JP2010059337A - Method of producing thermoplastic polymer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of producing a thermoplastic polymer composition having both excellent functionality such as flame retardancy and mechanical strength. <P>SOLUTION: There is provided the method for production of the thermoplastic polymer composition including a cross-linkable polymer rubber (A), a thermoplastic resin (B), a thermoplastic polymer additive (C) and a cross-linking agent (D). The method includes the steps of: (i) mixing the components (A), (B) and (C) to reduce the glass transition temperature (Tg) of a resin composition comprising the components (A) and (B); and (ii) cross-linking the resin composition by adding the cross-linking agent (D) simultaneously with the step (i) or successively to the step (i). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing a thermoplastic polymer composition. More specifically, the present invention relates to a method for producing a thermoplastic polymer composition having excellent functionality such as 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 materials such as automotive materials and electrical / electronic materials. In order to enhance the functionality, polymer additives such as flame retardants are added.
As a flame retardant method that is one of the functionalizations of thermoplastic polymers, it is known to add halogen-based, phosphorus-based, and inorganic flame retardants to thermoplastic polymers, which makes it difficult to some extent. Combustion has been achieved. However, in recent years, there has been a close need for fire safety, and there is a strong demand for development of flame retardant technology that has no deterioration in mechanical properties and has no environmental problems, along with development of more advanced flame retardant technology. ing.

As a flame retardant technology for thermoplastic polymers, a coating material (Patent Document 1) in which ammonium polyphosphate and a metal hydrate are blended with polypropylene and a styrene thermoplastic elastomer is disclosed.
On the other hand, as a cross-linking material, a thermoplastic halogen resin and antimony trioxide are blended with a specific halogen-based flame retardant, an electron beam cross-linked tube or a heat-shrinkable tube (Patent Document 2), or a mechanical material after cross-linking with respect to the initial stage. A flame-retardant electric wire having a specific value (Patent Document 3) is disclosed.
Moreover, in the manufacturing method of the resin composition of a thermoplastic resin and a liquid substance, the manufacturing method (patent document 4) which mixes both and lowers Tg of a thermoplastic resin and melt-extrudes with a melt extruder is disclosed. Yes.

JP-A-9-31267 Japanese Patent No. 2765361 Japanese Patent Laid-Open No. 10-168248 Japanese Patent Laid-Open No. 11-172009

However, although the coating material disclosed in Patent Document 1 is excellent in moldability and flexibility, it is inferior in wear resistance and durability because it is not crosslinked.
Moreover, although two bridge | crosslinking materials disclosed by patent document 2 and 3 are excellent in durability, since they do not have thermoplasticity, productivity is inferior.
Furthermore, Patent Document 4 does not mention at all the application of the crosslinking technique.
Therefore, the present situation is that development of a thermoplastic polymer composition excellent in functionality such as flame retardancy and satisfying mechanical strength is demanded.

  In view of the above circumstances, the problem to be solved by the present invention is to provide a method for producing a thermoplastic polymer composition having excellent functionality such as flame retardancy and mechanical strength.

As a result of intensive studies to solve the above problems, the present inventor includes a crosslinkable polymer rubber (A), a thermoplastic resin (B), a thermoplastic polymer additive (C), and a crosslinker (D). A method for producing a thermoplastic polymer composition, comprising:
(I) a step of mixing the components (A), (B) and (C) to lower the glass transition temperature (Tg) of the resin composition comprising the components (A) and (B);
(Ii) The step of crosslinking the resin composition by mixing the crosslinking agent (D) simultaneously with the step (i) or following the step (i).
It has been found that a thermoplastic polymer composition having significantly improved functionality such as flame retardancy and mechanical strength can be obtained by a method for producing a thermoplastic polymer composition comprising

That is, the present invention is as follows.
[1]
A method for producing a thermoplastic polymer composition comprising a crosslinkable polymer rubber (A), a thermoplastic resin (B), a thermoplastic polymer additive (C), and a crosslinker (D),
(I) a step of mixing the components (A), (B) and (C) to lower the glass transition temperature (Tg) of the resin composition comprising the components (A) and (B);
(Ii) The step of crosslinking the resin composition by mixing the crosslinking agent (D) simultaneously with the step (i) or following the step (i).
A method for producing a thermoplastic polymer composition, comprising:
[2]
The method for producing a thermoplastic polymer composition according to the above [1], wherein the component (A) is an aromatic vinyl-based thermoplastic polymer rubber.
[3]
The method for producing a thermoplastic polymer composition according to the above [2], wherein the aromatic vinyl-based thermoplastic polymer rubber is an aromatic vinyl-based random copolymer rubber and / or an aromatic vinyl-based block copolymer rubber. .
[4]
The method for producing a thermoplastic polymer composition according to any one of the above [1] to [3], wherein the component (B) is a polyphenylene ether resin and / or an aromatic vinyl resin.
[5]
The method for producing a thermoplastic polymer composition according to any one of the above [1] to [4], wherein the component (C) is a thermoplastic flame retardant.
[6]
The method for producing a thermoplastic polymer composition according to the above [5], wherein the thermoplastic flame retardant is a phosphorus flame retardant.

  By the method for producing a thermoplastic polymer composition of the present invention, a thermoplastic polymer composition having excellent functionality such as flame retardancy and mechanical strength can be obtained.

  Hereinafter, the best mode for carrying out the present invention (hereinafter referred to as the present embodiment) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

The method for producing the thermoplastic polymer composition of the present embodiment is as follows:
A method for producing a thermoplastic polymer composition comprising a crosslinkable polymer rubber (A), a thermoplastic resin (B), a thermoplastic polymer additive (C), and a crosslinker (D),
(I) a step of mixing the components (A), (B) and (C) to lower the glass transition temperature (Tg) of the resin composition comprising the components (A) and (B);
(Ii) including the step of crosslinking the resin composition by mixing the crosslinking agent (D) simultaneously with the step (i) or following the step (i).

  In step (i) in the production method of the present embodiment, components (A), (B) and (C) are mixed, and the glass transition temperature (Tg) of the resin composition comprising components (A) and (B). ). In the production method of the present embodiment, the glass transition temperature (Tg) of the resin composition comprising the components (A) and (B) is preferably 1 to 200 ° C, more preferably 10 to 100 ° C, and still more preferably. The temperature is lowered by 20 to 100 ° C, particularly preferably 20 to 50 ° C.

  While maintaining the thermoplasticity of the resin composition by this step, it is possible to crosslink with the crosslinking agent (D) in the step (ii) described later, and as a result, the functionality and mechanical properties of the thermoplastic polymer composition. The strength can be greatly improved. The reason why it is possible to impart both excellent functionality and mechanical strength by the manufacturing method of the present embodiment is that the level of crosslinking is only improved by lowering the Tg of the resin composition. Not only that, the morphology is estimated to have improved as well.

Hereinafter, each component in the step (i) of the present embodiment will be described.
[(A) component: crosslinkable polymer rubber]
Examples of the component (A) in the present embodiment include polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), isoprene rubber, chloroprene rubber, poly (styrene-isoprene) and other diene rubbers, and the like. Saturated polymer rubber (hydrogenated copolymer rubber) obtained by hydrogenating diene rubber, acrylic rubber such as polybutyl acrylate, ethylene-propylene copolymer, ethylene-octene copolymer, ethylene-propylene-diene monomer Examples thereof include a crosslinkable rubber-like polymer such as an ethylene / α-olefin copolymer such as a terpolymer (EPDM), or a thermoplastic elastomer containing the rubber component.

  Among these, since it has a good compatibility with the component (B) and tends to be uniformly dispersed in the composition, a diene rubber containing an aromatic vinyl monomer unit (hereinafter, aromatic). (Referred to as vinyl-based thermoplastic polymer rubber), and examples thereof include a copolymer rubber composed of a conjugated diene monomer and an aromatic vinyl monomer. The stereoregularity may be random (aromatic vinyl-based random copolymer rubber) or block (aromatic vinyl-based block copolymer rubber).

  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, Examples include 3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene, and the like, among which 1,3-butadiene, isoprene, and 1,3-pentadiene. Preferably, 1,3-butadiene and isoprene are more preferable. The conjugated diene monomers may be used alone or in combination of two or more.

  Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, t-butylstyrene, divinylbenzene, N, N-dimethyl-p-aminoethylstyrene, vinylpyridine, and the like. Among them, styrene and α-methylstyrene are preferable. The above aromatic vinyl monomers may be used alone or in combination of two or more.

  When the component (A) is a copolymer rubber composed of a conjugated diene monomer and an aromatic vinyl monomer, the composition ratio is conjugated when the stereoregularity is mainly random bonds. The diene monomer unit is preferably 10 to 49% by mass, more preferably 20 to 49% by mass, still more preferably 25 to 45% by mass, and the aromatic vinyl monomer unit is preferably 51 to 49% by mass. 90 mass%, More preferably, it is 51-80 mass%, More preferably, it is 25-45 mass%. On the other hand, when the stereoregularity is mainly composed of block bonds, the conjugated diene monomer unit is preferably 51 to 90% by mass, more preferably 51 to 80% by mass, and still more preferably 25 to 45% by mass. The aromatic vinyl monomer unit is preferably 10 to 49% by mass, more preferably 20 to 49% by mass, and still more preferably 25 to 45% by mass.

  Component (A) is a monomer copolymerizable with a conjugated diene such as an olefin, methacrylic ester, acrylic ester, unsaturated nitrile, or vinyl chloride monomer, if necessary. Hereinafter, a copolymerized monomer may be used.

  In the case of a copolymer containing an aromatic vinyl monomer and a monomer that can be copolymerized as necessary, a block-like aromatic vinyl monomer and a block are formed when random bonds are mainly used. A copolymerizable monomer may be included. The content of the block-like aromatic vinyl polymer is preferably 20% by mass or less and more preferably 10% by mass or less in the wholly aromatic vinyl monomer. On the other hand, in the case where the copolymer is mainly composed of block bonds, it may contain a random aromatic vinyl monomer and a random copolymerizable monomer. The content of the random aromatic vinyl polymer is preferably 20% by mass or less and more preferably 10% by mass or less in the wholly aromatic vinyl monomer.

  In the above copolymer rubber, when the stereoregularity is mainly random bonds, the vinyl bonds in the conjugated diene monomer part before hydrogenation are present evenly in the molecule. Or may include a plurality of blocks having different vinyl bond contents. The aromatic vinyl monomer is preferably bonded at random in the conjugated diene monomer portion, but may contain a block-like aromatic vinyl monomer. The content of the block-like aromatic vinyl polymer is preferably 50% by mass or less, more preferably 30% by mass or less in the wholly aromatic vinyl monomer.

  In the copolymer rubber, examples of the copolymer whose stereoregularity mainly includes a block bond include a copolymer having an aromatic vinyl block and a conjugated diene block, or a hydrogenated product thereof. Specific examples include a hydrogenated styrene-butadiene block copolymer and a hydrogenated styrene-isoprene block copolymer. Moreover, the unsaturated carboxylic acid or its anhydride, or the epoxy-modified block copolymer is also contained as needed.

  When the polymer block consisting of aromatic vinyl units is indicated by S and the polymer block consisting of conjugated dienes and / or partially hydrogenated units thereof is indicated by B, the block structure is 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), (SB) nX (where n is 3) An integer of ˜6, where X is a residue of a coupling agent such as silicon tetrachloride, tin tetrachloride, polyepoxy compound, etc.) and is a star-shaped (star) block copolymer having a B moiety as a bond center It is preferable. Among them, SB type 2, SBS type 3 and SBSB type 4 linear block copolymers are preferable.

  The hydrogenation rate of all olefinic double bonds of the aromatic vinyl-based thermoplastic polymer rubber is preferably 50% or more, more preferably 90% or more, and still more preferably 95% or more. The residual double bond in the main chain is preferably 5% or less, and the residual double bond in the side chain is preferably 5% or less.

  As a method for measuring the hydrogenation rate, a known NMR method can be used, and details thereof are described in, for example, WO01 / 48079. Specific examples of the hydrogenated polymer rubber include rubbery polymers obtained by partially or completely hydrogenating styrene-diene rubbers such as poly (styrene-butadiene) and poly (styrene-isoprene). be able to.

  The hydrogenated polymer rubber can be obtained by partially hydrogenating the above styrene / diene rubber by a known hydrogenation method. Examples of the hydrogenation method include F.I. L. Ramp, etal, J. et al. Amer. Chem. Soc. , 83, 4672 (1961), a method of hydrogenation using a triisobutylborane catalyst, Hung Yu Chen, J. et al. Polym. Sci. Polym. Letter Ed. , 15, 271 (1977), or hydrogenation using an organic cobalt-organic aluminum catalyst or organic nickel-organic aluminum catalyst described in Japanese Patent Publication No. 42-8704. The method etc. can be mentioned.

  Here, particularly preferable hydrogenation methods are described in JP-A-59-133203 and JP-A-60-220147 using a catalyst capable of hydrogenation under mild conditions of low temperature and low pressure. Or hydrogen 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 in an inert organic solvent. Examples include the method described in JP-A No. 62-207303, which is brought into contact.

  As the component (A) used in the present embodiment, a plurality of types may be mixed and used. In such a case, the workability can be further improved.

  In the present embodiment, 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 for controlling the ratio of the polymer, a method of increasing the overall molecular weight so that a portion having a molecular weight of 150,000 or less is 30% or less, or a method of removing a portion having a molecular weight of 150,000 or less by an operation such as extraction Alternatively, a polymerization method or the like may be mentioned so that a molecular weight of 150,000 or less is not selectively generated by a polymerization catalyst or the like.

  The glass transition temperature (Tg) of the component (A) is preferably 30 ° C. or lower. Here, Tg means a value measured by differential scanning calorimetry (DSC).

  The Mooney viscosity (ML) (based on ISO 289-985 (E)) measured at 100 ° C. of the component (A) is preferably 20 to 150, more preferably 50 to 120.

[(B) component: thermoplastic resin]
In the present embodiment, the component (B) is not particularly limited as long as it is compatible or uniformly dispersible with the component (A). For example, aromatic vinyl resins, polyphenylene ether resins, polyolefin resins, poly Examples include vinyl chloride resins, polyamide resins, polyester resins, polyphenylene sulfide resins, polycarbonate resins, polyoxyalkylene resins, and polymethacrylate resins. These may be used alone or in combination of two or more. Among these, aromatic vinyl resins, polyphenylene ether resins, and olefin resins are preferred because they have good compatibility with the component (A) and tend to be uniformly dispersed in the composition.

  The aromatic vinyl resin is 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. Is a main copolymer and may be a rubber-modified product or a rubber non-modified product. Specifically, an aromatic vinyl monomer such as styrene, α-methylstyrene, paramethylstyrene, or halogenated styrene is an essential component, and an unsaturated nitrile monomer such as acrylonitrile or methacrylonitrile, if necessary. And a copolymer containing monomers such as acrylic acid ester or methacrylic acid ester having an alkyl group having 1 to 8 carbon atoms, or acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimide, etc. Is preferred.

  In addition, the aromatic vinyl resin can be rubber-modified as required, and a rubber-modified polymer in which a rubber-like polymer is dispersed in a particle form in the polymer matrix is preferable. Specific 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), and AES resin. (Acrylonitrile-ethylenepropylene rubber-styrene copolymer) and the like.

  When component (B) is polyphenylene ether (hereinafter also referred to as PPE), poly (2,6-dimethyl-1,4-phenylene ether), 2,6-dimethylphenol and 2,3,6-trimethyl A copolymer with phenol or the like is preferable, and among them, poly (2,6-dimethyl-1,4-phenylene ether) is more preferable. The method for producing 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. Can be easily produced by oxidative polymerization. In addition, U.S. Pat. No. 3,306,1075, U.S. Pat. No. 3,257,357, U.S. Pat. No. 3,257,358, and Japanese Patent Publication No. 52-17880, JP, It can also be easily produced by the method described in Japanese Patent Laid-Open No. 50-51197.

  The reduced viscosity ηsp / C (0.5 g / dL, chloroform solution, measured at 30 ° C.) of the PPE is preferably in the range of 0.20 to 0.70 dL / g, preferably 0.30 to 0.60 dL / g. It is more preferable that it is in the range.

  In the case where the component (B) is an olefin resin, for example, ethylene or propylene resin or other ethylene and / or α-olefin copolymer containing 2 to 20 carbon atoms is used. Examples of the resin include propylene-based resins.

  Specific examples of the propylene resin include homoisotactic polypropylene, isotactic copolymer resins of propylene and other α-olefins such as ethylene, butene-1, pentene-1, and hexene-1 ( Block and random).

  Random copolymer resin with α-olefin mainly composed of propylene which is one of olefinic resins can be produced by high pressure method, slurry method, gas phase method, bulk method, solution method, etc. As the polymerization catalyst, a Ziegler-Natta catalyst, a single site, or a metallocene catalyst is preferable. In particular, when a narrow composition distribution and molecular weight distribution are required, a random copolymerization method using a metallocene catalyst is preferable.

  Moreover, as a melt index of an olefin resin, the thing of the range of 0.1-100 g / 10min (230 degreeC, 2.16kg load (0.212Pa)) is used preferably. From the viewpoint of heat resistance and mechanical strength of the thermoplastic polymer composition, it is preferably 100 g / 10 min or less, and from the viewpoint of fluidity and molding processability, it is preferably 0.1 g / 10 min or more.

  About content ratio in 100 mass parts of resin compositions which consist of (A) component and (B) component in this Embodiment, (A) component becomes like this. Preferably it is 1-99 mass parts, More preferably, it is 20-80. Part by mass, more preferably 30 to 70 parts by mass.

[(C) component: thermoplastic polymer additive]
The thermoplastic polymer additive of component (C) in the present embodiment is a component for imparting desirable properties such as flame retardancy to the thermoplastic polymer composition, and at the same time, components (A) and (B) It is a component for reducing Tg of the resin composition which consists of.

  The component (C) preferably has a viscosity at 100 ° C. of 1 million centistokes or less, more preferably 100,000 centistokes or less, and still more preferably 10,000 centistokes or less. When the viscosity of the component (C) at 100 ° C. is 10,000 centistokes or less, the dissolving power for the polymer composition tends to increase. In order to satisfy this condition, the component (C) is preferably a compound having a molecular weight of 1000 or less. Further, the component (C) may be either a polymer or an oligomer.

  Examples of the component (C) include plasticizers, heat stabilizers, light stabilizers, flame retardants, colorants, foaming agents, lubricants, fragrances, smoke suppressants, tackifiers, preservatives, heat retention agents, and impact resistance. Additives for polymers such as improvers, repellents, wetting agents, surfactants, emulsifiers, destabilizers, coagulants, antifoaming agents, antifreezing agents, creaming agents, thickeners, heat sensitive agents, foaming agents Or a solvent etc. are mentioned. Among these, a plasticizer, a heat stabilizer, a flame retardant, and a light stabilizer are preferable because of high compatibility with the polymer composition.

  The content of the component (C) in the thermoplastic polymer composition in the present embodiment is preferably 1 to 99% by mass, more preferably 1 to 50% by mass, still more preferably 5 to 50% by mass, and particularly preferably. Is 10-30 mass%.

  The flame retardant, which is one type of component (C) in the present embodiment, is one or more flame retardants selected from halogen-based, phosphorus-based, nitrogen-based, silicon-based, inorganic-based, char-forming agents, etc. Non-halogen type is preferable, and phosphorus flame retardant is more preferable.

  Examples of the halogen flame retardant include halogenated bisphenols, aromatic halogen compounds, halogenated polycarbonates, halogenated aromatic vinyl polymers, and the like.

  Examples of the phosphorus flame retardant include organic phosphorus compounds and inorganic phosphates. Examples of the organic phosphorus compound include phosphine, phosphine oxide, biphosphine, phosphonium salt, phosphinic acid salt, phosphate ester, phosphite ester and the like. More specifically, triphenyl phosphate, methyl neopentyl phosphite, pentaerythritol diethyl diphosphite, methyl neopentyl phosphate, phenyl neopentyl phosphate, pentaerythritol diphenyl diphosphate, dicyclopentyl high positive phosphate Dineopentyl hypophosphite, phenyl pyrocatechol phosphite, ethyl pyrocatechol phosphate, dipyrrocatechol high positive phosphate, and the like.

  Moreover, as an organic phosphorus compound, the aromatic phosphate ester monomer represented by following formula (1) and the aromatic phosphate ester condensate represented by following formula (2) are preferable.

(In the formula, Ar1, Ar2, Ar3, Ar4, Ar5, Ar7, Ar8 are each independently an aromatic group selected from a phenyl group that is unsubstituted or substituted with at least one hydrocarbon group having 1 to 10 carbon atoms. Ar6 represents a divalent aromatic group having 6 to 20 carbon atoms, and m represents an integer of 1 or more.)

  Examples of the silicon flame retardant include one or more flame retardants selected from silicone resins, silicone oils, polyorganosilicates, and silica.

  As said silicone oil or polyorganosilicate, the compound represented, for example by following formula (3) is preferable.

(Wherein, R ₁ to R ₄ represents a hydrocarbon group having 1 to 20 carbon atoms, p, q is 0 or 1, n is an integer of 1 or more.)

Here, R _{1 to} R ₄ are each a hydrocarbon group having 1 to 20 carbon atoms, and particularly preferably has a substituent selected from a methyl group, a phenyl group, a phenyl group substituted with an alkyl group, and an alkenyl group. . R _{1 to} R ₄ may be the same or different.

  The viscosity of the silicone oil and the polyorganosilicate is preferably 600 to 1000000 centistokes (25 ° C.), more preferably 90000 to 150,000 centistokes (25 ° C.).

  Examples of the plasticizer that is one type of component (C) include phthalic acid esters such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, phthalic acid mixed ester such as butyl benzyl phthalate, diisodecyl succinate, Aliphatic dibasic acid esters such as dioctyl adipate, glycol esters such as diethylene glycol dibenzoate, aliphatic acid esters such as butyl oleate and methyl acetylricinoleate, and epoxy plasticizers such as epoxidized soybean oil and epoxidized linseed oil In addition, trioctyl trimellitic acid, ethyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, tributyl acetyl citrate, chlorinated paraffin, polypropylene adipate, polyethylene sebacate, triacetin, tribute Phosphorus, toluenesulfonamide, alkylbenzenes, biphenyl, partially hydrogenated terphenyl, camphor, and the like.

[Step (ii)]
Step (ii) in the production method of the present embodiment is a step of crosslinking the resin composition by mixing the crosslinking agent (D) simultaneously with the step (i) or following the step (i).

[Component (D): Crosslinking agent]
The crosslinking agent (D) in the present embodiment has the crosslinking initiator (D-1) as an essential component, and if necessary, a polyfunctional monomer (D-2) or a monofunctional monomer (D-3). Containing. The crosslinking agent (D) is preferably used in an amount of 0.001 to 10 parts by mass, more preferably 0.005 to 3 parts by mass with respect to 100 parts by mass of the component (A). When the amount of the crosslinking agent (D) used is within the above range, the level of crosslinking is increased and the balance between the heat resistance and the rubber properties of the thermoplastic polymer composition tends to be improved.

  Examples of the crosslinking initiator (D-1) include radical initiators such as organic peroxides and organic azo compounds. Specifically, for example, 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-butyl) Peroxyketals such as peroxy) butane and n-butyl-4,4-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-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 peroxide Diacyl peroxides such as oxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide and m-trioyl peroxide; t -Butyl peroxyacetate, t-bu Tilperoxyisobutyrate, t-butylperoxy-2-ethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate, 2,5-dimethyl Peroxyesters such as -2,5-di (benzoylperoxy) hexane, t-butylperoxymaleic acid, t-butylperoxyisopropylcarbonate and cumylperoxyoctate; and t-butylhydroperoxide, Mention may be made of hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide and 1,1,3,3-tetramethylbutyl peroxide. it can.

  Among the above 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 content of the crosslinking initiator (D-1) is preferably 1 to 80% by mass and more preferably 10 to 50% by mass in the component (D). From the viewpoint of crosslinkability, it is preferably 1% by mass or more, and from the viewpoint of mechanical strength, it is preferably 80% by mass or less.

  In the present embodiment, the polyfunctional monomer (D-2) contained in the cross-linking agent (D) as necessary preferably has a radical polymerizable functional group as a functional group. It is more preferable to have it. The number of functional groups of the polyfunctional monomer (D-2) is 2 or more, but it is preferable to have 3 or more functional groups in combination with (D-3).

  Specific examples of the polyfunctional monomer (D-2) include, for example, divinylbenzene, triallyl isocyanurate, triallyl cyanurate, diacetone diacrylamide, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, trimethylolpropane tri Methacrylate, trimethylolpropane triacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, diisopropenylbenzene, P-quinonedioxime, P, P'-dibenzoylquinonedioxime, phenylmaleimide, allyl methacrylate N, N′-m-phenylene bismaleimide, diallyl phthalate, tetraallyloxyethane, 1,2-polybutadiene, etc. It is. Among the above compounds, triallyl isocyanurate is preferable. These polyfunctional monomers (D-2) may be used alone or in combination.

  The content of the polyfunctional monomer (D-2) is preferably 1 to 80% by mass, more preferably 10 to 50% by mass in the component (D). From the viewpoint of crosslinkability, it is preferably 1% by mass or more, and from the viewpoint of mechanical strength, it is preferably 80% by mass or less.

  In the present embodiment, the monofunctional monomer (D-3) contained as necessary in the crosslinking agent (D) is a vinyl monomer added to control the crosslinking reaction rate, preferably radical polymerization. For example, aromatic vinyl monomers, unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile, ester systems such as acrylate monomers and methacrylate monomers Monomers, unsaturated carboxylic acid monomers such as acrylic acid monomers and methacrylic acid monomers, unsaturated carboxylic acid anhydrides such as maleic anhydride monomers, N-substituted maleimide monomers, etc. be able to.

  The content of the monofunctional monomer (D-3) is preferably 1 to 80% by mass, more preferably 10 to 50% by mass in the component (D). From the viewpoint of crosslinkability, it is preferably 1% by mass or more, and from the viewpoint of mechanical strength, it is preferably 80% by mass.

  Particularly preferable crosslinking agent (D) is 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane (for example, trade name Perhexa manufactured by NOF Corporation) as the crosslinking initiator (D-1). 25B), 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 (for example, manufactured by NOF Corporation), polyallyl monomer (D-2), triallyl isocyanurate ( A combination with TAIC (for example, manufactured by Nippon Kasei Co., Ltd.) or divinylbenzene is preferable because it tends to exhibit excellent mechanical strength.

  In the present embodiment, within the range that does not impair the effect, in the thermoplastic polymer composition, other than the component (C), inorganic filler, plasticizer, organic / inorganic pigment, thermal stabilizer, antioxidant, It is possible to contain other additives such as ultraviolet absorbers, light stabilizers, foaming agents, antistatic agents, antibacterial agents and the like.

  For the production of the thermoplastic polymer composition in the present embodiment, a general method such as a Banbury mixer, a kneader, a single-screw extruder, a twin-screw extruder, etc. used for the production of ordinary resin compositions and elastomer compositions Can be adopted. In particular, a twin screw extruder is preferably used in order to achieve dynamic crosslinking efficiently. The twin-screw extruder disperses (A) (B), (A) (B) (C), or (A) (B) (C) (D) uniformly and finely, and further adds other additives. It is suitable for continuously producing a thermoplastic polymer composition by adding and causing a crosslinking reaction.

About the manufacturing method of the thermoplastic polymer composition in this Embodiment, it can manufacture via the following process steps (1) to (4), for example.
(1): After the components (A) and (B) are melt-mixed, the component (C) is added and melt-mixed, and then the component (D) is added and melt-mixed.
(2): After the components (A) and (B) are melt-mixed, the components (C) and (D) are added and melt-mixed.
(3): After the components (A), (B) and (C) are melt-mixed, the component (D) is added and melt-mixed.
(4): All components (A) to (D) are melted and mixed simultaneously.

  About (D) component, even if it adds from the beginning simultaneously with (A)-(C) component, even if it adds from the middle of an extruder, you may add separately at the beginning and the middle. Moreover, you may add a part of (A) and (B) component from the middle of an extruder.

  More specifically, for example, a method for producing a composition obtained by crosslinking a resin composition comprising an aromatic vinyl copolymer rubber (a), a polyphenylene ether (b), and a phosphate ester (c) by a dynamic crosslinking method. After (a) and (b) are melt-kneaded in the former stage of the extruder, (c) is fed from the middle with a third feeder, melt-kneaded to lower the Tg of the polymer composition and pelletize. Subsequently, after mixing the said pellet and crosslinking agent (d), the method of performing dynamic crosslinking with an extruder and obtaining a pellet is mentioned. In that case, you may implement the said 2 step process in 1 step.

  Further, as a particularly preferable melt extrusion method, a twin-screw extruder having a length L in the die direction from the raw material addition portion and L / D of 5 to 100 (where D is a barrel diameter) is used. The method to use is mentioned. 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 manufacturing apparatus used in the present embodiment may be a two-screw co-rotating extruder or a two-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. In the case where a larger kneading action is required, the same direction rotation / complete meshing type screw is preferable. In the case where a larger kneading action is required, the same direction rotation / complete meshing type screw is preferred.

Hereinafter, the present embodiment will be described in more detail with reference to Examples and Comparative Examples, but the present embodiment is not limited to these.
Test methods used for evaluating various physical properties in Examples and Comparative Examples are as follows.

(1) Flame retardancy Using a cone calorimeter III manufactured by Toyo Seiki Seisakusho, the heat generation rate (kW / m ² ) was measured by a method based on ASTM-E1354. 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. It can be judged that the smaller the value, the better the flame retardancy.

(2) Izod impact strength It measured by the method based on ASTM-D256. (23 ° C, 1/8 inch thickness test piece with V notch, unit: J / m)

(3) Glass transition temperature (Tg)
This was performed by differential scanning calorimetry (DSC). Specifically, using a thermal analyzer DT-40 manufactured by Shimadzu Corporation, a 5 mg sample was measured by raising the temperature at 10 ° C./min in a nitrogen stream.

(4) Melt flow rate (MFR)
It measured by the method based on ASTM D-1238. (Condition: 230 ° C / 10kg)

The following were used as each component in an Example and a comparative example.
(1) Crosslinkable polymer rubber (A): Aromatic vinyl-based thermoplastic polymer rubber (1-1) Aromatic vinyl-based random copolymer Styrene based on known methods described in WO01 / 48079 -An aromatic vinyl random copolymer was produced by hydrogenating a butadiene random copolymer. The hydrogenation rate was 99% and the number average molecular weight was 100,000. In this case, precursors having different styrene / butadiene composition ratios were used.
(1-2) Aromatic vinyl block copolymer An aromatic vinyl block copolymer is obtained by hydrogenating a styrene-butadiene block copolymer based on a known method described in WO01 / 48079. Manufactured. The hydrogenation rate was 99% and the number average molecular weight was 100,000. In this case, precursors having different styrene / butadiene composition ratios were used.

(2) Thermoplastic resin (B)
(2-1) Polystyrene Rubber unmodified polystyrene (PS)
MFR: 2.0 g / 10 min (230 ° C., 10 kg load)
(2-2) Polyphenylene ether Poly (2,6-dimethyl-1,4-phenylene ether) (PPE)
Reduced viscosity ηsp / C (0.5 g / dL, chloroform solution, measured at 30 ° C.): 0.50 dL / g
(2-3) Polybutylene terephthalate (PBT)
MFR: 1.0 g / 10 min (230 ° C., 10 kg load)
(2-4) Polyamide-6 (PA6)
MFR: 0.5 g / 10 min (230 ° C., 10 kg load)
(2-5) Polyoxymethylene (POM)
MFR: 0.5 g / 10 min (230 ° C., 10 kg load)

(3) Thermoplastic polymer additive (C)
(3-1) Bis (dibromopropyl) tetrabromobisphenol A ether (FR1)
Daiichi Kogyo Seiyaku Co., Ltd .: Halogen flame retardant (3-2) Aromatic phosphate ester condensate: bisphenol A bis (diphenyl phosphate) (FR2)
Bisphenol A-derived aromatic condensed phosphate ester (Daihachi Chemical Industry Co., Ltd., trade name: CR741)
(4) Crosslinking agent (D)
(4-1) Crosslinking initiator (D-1)
2,5-dimethyl-2,5-bis (t-butylperoxy) hexane (POX)
(4-2) Polyfunctional monomer (D-2)
Triallyl isocyanurate (TAIC)

[Examples 1 to 18 and Comparative Examples 1 to 6]
Using a twin-screw extruder, a thermoplastic polymer composition was produced by melt extrusion at 250 ° C. with the composition ratios shown in Tables 1 and 2. The production methods (1) to (5) in Tables 1 and 2 are as follows.
Production method (1): After the components (A) and (B) are melt-mixed, the component (C) is added and melt-mixed, and the component (D) is further added and melt-mixed.
Production method (2): After the components (A) and (B) are melt-mixed, the components (C) and (D) are added and melt-mixed.
Production method (3): After the components (A), (B) and (C) are melt-mixed, the component (D) is added and melt-mixed.
Production method (4): All components (A) to (D) are melt-mixed simultaneously.
Production method (5): After the components (A) and (B) are melt-mixed, the component (D) is added and melt-mixed, and the component (C) is further melt-mixed.

  From the thermoplastic polymer composition thus obtained, a 2 mm thick sheet molded product was produced using a T-die extruder, and various evaluations were performed. Here, as an evaluation of mechanical strength, the obtained thermoplastic polymer composition was added to the resin of component (B) blended in the composition, and Izod impact strength was measured. Specifically, it was melt-mixed at a mass ratio of (B) component / thermoplastic polymer composition = 90/10 and measured by the method described above. The measurement results are shown in Tables 1 and 2.

  The thermoplastic polymer composition obtained by the production method of the present invention includes automobile parts, automobile interior materials, automobile materials such as airbag covers, mechanical parts, electrical parts, cables, hoses, belts, toys, miscellaneous goods, It has industrial applicability to uses such as daily necessities, building materials, sheets, and films. Molding materials include foam molding materials, calendar molding materials, powder slush molding materials, multilayer molding materials, insert molding materials, coextrusion molding materials, injection molding materials, blow molding materials, extruded sheet molding materials, profile extrusion molding materials, Useful for fiber reinforced molding materials. Specifically, wallpaper, sealing material, edge material, waterproof sheet, tubular material, wire coating material, anti-slip material, cushioning material, swimming article, floor covering material, and the like, which play a large role in the industry.

Claims (6)

A method for producing a thermoplastic polymer composition comprising a crosslinkable polymer rubber (A), a thermoplastic resin (B), a thermoplastic polymer additive (C), and a crosslinker (D),
(I) a step of mixing the components (A), (B) and (C) to lower the glass transition temperature (Tg) of the resin composition comprising the components (A) and (B);
(Ii) The step of crosslinking the resin composition by mixing the crosslinking agent (D) simultaneously with the step (i) or following the step (i).
A method for producing a thermoplastic polymer composition, comprising:   The method for producing a thermoplastic polymer composition according to claim 1, wherein the component (A) is an aromatic vinyl-based thermoplastic polymer rubber.   The method for producing a thermoplastic polymer composition according to claim 2, wherein the aromatic vinyl-based thermoplastic polymer rubber is an aromatic vinyl-based random copolymer rubber and / or an aromatic vinyl-based block copolymer rubber.   The method for producing a thermoplastic polymer composition according to any one of claims 1 to 3, wherein the component (B) is a polyphenylene ether resin and / or an aromatic vinyl resin.   The method for producing a thermoplastic polymer composition according to claim 1, wherein the component (C) is a thermoplastic flame retardant.   The method for producing a thermoplastic polymer composition according to claim 5, wherein the thermoplastic flame retardant is a phosphorus-based flame retardant.