and other epoxy silanes, and N-β (aminoethyl) γ-amino Aminosilanes such as propyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane. Here, a silane coupling agent having a unit whose structure is similar to that of the thermoplastic resin is particularly preferable. For example, p-styryltrimethoxysilane is suitable for a styrene resin.

The treatment of the silane coupling agent on the silica surface is roughly divided into a wet method and a dry method. The wet method is a method in which silica is treated in a silane coupling agent solution and then dried. In the dry method, silica is charged into a device capable of high-speed stirring such as a Henschel mixer and stirred. In this method, the silane coupling agent solution is slowly added dropwise, followed by heat treatment.
The inorganic flame retardant as (C) includes aluminum oxide, magnesium hydroxide, hydrotalcite, calcium hydroxide, barium hydroxide, basic magnesium carbonate, zirconium hydroxide, tin oxide hydrate, etc. Inorganic metal compound hydrate, zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, aluminum oxide, iron oxide, titanium oxide, manganese oxide, magnesium oxide, zirconium oxide, Zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, tin oxide, antimony oxide, nickel oxide, copper oxide, tungsten oxide, etc. or a complex (alloy) thereof, aluminum, iron, titanium, manganese, Zinc, molybdenum, cobalt, bismuth, chromium Nickel, copper, tungsten, tin, elemental antimony or a complex thereof. These may be used alone or in combination of two or more. Among them, those selected from the group consisting of hydrates of inorganic metal compounds, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, and hydrotalcite have good flame retardancy and are economically advantageous. is there.

The char-forming agent as (C) is not limited as long as it is a compound that forms a carbonized film at the time of combustion. For example, a phenol resin is representative, and a novolac resin, a resole resin, or a cross-linked phenol resin, particularly a novolak resin. Is preferred. The resin is a thermoplastic resin obtained by condensing phenols and aldehydes in the presence of an acid catalyst such as sulfuric acid or hydrochloric acid.
The addition amount of (C) in the present invention is 1 to 500 parts by weight, preferably 1 to 300 parts by weight, more preferably, relative to 100 parts by weight of the resin component consisting of (A) and (B). It is 3-200 weight part, Most preferably, it is 5-100 weight part.
In the present invention, if necessary, a kind selected from a triazine skeleton-containing compound, a metal-containing compound, a silicone resin, a silicone oil, a polyorganosilicate, silica, an aramid fiber, a polyacrylonitrile fiber, a fluorine resin, and a phenol resin. The above flame retardant adjuvant can be mix | blended.
The amount of the flame retardant aid is preferably 0.001 to 500 parts by weight, more preferably 1 to 200 parts by weight, most preferably, with respect to 100 parts by weight of the polymer component composed of (A) and (B). 5 to 100 parts by weight.

Component (D) In the present invention, when it is necessary to further improve the crosslinking level, an ethylene / α-olefin copolymer (D) can be further added. (D) can be added before or after dynamic crosslinking, but is preferably added before dynamic crosslinking.
The ethylene / α-olefin copolymer (D) is more preferably a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. Examples of the α-olefin include propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1, heptene-1, octene-1, nonene-1, decene-1, undecene-1, and dodecene-1. Etc. Among them, hexene-1, 4-methylpentene-1, and octene-1 are preferable, and an α-olefin having 3 to 12 carbon atoms is particularly preferable, and propylene, butene-1, and octene-1 are most preferable.
Further, (D) can contain a monomer having an unsaturated bond, if necessary, for example, conjugated diolefins such as butadiene and isoprene, non-conjugated diolefins such as 1,4-hexadiene, Examples thereof include cyclic diene compounds such as cyclopentadiene and norbornene derivatives, and acetylenes. In particular, ethylidene norbornene (ENB) and dicyclopentadiene (DCP) are most preferable.

Further, (D) preferably has a glass transition temperature (Tg) of −10 ° C. or lower.
And the Mooney viscosity (ML) (ISO 289-1985 (E) conformity) measured at 100 degreeC of (D) has preferable 20-150, More preferably, it is 50-120.
(D) in the present invention is preferably produced using a known metallocene catalyst.
In general, a metallocene catalyst comprises 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 a polymer obtained in comparison with a Ziegler catalyst. The molecular weight distribution is narrow and the distribution of the α-olefin having 3 to 20 carbon atoms, which is a comonomer in the copolymer, is uniform.

(D) used in the present invention preferably has an α-olefin copolymerization ratio of 1 to 60% by weight, more preferably 10 to 50% by weight, and most preferably 20 to 45% by weight. The copolymerization ratio of α-olefin is preferably 60% by weight or less from the viewpoints of the hardness and tensile strength of the composition, and is preferably 1% by weight or more from the viewpoints of flexibility and mechanical strength.
The density of (D) is preferably in the range of 0.8 to 0.9 g / cm ³ . By using an ethylene / α-olefin copolymer having a density in this range, the thermoplastic resin composition of the present invention having excellent flexibility and rubber properties can be obtained.
(D) used in the present invention preferably has long chain branching. Due to the presence of long chain branching, it is possible to make the density smaller compared to the proportion (% by weight) of the α-olefin copolymerized without reducing the mechanical strength. An ethylene / α-olefin copolymer having high hardness and high strength can be obtained. The ethylene / α-olefin copolymer having a long chain branch is described in US Pat. No. 5,278,272.

Moreover, (D) desirably has a melting point peak of a thermobalance (DSC) at room temperature or higher. When it has a melting point peak, the form is stable in the temperature range below the melting point, it is easy to handle and has little stickiness.
The melt index (D) used in the present invention is preferably in the range of 0.01 to 100 g / 10 min (230 ° C., 2.16 kg load (0.212 Pa)), more preferably 0.2 to 10 g / 10 min. From the viewpoint of crosslinkability of the thermoplastic elastomer composition of the present invention, 100 g / 10 min or less is preferable, and from the viewpoint of fluidity and processability, 0.01 g / 10 min or more is preferable.
The amount of (D) is preferably 0.1 to 500 parts by weight, more preferably 1 to 100 parts by weight, most preferably 1 to 100 parts by weight of the polymer component consisting of (A) and (B). ~ 50 parts by weight.
(A) in the present invention is preferably crosslinked with (E) a crosslinking agent.
(E) The crosslinking agent contains (E-1) a crosslinking initiator as an essential component, and contains (E-2) a polyfunctional monomer and (E-3) a monofunctional monomer as necessary. The (E) crosslinking agent is used in an amount of 0.001 to 10 parts by weight, preferably 0.005 to 3 parts by weight, based on 100 parts by weight of (A). Within the above range, the level of crosslinking increases and the balance between the heat resistance of the composition and the rubber properties is improved.

  Here, examples of the (E-1) crosslinking initiator include radical initiators such as organic peroxides and organic azo compounds, and specific examples thereof include 1,1-bis (t-butylperoxy). −3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1- Bis (t-butylperoxy) cyclododecane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl-4,4-bis (t Peroxyketals such as -butylperoxy) butane and n-butyl-4,4-bis (t-butylperoxy) valerate; di-t-butyl peroxide, dicumyl peroxide, -Butyl cumyl peroxide, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, α, α'-bis (t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5 -Dialkyl peroxides such as bis (t-butylperoxy) hexane and 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3; acetyl peroxide, isobutyryl peroxide, octanoyl Diacyl peroxides such as peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide and m-trioyl peroxide; t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxylaurate, t-butyl peroxybenzoate, di-t-butyl peroxyisophthalate, 2,5 -Peroxyesters such as dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, and cumylperoxyoctate; and t-butylhydro Hydroperoxides such as peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide and 1,1,3,3-tetramethylbutyl peroxide To mention That.

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 (E-1) is preferably used in an amount of 1 to 80% by weight, more preferably 10 to 50% by weight in the component (E). 1% by weight or more is preferable from the viewpoint of crosslinkability, and 80% by weight or less is preferable from the viewpoint of mechanical strength.
In the present invention, the (E-2) polyfunctional monomer contained in the (E) crosslinking agent as necessary is preferably a radically polymerizable functional group as the functional group, and particularly preferably a vinyl group. Although the number of functional groups is 2 or more, it is effective particularly in the case of having 3 or more functional groups in combination with (E-3). Specific examples include divinylbenzene, triallyl isocyanurate, triallyl cyanurate, diacetone diacrylamide, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, ethylene glycol dimethacrylate, Triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, diisopropenylbenzene, P-quinonedioxime, P, P'-dibenzoylquinonedioxime, phenylmaleimide, allyl methacrylate, N, N'-m-phenylenebismaleimide, diallyl Phthalate, tetraallyloxyethane, 1,2-polybutadiene and the like are preferably used. Triaryl isocyanurate is particularly preferable. These polyfunctional monomers may be used in combination.

The (E-2) is preferably used in an amount of 1 to 80% by weight, more preferably 10 to 50% by weight in the component (E). 1% by weight or more is preferable from the viewpoint of crosslinkability, and 80% by weight or less is preferable from the viewpoint of mechanical strength.
The (E-3) used in the present invention is a vinyl monomer added to control the crosslinking reaction rate, preferably a radical polymerizable vinyl monomer, an aromatic vinyl monomer, acrylonitrile. , Unsaturated nitrile monomers such as methacrylonitrile, ester monomers such as acrylic acid ester monomers and methacrylic acid ester monomers, unsaturated carboxylic acids such as acrylic acid monomers and methacrylic acid monomers Examples thereof include unsaturated carboxylic acid anhydrides such as acid monomers and maleic anhydride monomers, and N-substituted maleimide monomers.

The (E-3) is preferably used in an amount of 1 to 80% by weight, more preferably 10 to 50% by weight in the component (E). 1% by weight or more is preferable from the viewpoint of crosslinkability, and 80% by weight is preferable from the viewpoint of mechanical strength.
In the present invention, the most preferable combination of (E) crosslinking agents is 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane (trade name Perhexa 25B, manufactured by NOF Corporation as a crosslinking initiator. ) Or 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 manufactured by Nippon Oil & Fats Co., Ltd. and triallyl isocyanurate (TAIC) manufactured by Nippon Kasei Co., Ltd. ) And divinyl benzene exhibit excellent mechanical strength.

In the present invention, other inorganic fillers, plasticizers, organic / inorganic pigments, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, foaming agents, antistatic agents, antibacterial agents, and the like are not impaired. It is possible to contain an agent.
For the production of the composition of the present invention, it is possible to adopt a general method such as a Banbury mixer, a kneader, a single screw extruder, a twin screw extruder or the like used for the production of ordinary resin compositions and elastomer compositions. It is. In particular, a twin screw extruder is preferably used in order to achieve dynamic crosslinking efficiently. The twin-screw extruder disperses (A), (B) or (A), (B), (C), or (A), (B), (C), (D) uniformly and finely, Furthermore, other components are added to cause a crosslinking reaction, which is more suitable for continuously producing the composition of the present invention.

The thermoplastic polymer rubber composition of the present invention may be crosslinked by first producing (A), (B), (C), (D) in the first stage in the same extruder and then adding (E). And each component may be manufactured and melt-mixed using a plurality of extruders.
About the manufacturing method of the composition of this invention, it can manufacture via the following process steps, for example. That is, it is preferable that (A), (B), (C), and (D) are thoroughly mixed and melt-kneaded. (E) may be added from the beginning together with (A) to (D), may be added from the middle of the extruder, or may be added separately at the beginning and midway. You may add a part of (A) and (B) from the middle of an extruder. Specifically, it is composed of an aromatic vinyl random copolymer rubber (a), polystyrene (b-1), polyphenylene ether (b-2), phosphate ester (c), ethylene / propylene / diene rubber (d). As a method for producing a composition in which the composition is crosslinked by a dynamic crosslinking method, (a), (b-1), (b-2) and (d) are melt-kneaded in the former stage of the extruder, and then a third feeder. In the middle, (c) is fed and pelletized after melt-kneading. Subsequently, after mixing the said pellet and (e) crosslinking agent, the method of dynamic-crosslinking with an extruder and obtaining a pellet is mentioned. In that case, you may manufacture the said 2 step process in 1 step.

Further, a particularly preferable 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 of a main feed portion and a side feed portion that are different in distance from the tip portion, and is provided between the plurality of supply portions and between the tip portion and the above It is preferable that a needing portion is provided between the tip portion and the supply portion at a short distance, and the length of the needing portion is 3D to 10D.
In addition, one twin-screw extruder of the production apparatus used in the present invention may be a twin-screw co-rotating extruder or a bi-shaft counter-rotating extruder. As for the engagement of the screws, there are a non-engagement type, a partial engagement type, and a complete engagement type, and any type may be used. When applying a low shearing force to obtain a uniform resin at a low temperature, a different direction rotation / partial meshing type screw is preferred. When larger kneading is required, a co-rotating and fully meshing screw is preferable.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these. In these examples and comparative examples, the test methods used for evaluating various physical properties are as follows.
1. Flame retardant The calorific value (kW / m ² ) is measured by a method based on ASTM-E1354 using a cone calorimeter III manufactured by Toyo Seiki Seisakusho. As a measuring condition, radiation heat ^{(Radiant Heat Flux) 50kW / m} 2), the sample placed horizontally, and the sample surface area 0.006 m ^2.
2. Rubber properties (recovery angle)
A 2mm thick sheet is bent 180 degrees in a 23 ° C room, placed on a horizontal surface in that state, and then a 1kg weight is removed after 10 seconds. After the shape has fully recovered, the angle between the horizontal surface and the bent sheet is measured. And the recovery angle. The smaller the recovery angle, the higher the recovery and the higher rubber properties.
The cushion feeling when the sheet is pressed with a finger is used as an index of rubber characteristics, and evaluation is performed according to the following criteria.
◎ Very good ○ Good △ Good, but slightly inferior to cushioning × No cushion feeling

3. Tensile strength at break [MPa]
Evaluation is performed at 23 ° C. according to JIS K6251 from a sheet having a thickness of 2 mm. The following are used for each component used in Examples and Comparative Examples.
(A) Aromatic vinyl-based thermoplastic polymer rubber (A)
1) Aromatic vinyl random copolymer Manufactured by hydrogenating a styrene / butadiene random copolymer based on a known method described in WO01 / 48079. The hydrogenation rate is 99% and the number average molecular weight is 100,000. In this case, precursors having different styrene / butadiene composition ratios are used.
2) Aromatic vinyl block copolymer Manufactured by hydrogenating a styrene / butadiene block copolymer based on a known method described in WO01 / 48079. The hydrogenation rate is 99% and the number average molecular weight is 100,000. In this case, precursors having different styrene / butadiene composition ratios are used.

(B) Thermoplastic resin (B)
1) Polystyrene Rubber unmodified polystyrene (referred to as PS) MFR: 0.5 g / 10 min (230 ° C., 2.16 kg load)
2) Polyphenylene ether poly (2,6-dimethyl-1,4-phenylene ether) (referred to as PPE) reduced viscosity ηsp / C (0.5 g / dl, chloroform solution, measured at 30 ° C.) is 0.50 dl / g
3) Polypropylene Isotactic homopolypropylene (referred to as PP) MFR: 0.5 g / 10 min (230 ° C., 2.16 kg load)

(C) Flame retardant (C)
1) Bis (dibromopropyl) tetrabromobisphenol A ether (FR1)
Halogen flame retardant manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (referred to as FR1)
2) Aromatic phosphate ester condensate: bisphenol A bis (diphenyl phosphate) (FR2)
Commercially available aromatic condensed phosphate ester derived from bisphenol A {manufactured by Daihachi Chemical Industry Co., Ltd., trade name: CR741 (referred to as FR2)}
3) Magnesium hydroxide (FR3)
Kyowa Chemical Industry Co., Ltd. (referred to as FR3)
4) Red phosphorus (FR4)
Made by Rin Chemical Industry Co., Ltd. (referred to as FR4)

(D) Ethylene / α-olefin copolymer (D)
1) Copolymer of ethylene and octene-1 (TPE-1)
It was produced by a method using a metallocene catalyst described in JP-A-3-16388. The composition ratio of ethylene / octene-1 in the copolymer is 72/28 (weight ratio), and the Mooney viscosity is 100. (Referred to as TPE-1)
2) Copolymer of ethylene / propylene / ethylidene norbornene (ENB) (TPE-2)
It is produced by a method using a metallocene catalyst described in JP-A-3-163088. The composition ratio of ethylene / propylene / ENB of the copolymer is 72/24/4 (weight ratio), and the Mooney viscosity is 100. (Referred to as TPE-2)
3) Ethylene / propylene / ethylidene norbornene (ENB) copolymer (TPE-3) produced by a method using an ordinary Ziegler catalyst. The composition ratio of ethylene / propylene / ENB of the copolymer is 72/24/4 (weight ratio), and the Mooney viscosity is 105. (Referred to as TPE-3)

(E) Cross-linking agent (E)
1) Cross-linking initiator (E-1)
2,5-dimethyl-2,5-bis (t-butylperoxy) hexane (referred to as POX)
2) Polyfunctional monomer (E-2)
Triallyl isocyanurate (referred to as TAIC)

[Examples 1-16 and Comparative Examples 1-2]
Using a twin screw extruder, the compositions described in Tables 1 and 2 are melt extruded at 200 ° C. to produce the final composition.
A 2 mm thick sheet molded product is produced from the composition thus obtained using a T-die extruder and subjected to various evaluations. The results are shown in Tables 1 and 2.

  The composition of the present invention includes automotive parts, automotive interior materials, automotive materials such as airbag covers, mechanical parts, electrical parts, cables, hoses, belts, toys, sundries, daily necessities, building materials, sheets, films, etc. It can be used in a wide range of applications. Molding materials include foam molding materials, calender molding materials, powder slush molding materials, multilayer molding materials, insert molding materials, co-extrusion molding materials, injection molding materials, blow molding materials, extrusion sheet molding materials, profile extrusion molding materials, fibers Useful for reinforced molding materials. Specifically, it is wallpaper, sealing material, edge material, waterproof sheet, tubular material, wire coating material, anti-slip material, cushioning material, swimming article, floor covering material, and plays a significant role in the industry.

Claims (10)

  A dynamically crosslinked thermoplastic polymer composition comprising an aromatic vinyl-based thermoplastic polymer rubber (A), a thermoplastic resin (B), and a flame retardant (C).   The thermoplastic polymer composition according to claim 1, wherein (A) is an aromatic vinyl-based thermoplastic random copolymer rubber (A-1).   (A) is a thermoplastic copolymer rubber mainly composed of random bonds composed of 10 to 49% by weight of conjugated diene monomer units and 51 to 90% by weight of aromatic vinyl monomer units, and is olefinic The thermoplastic polymer composition according to claim 1 or 2, wherein a double bond hydrogenation rate is 50% or more.   The thermoplastic polymer composition according to any one of claims 1 to 3, wherein (B) is an aromatic vinyl resin and / or a polyphenylene ether resin.   The thermoplastic polymer composition according to any one of claims 1 to 4, wherein (C) is a non-halogen flame retardant.   The thermoplastic polymer composition according to claim 5, wherein (C) is a phosphorus-based flame retardant.   The thermoplastic polymer composition according to any one of claims 1 to 6, further comprising an ethylene / α-olefin copolymer (D).   The thermoplastic polymer composition according to claim 7, wherein (D) is an ethylene / α-olefin copolymer containing ethylene and an α-olefin having 3 to 20 carbon atoms, produced using a metallocene catalyst.   The thermoplastic polymer composition according to any one of claims 1 to 8, which is crosslinked with a crosslinking agent (E).   A thermoplastic polymer composition comprising an aromatic vinyl-based thermoplastic polymer rubber (A) and a thermoplastic resin (B), wherein (A) is a conjugated diene monomer unit and an aromatic vinyl monomer A copolymer rubber having a hydrogenation rate of olefinic double bonds of 50% or more, and an aromatic vinyl monomer unit block and an ethylene / α-olefin monomer unit after hydrogenation Aromatic vinyl-based thermoplastic random copolymer rubber (A-2) formed from a random block of ethylene, an α-olefin, and an aromatic vinyl monomer unit, wherein the thermoplastic resin (B ) Is an olefin resin or a thermoplastic resin containing an olefin resin.