JP2007211184A - Thermoplastic elastomer composition and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for stably producing a thermoplastic elastomer composition which is excellent in a balance between mechanical characteristics such as flexibility and elastic recovery and molding processability. <P>SOLUTION: This method for producing the thermoplastic elastomer composition, comprising supplying a raw material composition comprising an un-cross-linked rubber, a thermoplastic resin, and a cross-linking agent into a raw material introduction portion of the continuous counter-rotating twin-screw kneader of an extruder manufactured by disposing the continuous counter-rotating twin-screw kneader on the upper flow side and a corotating twin-screw extruder on the downstream side in series, thereby mixing and dispersing the raw material composition with the continuous counter-rotating twin-screw kneader, and then supplying the kneaded product to the corotating twin-screw extruder with the continuous counter-rotating twin-screw kneader to produce the dynamically cross-linked thermoplastic elastomer composition, is characterized in that the cross-link degree Z of a cross-linked polymer component in the kneaded product at the exit of the extruder is 80 to 100%, and the cross-link degree Zi of a cross-linked polymer component in the kneaded product at the exit of the kneader is ≤85% of the cross-link degree Z. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a thermoplastic elastomer composition having an excellent balance between mechanical properties such as flexibility and elastic recovery and moldability. Moreover, this invention relates to the manufacturing method of the thermoplastic elastomer composition which can manufacture this thermoplastic elastomer composition stably.

  A thermoplastic elastomer composition obtained by dynamically heat-treating an uncrosslinked rubber and a polyolefin resin in the presence of a crosslinking agent can be easily processed into a molded product. This thermoplastic elastomer composition is widely used in various technical fields.

  The manufacturing method of this thermoplastic elastomer is disclosed by the following patent documents 1 and 2, for example. Patent Document 1 discloses a method of continuous production using two kneaders connected in series. Patent Document 2 discloses a method for producing a thermoplastic elastomer composition containing a crosslinked rubber having a small average particle size and a narrow particle size distribution. In this method, a mixing step of mixing and dispersing a raw material composition containing an uncrosslinked rubber and a polyolefin-based resin and a crosslinking step of dynamically crosslinking a kneaded product are successively performed. This method is characterized in that, before the crosslinking step, the temperature of the kneaded product obtained in the mixing step is controlled within ± 30 ° C. of the one-minute half-life temperature of the organic peroxide (crosslinking agent) used. To do.

JP-A-11-310646 JP 2002-201313 A

  In recent years, the development of a thermoplastic elastomer composition excellent in the balance between mechanical properties such as flexibility and elastic recovery and molding processability is equal to or higher than that of the thermoplastic elastomer composition produced by the above production method. It is desired. In addition, development of a method for producing this thermoplastic elastomer more stably is desired.

  The present invention has been made in view of the above circumstances. An object of the present invention is to provide a thermoplastic elastomer composition having an excellent balance between mechanical properties such as flexibility and elastic recovery and moldability. Moreover, an object of this invention is to provide the manufacturing method of the thermoplastic elastomer composition which can manufacture this thermoplastic elastomer composition stably.

The present invention is shown below.
(1) An uncrosslinked rubber (A), a thermoplastic resin (B), and a raw material composition containing a crosslinking agent (C) are rotated upstream in a continuous different-direction rotating biaxial kneader and downstream in the same direction. Supplied from the raw material introduction part of the continuous different-direction rotating twin-screw kneader of the extrusion device in which twin-screw extruders are arranged in series, and the raw material composition is mixed and dispersed by the continuous different-direction rotating twin-screw kneader. Thereafter, a kneaded product obtained by the continuous different-direction rotating twin-screw kneader is supplied to the same-direction rotating twin-screw extruder to obtain a dynamically crosslinked thermoplastic elastomer composition. The cross-linking degree Z of the cross-linked polymer component in the kneaded product at the outlet of the same-direction rotating twin-screw extruder is 80 to 100%, and the outlet of the continuous different-direction rotating twin-screw kneader is The degree of crosslinking Z _i of the crosslinked polymer component in the kneaded product is the degree of crosslinking Z The manufacturing method of the thermoplastic-elastomer composition characterized by being 85% or less of these.
(2) When the melting point of the thermoplastic resin (B) is Tm, the temperature of the kneaded material at the outlet of the continuous different-direction rotating biaxial kneader is Tm (° C.) or more and [Tm + 100] (° C.) or less. A method for producing a thermoplastic elastomer composition according to the above (1).
(3) the crosslinking agent (C) contains an organic peroxide, the melting point of the thermoplastic resin (B) Tm, when the one minute half-life temperature of the organic peroxide and T _h, the continuous The temperature of the kneaded material at the outlet of the two-direction rotating biaxial kneader is Tm (° C.) or more and [Tm + 100] (° C.) or less, and [T _h -30] (° C.) or more [T _h +30] ( C.) The method for producing a thermoplastic elastomer composition according to the above (1) or (2), which is:
(4) The kneaded product at the outlet of the continuous different-direction rotating twin-screw kneader has a phase structure in which the rubber component / thermoplastic resin is in the sea / island structure, and a phase in which the rubber component / thermoplastic resin is in the island / sea structure. The structure or the rubber component / thermoplastic resin each has a phase structure having a bicontinuous structure, and the kneaded product at the outlet of the same-direction rotating twin-screw extruder converts the cross-linked rubber component / thermoplastic resin into an island / sea. The manufacturing method of the thermoplastic elastomer composition in any one of said (1) thru | or (3) provided with the phase structure made into a structure.
(5) The method for producing a thermoplastic elastomer composition according to any one of (1) to (4), wherein a temperature of a cylinder of the continuous different-direction rotating twin-screw kneader is Tm (° C.) or less.
(6) The thermoplastic resin as described in any one of (1) to (5) above, wherein the temperature of the cylinder of the same-direction rotating twin-screw extruder is [Tm-30] (° C) or more and [Tm + 200] (° C) or less. A method for producing an elastomer composition.
(7) The thermoplastic resin (B) is a polyolefin resin, and the temperature of the kneaded material at the outlet of the continuous different-direction rotating biaxial kneader is Tm (° C.) or more and [Tm + 100] (° C.) or less, and the continuous And the difference between the temperature of the kneaded material at the outlet and the temperature of the cylinder is 100 ° C. or less, and the same direction rotating biaxial The temperature of the kneaded product at the exit of the extruder is [Tm + 10] (° C.) or more and [Tm + 200] (° C.) or less, and the temperature of the cylinder of the same-direction rotating twin screw extruder is [Tm−30] (° C.) or more [Tm + 200]. The thermoplastic elastomer composition according to any one of (1) to (6) above, wherein the difference between the temperature of the kneaded product at the outlet and the temperature of the cylinder is 100 ° C. or less. Production method.
(8) The melting point of the polyolefin-based resin is 60 to 200 ° C., the temperature of the kneaded material at the outlet of the continuous different-direction rotating biaxial kneader is 60 to 200 ° C., and the continuous different-direction rotating biaxial kneader. The temperature of the cylinder is 30 to 100 ° C., and the difference between the temperature of the kneaded product at the outlet and the temperature of the cylinder is 100 ° C. or less,
The temperature of the kneaded product at the outlet of the same-direction rotating twin-screw extruder is 70 to 400 ° C., the temperature of the cylinder of the same-direction rotating twin-screw extruder is 20 to 400 ° C., and the temperature of the kneaded product at the outlet The method for producing a thermoplastic elastomer composition according to claim 7, wherein a difference from the temperature of the cylinder is 100 ° C or less.
(9) The specific energy E1 of the continuous different-direction rotating twin-screw kneader is 0.01 to 2.0 kW · hr / kg, and the specific energy E2 of the same-direction rotating twin-screw extruder is 0.1 to 10 kW · hr. / Kg and the method for producing a thermoplastic elastomer composition according to any one of (1) to (8), wherein E1 <E2.
(10) The above (1) to (1), wherein the shearing force applied by the continuous different-direction rotating twin-screw kneader and the same-direction rotating twin-screw extruder is a shear rate of 100 to 20,000 / sec. (9) The method for producing a thermoplastic elastomer composition according to any one of (9).
(11) The thermoplastic elastomer composition according to any one of (1) to (10), wherein the uncrosslinked rubber (A) is a crumb-like and / or powdery uncrosslinked rubber. Production method.
(12) A thermoplastic elastomer composition obtained by the method according to any one of (1) to (11) above.

  According to the method for producing a thermoplastic elastomer composition of the present invention, a thermoplastic elastomer composition having a desired degree of crosslinking can be produced efficiently. Moreover, the thermoplastic elastomer composition excellent in the balance of mechanical properties and molding processability can be obtained by continuously carrying out mixing and dispersion of the above components and dynamic crosslinking.

  Since the thermoplastic elastomer composition of the present invention is dynamically cross-linked, it can be easily processed by injection molding, extrusion molding, hollow molding, compression molding, vacuum molding, laminate molding, calendar molding, and the like. When the thermoplastic elastomer composition of the present invention is used, a thermoplastic elastomer molded article having excellent mechanical properties such as rubber elasticity can be obtained.

Hereinafter, the present invention will be described in detail.
The method for producing a thermoplastic elastomer composition of the present invention comprises a raw material composition containing an uncrosslinked rubber (A), a thermoplastic resin (B), and a crosslinking agent (C). Supplied from the raw material introduction part of the twin-screw kneader and the continuous different-direction rotary twin-screw kneader of the extrusion device in which the same-direction rotary twin-screw extruder is arranged in series downstream, The raw material composition is mixed and dispersed by a shaft kneader, and then the kneaded product by the continuous different-direction rotating twin-screw kneader is supplied to the same-direction rotating twin-screw extruder, so that a dynamically crosslinked thermoplastic elastomer is obtained. A composition production method, wherein the cross-linking degree Z of the cross-linked polymer component in the kneaded product at the outlet of the same-direction rotating twin-screw extruder is 80 to 100%, and the continuous different-direction rotating twin-screw kneading is performed. The degree of crosslinking Z _i of the crosslinked polymer component in the kneaded product at the exit of the machine is: The crosslinking degree Z is 85% or less.

The degree of crosslinking Z and Z _i means the cyclohexane insoluble content of rubber. A method for measuring the insoluble content of cyclohexane in the rubber will be described later. The melting point Tm of the thermoplastic resin (B) is a melting point measured according to JIS K7121. When the said thermoplastic resin (B) contains 2 or more types of thermoplastic resins, said Tm shall be the higher one.

(1) Raw material composition The raw material composition used for the manufacturing method of the thermoplastic elastomer composition of this invention contains an uncrosslinked rubber (A), a thermoplastic resin (B), and a crosslinking agent (C).

(1-1) Uncrosslinked rubber (A)
As long as the uncrosslinked rubber (A) can form a crosslinked structure with a crosslinking agent, there is no particular limitation on the type and structure thereof. The uncrosslinked rubber (A) is used in a broad sense including an elastomer.

  Specific examples of the uncrosslinked rubber (A) include, for example, ethylene copolymer rubber (ethylene / α-olefin copolymer rubber, ethylene / acrylate rubber, etc.), diene rubber (isoprene rubber, butadiene rubber, styrene / butadiene). Rubber, natural rubber, chloroprene rubber, isobutylene-isoprene copolymer rubber (butyl rubber), norbornene rubber, 1,2-polybutadiene, etc.), nitrile rubber, hydrogenated nitrile rubber, acrylic rubber, fluorine rubber, chlorosulfonated polyethylene rubber , Epichlorohydrin rubber, silicone rubber, urethane rubber, polysulfide rubber, and phosphazene rubber. Of these, ethylene / α-olefin copolymer rubber is preferably used. Moreover, the said uncrosslinked rubber (A) may be used individually by 1 type, and may be used together 2 or more types.

  The “ethylene / α-olefin copolymer rubber” (hereinafter also simply referred to as “copolymer rubber”) is a monomer comprising an ethylene monomer unit and an α-olefin having 3 or more carbon atoms excluding ethylene. A copolymer containing units. The ethylene / α-olefin copolymer rubber may be used alone or in combination of two or more.

  The content of the ethylene monomer unit is preferably 30 to 95 mol%, more preferably 35 to 90 mol%, particularly preferably when the total amount of monomer units constituting the copolymer rubber is 100 mol%. Is 45 to 85 mol%. When the content of the ethylene monomer unit is within the above range, a thermoplastic elastomer composition having sufficient flexibility and mechanical strength can be obtained, which is preferable.

  Carbon number of the alpha olefin which comprises this copolymer rubber is 3-12 normally, Preferably it is 3-10, More preferably, it is 3-8. Specific examples of the α-olefin include propene (hereinafter referred to as “propylene”), 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, Examples include 4-methyl-1-pentene, 3-ethyl-1-pentene, 1-octene, 1-decene, and 1-undecene. The said alpha olefin may be used individually by 1 type, and may use 2 or more types together. Propylene, 1-butene, 1-hexene and 1-octene are preferable as the α-olefin, and propylene and 1-butene are more preferable.

  The content of the monomer unit composed of the α-olefin is preferably 5 to 55 mol%, more preferably 10 to 53 mol, when the total amount of the monomer units constituting the copolymer rubber is 100 mol%. %, Particularly preferably 15 to 45 mol%. It is preferable for the content of the α-olefin to be in the above range since a thermoplastic elastomer composition having the required rubber elasticity and high durability can be obtained.

  The copolymer rubber may further contain a monomer unit composed of a non-conjugated diene as necessary. Specific examples of the non-conjugated diene include (1) linear acyclic diene compounds such as 1,4-hexadiene, 1,5-hexadiene, and 1,6-hexadiene, and (2) 5-methyl- 1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, 5,7-dimethylocta-1,6-diene, 3,7-dimethyl-1,7-octadiene, 7-methylocta-1,6 -Diene and branched chain acyclic diene compounds such as dihydromyrcene, and (3) tetrahydroindene, methyltetrahydroindene, dicyclopentadiene, bicyclo [2.2.1] -hepta-2,5-diene, 5 -Methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, Beauty 5- cyclohexylidene-2-norbornene, alicyclic diene compounds such as 5-vinyl-2-norbornene. The said nonconjugated diene may be used individually by 1 type, and may use 2 or more types together. As the non-conjugated diene, 1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene and the like are preferable.

  The content of the monomer unit composed of the non-conjugated diene is preferably 0 to 15 mol%, more preferably 0 to 12 mol, when the total amount of monomer units constituting the copolymer rubber is 100 mol%. %, Particularly preferably 0 to 10 mol%.

  As the copolymer rubber, an ethylene / α-olefin binary copolymer, an ethylene / α-olefin / non-conjugated diene ternary copolymer, and a quaternary copolymer obtained by copolymerizing another monomer. Etc. are preferably used. The ethylene / α-olefin binary copolymer includes an ethylene / propylene binary copolymer (hereinafter referred to as “EPM”) and an ethylene / 1-butene binary copolymer (hereinafter simply referred to as “EBM”). ) Is particularly preferably used. Examples of the ethylene / α-olefin / non-conjugated diene terpolymer include ethylene / propylene / dicyclopentadiene terpolymer, ethylene / propylene / 5-ethylidene-2-norbornene terpolymer, An ethylene / 1-butene / dicyclopentadiene terpolymer and an ethylene / 1-butene / 5-ethylidene-2-norbornene terpolymer are particularly preferably used.

  As the copolymer rubber, in addition to the binary copolymer and the ternary copolymer, modified copolymers obtained by modifying these polymers can be used. Examples of the modified copolymer include a polymer in which a hydrogen atom of a polymer such as the binary copolymer and the ternary copolymer is substituted with a halogen atom, an epoxy group, or a carboxyl group, and the like. And polymers obtained by graft polymerization of various monomers. More specifically, for example, [1] a halogenated copolymer in which a part of hydrogen atoms of the polymer is substituted with a halogen atom such as a chlorine atom or a bromine atom, [2] ] Vinyl chloride, vinyl acetate, (meth) acrylic acid, derivatives of (meth) acrylic acid [methyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, etc.], maleic acid, maleic acid derivatives ( Unsaturated monomers such as maleic anhydride, maleimide, dimethyl maleate, etc.) and conjugated dienes (butadiene, isoprene, chloroprene, etc.) such as the above binary copolymer, the above terpolymer and the above halogenated copolymer, etc. And a graft copolymer obtained by graft polymerization with respect to. The above modified copolymers may be used alone or in combination of two or more.

  The intrinsic viscosity [η] (measured in decalin solvent at 135 ° C.) of the ethylene / α-olefin copolymer rubber is preferably 2.0 to 7.0 dl / g, more preferably 3.0 to 6 0.8 dl / g, more preferably 4.0 to 6.5 dl / g. It is preferable for the intrinsic viscosity to be within the above-mentioned range since a thermoplastic elastomer composition having the necessary rubber elasticity and molding processability can be obtained while suppressing the bleeding out of the mineral oil softener. The intrinsic viscosity [η] can be controlled within the above range by adjusting conditions such as the amount of catalyst and the amount of molecular weight regulator (for example, hydrogen) when the copolymer rubber is produced.

  The crystallinity of the ethylene / α-olefin copolymer rubber by X-ray diffraction is preferably 20% or less, more preferably 15% or less. It is preferable for the crystallinity to be in the above-mentioned range since a decrease in flexibility of the obtained molded part (A) can be suppressed.

  Furthermore, the iodine value of the ethylene / α-olefin copolymer rubber is preferably 5 to 30, more preferably 7 to 20. When the iodine value is in the above range, the crosslinking density in the obtained molded part (A) can be adjusted to an appropriate range, and the mechanical properties of the molded part (A) can be improved.

  The ethylene / α-olefin copolymer rubber can be obtained, for example, by a polymerization method using a medium / low pressure method. Specific examples of the polymerization method by the medium / low pressure method include, for example, monomers (ethylene and α-) in the presence of a catalyst comprising a Ziegler-Natta catalyst, a soluble vanadium compound, and an organic aluminum compound. Examples thereof include a method of polymerizing an olefin and, if necessary, a non-conjugated diene) while supplying hydrogen as a molecular weight regulator as necessary. The polymerization can also be carried out by a gas phase method (fluidized bed or stirred bed) or a liquid phase method (slurry method or solution method).

Specifically, for example, a reaction product of at least one of VOCl ₃ and VCl ₄ and an alcohol is preferably used as the soluble vanadium compound. Examples of the alcohol include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, t-butanol, n-hexanol, n-octanol, 2-ethylhexanol, n-decanol, and n-dodecanol. Of these, alcohols having 3 to 8 carbon atoms are preferably used.

  Specific examples of the organoaluminum compound include triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum. Examples thereof include dichloride, butylaluminum dichloride, and methylaluminoxane which is a reaction product of trimethylaluminum and water. Of these, ethyl aluminum sesquichloride, butyl aluminum sesquichloride, a mixture of ethyl aluminum sesquichloride and triisobutyl aluminum, and a mixture of triisobutyl aluminum and butyl aluminum sesquichloride are particularly preferably used.

  Furthermore, a hydrocarbon solvent is preferably used as the solvent. As the hydrocarbon solvent, n-pentane, n-hexane, n-heptane, n-octane, isooctane, and cyclohexane are particularly preferably used. The said solvent may be used individually by 1 type, and may use 2 or more types together.

  As the uncrosslinked rubber (A), an oil-extended rubber obtained by adding a mineral oil softener to the uncrosslinked rubber (A) can also be used. For example, an oil-extended rubber obtained by adding a mineral oil softener to the copolymer rubber can be used as the copolymer rubber. The oil-extended rubber is preferable because it is easy to handle in producing the thermoplastic elastomer composition of the present invention. The content ratios of the uncrosslinked rubber (A) and the mineral oil softener in the oil-extended rubber are each preferably 20 to 80% by mass, more preferably 25 to 75% by mass, and 30 It is especially preferable that it is -70 mass%. The mineral oil softener will be described later.

  There is no particular limitation on the form of the uncrosslinked rubber (A) (the copolymer rubber, the oil-extended rubber, etc.). The uncrosslinked rubber (A) may be in any form of bale, crumb, pellet, and powder (including a bale pulverized product). The “crumb” is crumb-like or granular rubber. As the crumb size, the number average particle diameter is 5 cm or less, more preferably 4 cm or less, and still more preferably 3 cm or less. The number average particle diameter is usually 0.01 mm or more, preferably 0.1 mm or more, more preferably 1 mm or more. The crumb having a number average particle size of 5 cm or less is preferable because the thermoplastic elastomer composition can be stably and quantitatively supplied to the different-direction continuous kneader during production. The powdered rubber may be a rubber in a state obtained by solidifying and drying the rubber, or may be a rubber obtained by mechanically pulverizing crumbs or bale rubber obtained by solidifying crumbs.

  When the sum total of the said uncrosslinked rubber (A) and the said thermoplastic resin (B) is 100 mass parts, the compounding quantity of this uncrosslinked rubber (A) is 20-95 mass parts, Preferably it is 40-94. The mass is more preferably 60 to 93 parts by mass. It is preferable for the amount of the uncrosslinked rubber (A) to be 20 parts by mass or more because the flexibility and elasticity of the resulting thermoplastic elastomer composition can be improved. Further, the blending amount of the uncrosslinked rubber (A) is preferably 95 parts by mass or less, since the fluidity of the finally obtained thermoplastic elastomer composition is improved and the molding processability can be improved.

(1-2) Thermoplastic resin (B)
Specific examples of the thermoplastic resin (B) include, for example, polyolefin resins; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, and polybutylene naphthalate; poly Acrylic resins such as methyl methacrylate; Styrene resins such as polystyrene and acrylonitrile / butadiene / styrene copolymers; Polyamide resins; Polycarbonate resins; Polyacetal resins; Urethane resins; Polyarylate resins; Polyphenylene ethers; Polyphenylene sulfides; Fluorine resins such as tetrafluoroethylene, polyvinyl fluoride, and polyvinylidene fluoride; polyether ketone and polyether agent Ketone resins such as ruketone; sulfone resins such as polysulfone and polyethersulfone; polyvinyl acetate; polyethylene oxide; polyvinyl alcohol; polyvinyl ether; polyvinyl butyral; vinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride; Etc. The ionomer resin includes units composed of ethylene units and unsaturated carboxylic acids (acrylic acid, methacrylic acid, maleic anhydride, etc.), and the carboxyl groups are polyvalent (Mg, Ca, Mn, Co, Ni, Cu, Zn). , Pb, etc.) and / or a resin neutralized at a predetermined ratio by monovalent (Li, Na, etc.) metal ions. The ionomer resin may contain other units (units composed of alkyl (meth) acrylate (methyl, ethyl, etc.) ester, vinyl acetate, etc.) as necessary. As the above-mentioned various resins, those usually used can be used. As said thermoplastic resin (B), polyolefin resin etc. are preferable. In addition, the said thermoplastic resin (B) can be used irrespective of the presence or absence of crystallinity. The said thermoplastic resin (B) may be used individually by 1 type, and may be used together 2 or more types.

  The polyolefin resin is not particularly limited in its structure and the like as long as it is a resin containing one or more units composed of olefins having 2 or more carbon atoms. The polyolefin resin may be a crystalline polyolefin resin alone, an amorphous polyolefin resin alone, or a combination of both. The polyolefin resin is preferably a combination of both.

  There is no particular limitation on the structure or the like of the above “crystalline polyolefin resin” (hereinafter, also simply referred to as “crystalline polymer (b1)”). As the crystalline polymer (b1), a polymer containing an α-olefin monomer unit as a main component is preferably used. That is, when the total amount of the monomer units constituting the crystalline polymer (b1) is 100 mol%, the α-olefin monomer units are contained in an amount of 80 mol% or more, more preferably 90 mol% or more. Polymers are preferred. The crystalline polymer (b1) may be an α-olefin homopolymer, a copolymer of two or more α-olefins, or a copolymer with a monomer that is not an α-olefin. Moreover, the mixture of these 2 or more types of different polymers and / or copolymers may be sufficient.

  As the α-olefin constituting the crystalline polymer (b1), it is preferable to use an α-olefin having 3 or more carbon atoms, and, like the copolymer rubber, 3 to 12 carbon atoms, preferably 3 to 10 carbon atoms. More preferably, it is more preferable to use 3 to 8 α-olefin. In the case where the crystalline polymer (b1) is a copolymer with ethylene, the content of the ethylene monomer unit when the total amount of the monomer units constituting the copolymer is 100 mol%. The amount is preferably 40 mol% or less (more preferably 20 mol% or less), that is, the content of the α-olefin monomer unit is preferably 60 mol% or more (more preferably 80 mol% or more).

  When the crystalline polymer (b1) is a copolymer, the copolymer may be a random copolymer or a block copolymer. However, in the case of a random copolymer, in order to obtain a copolymer having the following crystallinity, when the total amount of monomer units constituting the random copolymer is 100 mol%, a single amount excluding α-olefin The total content of body units is preferably 15 mol% or less, more preferably 10 mol% or less. Such a random copolymer can be obtained, for example, by the same method as that for the copolymer rubber. Moreover, in the block copolymer, in order to obtain a copolymer having the following crystallinity, when the total amount of units constituting the block copolymer is 100 mol%, monomer units other than α-olefin are included. The total content is preferably 40 mol% or less, more preferably 20 mol% or less. Such a block copolymer can be obtained by living polymerization using a Ziegler-Natta catalyst.

The crystalline polymer (b1) has crystallinity. This crystallinity can be expressed by the degree of crystallinity by X-ray diffraction measurement. The crystallinity of the crystalline polymer (b1) as measured by X-ray diffraction can be 50% or more, more preferably 53% or more, and still more preferably 55% or more. The crystallinity is closely related to the density. For example, in the case of polypropylene, the density of α-type crystal (monoclinic crystal) is 0.936 g / cm ³ , the density of smectic crystal (crystal quasi-hexagonal) is 0.886 g / cm ³ , and an amorphous (atactic) component The density of is 0.850 g / cm ³ . Furthermore, in the case of poly-1-butene, the density of the isotactic crystal component is 0.91 g / cm ^3, the density of the amorphous (atactic) component is 0.87 g / cm ^3. Therefore, when an attempt is made to obtain the crystalline polymer (b1) having a crystallinity of 50% or more, the density is 0.89 g / cm ³ or more (more preferably 0.90 to 0.94 g / cm ³ ). It is preferable. It is preferable that the crystallinity is 50% or more and the density is 0.89 g / cm ³ or more because a decrease in heat resistance and strength can be suppressed.

  The maximum peak temperature by differential scanning calorimetry of the crystalline polymer (b1), that is, the melting point is usually 100 ° C. or higher, preferably 120 ° C. or higher. The maximum peak temperature of the crystalline polymer (b1) by differential scanning calorimetry is a temperature measured according to JIS K7121. It is preferable for the melting point to be 100 ° C. or higher because the resulting thermoplastic elastomer composition exhibits sufficient heat resistance and strength. Moreover, although the said melting | fusing point changes with the monomers comprised, it is preferable that it is 120 degreeC or more. When two or more crystalline polymers (b1) are included, the “melting point” is an average temperature calculated from the content and melting point of each component.

  The melt flow rate (hereinafter simply referred to as “MFR”) of the crystalline polymer (b1) at a temperature of 230 ° C. and a load of 2.16 kg is usually 0.1 to 100 g / 10 minutes, preferably 0.5 to 80 g / 10 min. When the MFR is 0.1 g / 10 min or more, the kneadability and extrusion processability of the resulting thermoplastic elastomer composition will be sufficient, which is preferable. On the other hand, when the MFR is 100 g / 10 min or less, a decrease in strength of the resulting thermoplastic elastomer composition can be suppressed, which is preferable.

Accordingly, the crystalline polymer (b1) has a crystallinity of 50% or more, a density of 0.89 g / cm ³ or more, an ethylene unit content of 20 mol% or less, a Tm of 100 ° C. or more, and an MFR of It is particularly preferable to use polypropylene and / or a copolymer of propylene and ethylene having a melting point of 140 to 170 ° C. for 0.1 to 100 g / 10 minutes.

  There is no particular limitation on the structure or the like of the above “amorphous polyolefin resin” (hereinafter also simply referred to as “amorphous polymer (b2)”). As the amorphous polymer (b2), a polymer containing an α-olefin monomer unit as a main component is preferably used. That is, when the total amount of monomer units constituting the amorphous polymer (b2) is 100 mol%, the α-olefin monomer unit is contained in an amount of 50 mol% or more, more preferably 60 mol% or more. Preferred is a polymer. The amorphous polymer (b2) may be a homopolymer of α-olefin, a copolymer of two or more α-olefins, or a copolymer with a monomer that is not an α-olefin. . Moreover, the mixture of 2 or more types of these different polymers and / or copolymers may be sufficient.

  As the α-olefin constituting the amorphous polymer (b2), an α-olefin having 3 or more carbon atoms is preferably used. Like the copolymer rubber, the α-olefin has 3 to 12 carbon atoms, preferably 3 to 3 carbon atoms. More preferably, an α-olefin of 10, more preferably 3-8 is used.

  Specific examples of the amorphous polymer (b2) include homopolymers such as atactic polypropylene and atactic poly-1-butene, propylene (containing 50 mol% or more), and other α-olefins (ethylene). , 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, etc.), and 1-butene (containing 50 mol% or more) and other and copolymers with α-olefins (ethylene, propylene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, etc.). Examples of the amorphous polymer (b2) include atactic polypropylene (propylene content 50 mol% or more), a copolymer of propylene (50 mol% or more) and ethylene, and a copolymer of propylene and 1-butene. It is particularly preferable to use This atactic polypropylene can be obtained as a by-product of polypropylene that can be used as the crystalline polymer (b1). Atactic polypropylene and atactic poly-1-butene can also be obtained by polymerization using a zirconocene compound-methylaluminoxane catalyst.

  When the crystalline polymer (b2) is a copolymer, the copolymer may be a random copolymer or a block copolymer. However, in the case of a block copolymer, the α-olefin monomer unit as a main component (in the above copolymer, propylene unit, 1-butene unit) needs to be bonded with an atactic structure. Further, when the amorphous copolymer (b2) is a copolymer of an α-olefin having 3 or more carbon atoms and ethylene, the total amount of monomer units constituting the amorphous copolymer (b2) Is 100 mol%, the content of the α-olefin monomer unit is preferably 50 mol% or more, more preferably 60 to 100 mol%. The random copolymer can be obtained by the same method as that for the copolymer rubber. The block copolymer can be obtained by living polymerization using a Ziegler-Natta catalyst.

The melt viscosity at 190 ° C. of the amorphous polymer (b2) is preferably 50 Pa · s or less, more preferably 0.1 to 30 Pa · s, and still more preferably 0.2 to 20 Pa · s. When the viscosity is 50 Pa · s or less, it is preferable that the adhesive strength with the adherend can be suppressed when injection-sealing with a vulcanized rubber or a thermoplastic elastomer. The crystallinity of the amorphous polymer (b2) by X-ray diffraction measurement is preferably less than 50%, more preferably 30% or less, and still more preferably 20% or less. This crystallinity is closely related to the density as described above. The density is preferably 0.85 to 0.89 g / cm ³ , more preferably 0.85 to 0.88 g / cm ³ . Furthermore, the number average molecular weight M _n of the amorphous polymer (b2) is preferably 1000 to 20000, more preferably 1500 to 15000. When the melt viscosity is 50 Pa · s or less, when the crystallinity is 50% or less, and when the density is 0.89 g / cm ³ or less, when the resin is injection-fused with vulcanized rubber or thermoplastic elastomer, Since it can suppress that the adhesive strength with a kimono body falls, it is preferable.

  When the total amount of the uncrosslinked rubber (A) and the thermoplastic resin (B) is 100 parts by mass, the amount of the thermoplastic resin (B) is preferably 5 to 80 parts by mass, more preferably It is 6-60 mass parts, More preferably, it is 7-40 mass parts. When the blending amount of the thermoplastic resin (B) is 5 parts by mass or more, the phase structure (morphology) of the finally obtained thermoplastic elastomer composition is a good sea / It is preferable because it has an island structure (thermoplastic resin is the sea (matrix) and cross-linked rubber is the island (domain)), and the molding processability and mechanical properties can be improved. On the other hand, when the amount of the thermoplastic resin (B) is 80 parts by mass or less, the flexibility and rubber elasticity of the resulting thermoplastic elastomer composition can be improved, which is preferable.

(1-3) Crosslinking agent (C)
The crosslinking agent (C) is not particularly limited as long as it can crosslink at least the uncrosslinked rubber (A). Specific examples of the crosslinking agent (C) include organic peroxides, phenol resins, sulfur, sulfur compounds, p-quinones, p-quinone dioxime derivatives, bismaleimide compounds, epoxy compounds, silane compounds, amino acids, and the like. Examples thereof include resins, polyols, polyamines, triazine compounds, and metal soaps. The said crosslinking agent (C) may be used individually by 1 type, and may use 2 or more types together. As said crosslinking agent (C), an organic peroxide and / or a phenol resin are preferable, and an organic peroxide is especially preferable.

The organic peroxide is 1 minute half-life temperature T _h is, Tm organic peroxide is in the range of (the thermal melting point of the thermoplastic resin _{(B)) ≦ T h ≦} Tm + 90 (℃) are preferred. When the T _h is above Tm above, the Ri melt kneading uncrosslinked rubber (A) and the thermoplastic resin (B) but starts crosslinking reaction since sufficiently performed, the uncrosslinked rubber (A) Since it can fully bridge | crosslink, the rubber elasticity and mechanical strength of the thermoplastic elastomer composition obtained can be improved.

  Specific examples of the organic peroxide include 1,3-bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexene-3, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, 2,2'-bis (t-butylperoxy) -p-isopropylbenzene, dicumyl peroxide, di-t-butylper Oxide, t-butyl peroxide, p-menthane peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, dilauroyl peroxide, diacetyl peroxide, t-butylperoxy Benzoate, 2,4-dichlorobenzoyl peroxide, p-chlorobenzoyl peroxide, benzoyl peroxide, di (t-butyl Rupaokishi) perbenzoate, n- butyl-4,4-bis (t-butylperoxy) valerate, t- butyl peroxy isopropyl carbonate. As the organic peroxide, an organic peroxide having a relatively high decomposition temperature is preferably used. Examples of the organic peroxide having a relatively high decomposition temperature include 1,3-bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne- 3,2,5-dimethyl-2,5-di (t-butylperoxy) hexane and the like. In addition, the said organic peroxide may be used individually by 1 type, and may use 2 or more types together.

  When an organic peroxide is used as the crosslinking agent (C), the amount used is 0.05 to 10 with respect to a total of 100 parts by mass of the uncrosslinked rubber (A) and the thermoplastic resin (B). It can be made into a mass part, Preferably it is 0.1-5 mass part. When the amount of the organic peroxide used is 0.05 parts by mass or more, the degree of crosslinking can be increased, and the rubber elasticity and mechanical strength of the finally obtained thermoplastic elastomer composition can be improved. Moreover, the molding processability and mechanical physical property of the thermoplastic elastomer finally obtained can be improved as the usage-amount of the said phenol resin is 10 mass parts or less.

  Furthermore, when the said crosslinking agent (C) contains an organic peroxide, a crosslinking reaction advances gently by using together with a crosslinking adjuvant, and especially uniform bridge | crosslinking can be formed. Examples of the crosslinking aid include sulfur or sulfur compounds (powder sulfur, colloidal sulfur, precipitated sulfur, insoluble sulfur, surface-treated sulfur, dipentamethylene thiuram tetrasulfide, etc.), oxime compounds (p-quinone oxime, p, p′- Dibenzoylquinone oxime) and multifunctional monomers (ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di) (Meth) acrylate, trimethylolpropane tri (meth) acrylate, diallyl phthalate, tetraallyloxyethane, triallyl cyanurate, N, N′-m-phenylene bismaleimide, N, N′-toluylene bismaleimi , Maleic anhydride, divinylbenzene, di (meth) zinc acrylate and the like) and the like. In particular, p, p'-dibenzoylquinone oxime, N, N'-m-phenylenebismaleimide, and divinylbenzene are preferably used as the crosslinking aid. The said crosslinking adjuvant may be used individually by 1 type, and may use 2 or more types together. Of the above-mentioned crosslinking aids, N, N′-m-phenylenebismaleimide has an action as a crosslinking agent, and therefore can be used as the crosslinking agent (C).

  The amount of the crosslinking aid used is 10 parts by mass or less, preferably 0.2 to 10 parts by mass, more preferably 100 parts by mass in total of the uncrosslinked rubber (A) and the thermoplastic resin (B). Is 0.2-5 parts by mass. By making the usage-amount of the said crosslinking adjuvant into the said range, a crosslinking degree can be made into an appropriate range. As a result, it is possible to suppress the deterioration of molding processability and the deterioration of mechanical properties of the obtained thermoplastic elastomer composition.

  Specific examples of the phenol resin include p-substituted phenol compounds represented by the following general formula (I), o-substituted phenol-aldehyde condensates, m-substituted phenol-aldehyde condensates, and brominated alkylphenols. Examples include aldehyde condensates. As the phenol resin, a p-substituted phenol compound is particularly preferably used. The p-substituted phenol compound is obtained by a condensation reaction between a p-substituted phenol and an aldehyde (preferably formaldehyde) in the presence of an alkali catalyst. In addition, the said phenol resin may be used individually by 1 type, and may be used together 2 or more types.

  In said general formula (I), n is an integer of 0-10. X is at least one of a hydroxyl group, a halogenated alkyl group, and a halogen atom. R is a saturated hydrocarbon group having 1 to 15 carbon atoms.

  The usage-amount of the said phenol resin becomes like this. Preferably it is 0.2-10 mass parts with respect to 100 mass parts of said raw material compositions, More preferably, it is 0.5-5 mass parts. If the amount of the phenol resin used is 0.2 parts by mass or more, the degree of crosslinking can be increased, and the rubber elasticity and mechanical strength of the finally obtained thermoplastic elastomer composition can be improved. Moreover, the moldability of the thermoplastic elastomer finally obtained can be improved as the usage-amount of the said phenol resin is 10 mass parts or less.

  Although the said phenol resin can be used individually, in order to adjust a crosslinking rate, a crosslinking accelerator can be used together. Examples of the crosslinking accelerator include metal halides (such as stannous chloride and ferric chloride), organic halides (such as chlorinated polypropylene, butyl bromide rubber, and chloroprene rubber). In addition to the crosslinking accelerator, it is more desirable to use a metal oxide such as zinc oxide or a dispersant such as stearic acid.

(1-4) Additives The raw material composition used in the method for producing the thermoplastic elastomer composition of the present invention may contain other additives as necessary as long as the performance is not impaired. Examples of the additives include softeners, anti-aging agents, lubricants, fillers, ultraviolet absorbers, fluorine powders, silicone powders, pigments, processing aids, mold release agents, flame retardants, antistatic agents, and antifungal agents. 1 type, or 2 or more types, such as a coloring agent and a heat stabilizer. These contents will be described later.

(2) Method for Producing Thermoplastic Elastomer Composition In the present invention, a continuous different-direction rotating twin-screw kneader (hereinafter also referred to as “upstream-side kneader”) upstream, and a same-direction rotating twin-screw extruder downstream ( Hereinafter, an extrusion apparatus in which “downstream side extruders”) are arranged in series is used. In the present invention, the raw material composition supplied to the raw material introduction portion of the upstream kneader is mixed and dispersed, and then the kneaded product is supplied to the downstream extruder to dynamically crosslink. The term “dynamically cross-linking” refers to performing cross-linking by applying both shearing force and heating.

  The continuous different-direction rotating biaxial kneader is an apparatus in which a rotor, a screw, a paddle (feed and return), a disk, and the like are arranged on a kneading shaft in a cylinder. The cylinder may include a heating device and a cooling device. The continuous different-direction rotating twin-screw kneader includes a type in which two screws are engaged and a type in which the two screws are not engaged. Any type of kneader may be used. In this kneader, the ratio (L / D) between the effective screw length L and the outer diameter D is preferably 2 to 20, more preferably 2 to 15. Examples of the continuous different-direction rotating twin-screw kneader include commercially available high-speed twin-screw continuous mixer “CIM” (trade name) manufactured by Nippon Steel Works and “Mixtron FCM / NCM / LCM” manufactured by Kobe Steel. / ACM "(trade name) or the like can be used.

  The same-direction rotating twin-screw extruder is an apparatus having a cylinder, a hopper, a vent port, and the like in which a screw is disposed on an internal rotating shaft. The same-direction rotating twin-screw extruder can include a heating device and a cooling device. The same-direction rotating twin-screw extruder includes a type in which two screws mesh with each other and a type in which they do not mesh with each other, but any type of extruder may be used. Moreover, in this extruder, ratio (L / D) of the screw effective length L and the outer diameter D becomes like this. Preferably it is 30 or more, More preferably, it is 36-60. Examples of the above-mentioned co-rotating twin-screw extruder include commercially available “GT / PCM series” (trade name) manufactured by Ikekai Co., Ltd., “KTX” (trade name) manufactured by Kobe Steel Co., Ltd., manufactured by Nippon Steel Works, Ltd. “TEX” (trade name), “TEM” (trade name) manufactured by Toshiba Machine Co., Ltd., “ZSK” (trade name) manufactured by Warner Corporation, and the like can be used.

  In the extrusion apparatus, the upstream kneader and the downstream extruder may be directly connected without being connected. In addition, the upstream kneader and the downstream extruder may be connected by a transfer pipe, and are connected by a twin-screw cone screw feeder disposed between the upstream kneader and the downstream extruder. May be. The upstream-side kneader and the downstream-side extruder are usually connected by a transfer pipe. The length of the transfer pipe is usually 5 m or less, preferably about 0.3 to 3 m. The transfer pipe is preferably a closed system. Moreover, the said piping for conveyance may be provided with a heating apparatus and a cooling device.

  In the present invention, the raw material composition is usually obtained by previously mixing each predetermined amount of the raw material components. The mixing method is not particularly limited. The mixing method can be selected depending on the properties (crumb shape, veil shape, etc.) of the uncrosslinked rubber (A), the crosslinking agent, the crosslinking aid, and the like. Examples of the mixing method include mixing with a Henschel mixer, a drum tumbler, and the like.

  There is no particular limitation on the method of charging the raw material composition into the upstream kneader. For example, all of the raw material composition may be charged simultaneously, or the raw material composition may be divided (such as intermittently) and charged. In the upstream kneader, after the raw material composition is charged, sufficient agitation is performed with high shearing force by the paddle as the kneading shaft and the rotor rotate. As a result, a kneaded product in which the uncrosslinked rubber (A) and the crosslinking agent (C) are highly finely dispersed can be obtained.

  You may perform mixing and dispersion | distribution of the said raw material composition in the said upstream kneader, heating a cylinder. However, when the raw material composition is mixed and dispersed, the temperature of the mixture rises due to frictional heat of the raw material components contained in the raw material composition without heating. And when the temperature of a mixture rises too much, the crosslinking reaction rate by the said crosslinking agent (C) will become large, and the crosslinking degree of a crosslinkable polymer component will become high too much. Therefore, when mixing and dispersing the raw material composition in the upstream kneader, the cylinder is usually cooled. Specifically, for example, the temperature of the cylinder of the upstream side kneader is preferably Tm (° C) or less, more preferably [Tm-10] (° C) or less, and further preferably [Tm-20] (° C) or less. (Normally 30 ° C or higher).

  The kneading time of the raw material composition in the upstream kneader is the kind of the uncrosslinked rubber (A), the thermoplastic resin (B), the crosslinking agent (C), etc., and the throughput of the raw material composition. And the volume of the cylinder, the number of rotations of the rotor, the kneading temperature, the specific energy, and the like.

  The specific energy (value obtained by dividing the drive power (kW) by the extrusion amount (kg / hr)) E1 of the upstream kneader is preferably 0.01 to 2.0 kW · hr / kg, more preferably 0.05. It is -1.5kW * hr / kg, More preferably, it is 0.1-1.0kW * hr / kg. It is preferable that E1 is in the above range because productivity is improved, mixing and dispersibility is improved, and the discharge amount on the downstream side of the extruder is stabilized.

  The temperature of the kneaded product at the outlet of the upstream kneader is preferably Tm (° C.) or more and [Tm + 100] (° C.) or less, more preferably Tm (° C.) or more and [Tm + 90] (° C.) or less, and more preferably Tm ( ° C) to [Tm + 80] (° C). If the said temperature is less than Tm (degreeC), the said unmelted said thermoplastic resin (B) may mix in a composition, and mixing dispersibility may deteriorate. On the other hand, when the said temperature exceeds [Tm + 100] (degreeC), the mechanical physical property of the thermoplastic elastomer composition obtained may deteriorate. Specifically, the temperature of the kneaded product at the outlet of the upstream kneader can be set to, for example, 60 to 300 ° C (preferably 70 to 280 ° C, particularly preferably 80 ° C to 250 ° C). The temperature of the kneaded product at the outlet of the upstream kneader depends on the Tm of the thermoplastic resin (B) used. More specifically, for example, when a polyolefin resin, particularly a polyolefin resin having a Tm of 60 to 200 ° C. is used as the thermoplastic resin (B), the temperature of the kneaded product at the outlet of the upstream kneader is It can be a range.

  The temperature of the kneaded material at the outlet of the upstream side kneader can be in a certain range in relation to the temperature of the cylinder of the upstream side kneader. In the present invention, the difference between the temperature of the kneaded product at the outlet of the upstream side kneader and the temperature of the cylinder of the upstream side kneader is 100 ° C. or less (preferably 95 ° C. or less, particularly preferably 90 ° C. or less [for example, 0 to 90 ° C]). The “difference between the temperature of the kneaded product at the outlet of the upstream kneader and the temperature of the cylinder of the upstream kneader” refers to the temperature of the kneaded product at the outlet of the upstream kneader. The value minus the temperature. For example, in the present invention, the temperature of the kneaded product at the outlet of the upstream side kneader is 60 to 200 ° C. (preferably 70 to 180 ° C., particularly preferably 80 ° C. to 150 ° C.), and the temperature of the cylinder of the upstream side kneader. 30 to 100 ° C. (preferably 35 to 95 ° C., particularly preferably 40 to 90 ° C.), and the difference between the temperature of the kneaded material at the outlet of the upstream kneader and the temperature of the cylinder of the upstream kneader is 100 Or less (preferably 95 ° C. or less, particularly preferably 90 ° C. or less). More specifically, for example, when a polyolefin resin, particularly a polyolefin resin having a Tm of 60 to 200 ° C. is used as the thermoplastic resin (B), the kneaded material at the outlet of the upstream kneader, the upstream The difference between the temperature of the cylinder of the side kneader and the temperature of the kneaded material at the outlet of the upstream kneader and the temperature of the cylinder of the upstream kneader can be in the above range.

  The kneaded product at the outlet of the upstream side kneader includes the types of the uncrosslinked rubber (A), the thermoplastic resin (B), the crosslinker (C), etc., and the throughput and kneading conditions of the raw material composition. Etc. to form various phase structures. In the present invention, the kneaded product at the outlet of the upstream side kneader is composed of a rubber component containing the uncrosslinked rubber (A) and the crosslinked rubber and the thermoplastic resin (B). , And a phase structure of either of the two continuous structures is formed (schematic diagrams of each structure are shown in FIGS. 1A, 1B, and 1C). In addition, the shape and size of the portion corresponding to the island in the phase structure are not particularly limited, but the shape is usually spherical, elliptical, rod-like, or the like.

  Thereafter, the kneaded product is introduced into the downstream extruder. For example, in an extrusion apparatus in which the upstream kneader and the downstream extruder are connected by a conveying pipe, the upstream kneader and the downstream extruder are introduced into the downstream extruder through the conveying pipe.

  The temperature of the cylinder of the downstream extruder is preferably [Tm-30] (° C) or more and [Tm + 200] (° C) or less, more preferably [Tm-20] (° C) or more and [Tm + 180] (° C) or less. More preferably, it can be controlled to [Tm−10] (° C.) or more and [Tm + 150] (° C.) or less. If the said temperature is [Tm-30] (degreeC) or more, mixing dispersibility can be improved. Moreover, the thermal deterioration of the obtained thermoplastic elastomer can be suppressed as the said temperature is [Tm + 200] (degreeC) or less.

  The specific energy E2 of the downstream extruder is preferably 0.1 to 10 kW · hr / kg, more preferably 0.15 to 8.0 kW · hr / kg, and still more preferably 0.2 to 6.0 kW · hr. / Kg. It is preferable that E2 is within the above range because productivity is improved, mixing and dispersibility is improved, and the discharge amount on the downstream side of the extruder is stabilized. In the present invention, E2 can be larger than E1 (E1 <E2). This is preferable because a kneaded material in which the raw material composition is well dispersed can be obtained.

  The temperature of the kneaded material at the outlet of the downstream extruder is preferably [Tm + 30] (° C.) or more and [Tm + 200] (° C.) or less, more preferably [Tm + 40] (° C.) or more and [Tm + 180] (° C.) or less. It is preferably [Tm + 50] (° C.) or more and [Tm + 150] (° C.) or less. By making the said temperature into the said range, since the thermal deterioration of a kneaded material can be suppressed, it is preferable. Specifically, as the temperature of the kneaded product at the outlet of the downstream extruder, for example, in the present invention, the temperature of the kneaded product at the outlet of the downstream extruder is set to 70 to 400 ° C. (preferably 80 to 350 ° C., particularly Preferably it can be set to 100-300 degreeC. Moreover, the temperature of the kneaded material at the outlet of the downstream extruder also depends on the Tm of the thermoplastic resin (B) used. More specifically, for example, when a polyolefin resin, particularly a polyolefin resin having a Tm of 60 to 200 ° C. is used as the thermoplastic resin (B), the temperature of the kneaded material at the outlet of the downstream extruder is set to It can be a range.

  The temperature of the kneaded material at the outlet of the downstream extruder can be set within a certain range in relation to the temperature of the cylinder of the downstream extruder. In the present invention, the difference between the temperature of the kneaded product at the outlet of the downstream extruder and the temperature of the cylinder of the downstream extruder is 100 ° C. or less (preferably 95 ° C. or less, particularly preferably 90 ° C. or less [for example, 0 to 90 ° C]). The difference between the temperature of the kneaded product at the outlet of the downstream extruder and the temperature of the cylinder of the downstream extruder is determined from the temperature of the kneaded product at the outlet of the downstream extruder from the temperature of the cylinder of the downstream extruder. The value minus the temperature. For example, in the present invention, the temperature of the kneaded product at the outlet of the downstream extruder is 70 to 400 ° C. (preferably 80 to 350 ° C., particularly preferably 100 to 300 ° C.), and the temperature of the cylinder of the downstream extruder is 20 to 400 ° C. (preferably 50 to 380 ° C., particularly preferably 80 to 350 ° C.), and the difference between the temperature of the kneaded material at the outlet of the downstream extruder and the temperature of the cylinder of the downstream extruder is 100 ° C. Or less (preferably 95 ° C. or less, particularly preferably 90 ° C. or less [eg, 0 to 90 ° C.]). More specifically, for example, when a polyolefin resin, particularly a polyolefin resin having a Tm of 60 to 200 ° C. is used as the thermoplastic resin (B), the kneaded material at the outlet of the downstream extruder, the downstream The difference between the temperature of the cylinder of the side extruder and the temperature of the kneaded material at the outlet of the downstream side extruder and the temperature of the cylinder of the downstream side extruder can be within the above range.

  The shearing force applied by the upstream kneader and the downstream extruder is preferably 100 to 20,000 / second, more preferably 150 to 15,000 / second in terms of shear rate, and more preferably 200 -10,000 / sec are preferable. It is preferable that the shear rate is in the above range because the mechanical strength of the resulting thermoplastic elastomer composition can be improved.

  In the present invention, in order to obtain a thermoplastic elastomer composition having excellent performance, the specific energies of the upstream kneader and the downstream extruder, the cylinder temperature, the outlet temperature, and the like can be appropriately combined. By appropriately combining the above elements, the production method of the present invention can be made a production method more suitable for the purpose and effect.

In the present invention, the crosslinking degree Z of the crosslinked polymer component in the kneaded product at the outlet of the downstream extruder is 80 to 100%, preferably 85 to 100%, particularly preferably 90 to 100%, and the upstream side. The crosslinking degree Z _i of the crosslinked polymer component in the kneaded product at the outlet of the kneader is 85% or less, preferably 80% or less, particularly preferably 75% or less (for example, 30 to 75%) of the crosslinking degree Z. . If the degree of crosslinking Z is less than 80%, the resulting thermoplastic elastomer composition tends to be inferior in rubber elasticity and mechanical strength, which is not preferable. On the other hand, if the degree of crosslinking Z _i exceeds 85% of the degree of crosslinking Z, the rubber component in the thermoplastic elastomer composition becomes a coarse crosslinked gel, which may undesirably deteriorate the appearance of the molded product.

The crosslinking degree Z and Z _i mean the cyclohexane insoluble content of the rubber, and the method for measuring the cyclohexane insoluble content is as follows.
About 200 mg of the obtained thermoplastic elastomer composition is weighed and finely cut. The resulting strip is then immersed in 100 ml cyclohexane at 23 ° C. for 48 hours in a sealed container. The sample after the immersion is taken out on a filter paper and dried under reduced pressure at 105 ° C. for 1 hour in a vacuum dryer. The cyclohexane insoluble content is obtained by the following formula from the dry residue mass obtained by subtracting the mass of the cyclohexane insoluble component such as the thermoplastic resin and filler from the dry residue mass and the theoretical rubber mass in the sample before immersion.
Cyclohexane insoluble matter [mass%] = [dry residue mass ÷ theoretical rubber mass before immersion] × 100

In the present invention, specific combinations of operating conditions of the upstream side kneader and the downstream side extruder are, for example, as follows (1) to (5).
(1) Upstream side kneader: the temperature of the kneaded product at the outlet is 60 to 200 ° C (preferably 70 to 180 ° C, particularly preferably 80 to 150 ° C), and the cylinder temperature is 30 to 100 ° C (preferably 35 to 95 ° C). The difference between the temperature of the kneaded product at the outlet and the cylinder temperature is 100 ° C. or less (preferably 95 ° C. or less, particularly preferably 90 ° C. or less [eg, 0 to 90 ° C.]). .
Downstream extruder: the temperature of the kneaded product at the outlet is 70 to 400 ° C (preferably 80 to 350 ° C, particularly preferably 100 to 300 ° C), and the cylinder temperature is 20 to 400 ° C (preferably 50 to 380 ° C, particularly preferably). 80 to 350 ° C.) and the difference between the temperature of the kneaded product at the outlet and the cylinder temperature is 100 ° C. or less (preferably 95 ° C. or less, particularly preferably 90 ° C. or less [eg 0 to 90 ° C.]).
The numbers outside the parentheses can be combined with the numbers within the parentheses as appropriate.
(2) The following operating conditions can be further combined with the operating conditions of (1) above.
Specific energy E1 of the upstream kneader is 0.01 to 2.0 kW · hr / kg (preferably 0.05 to 1.5 kW · hr / kg, particularly preferably 0.1 to 1.0 kW · hr / kg). A downstream extruder; specific energy E2 of 0.1 to 10 kW · hr / kg (preferably 0.15 to 8.0 kW · hr / kg, particularly preferably 0.2 to 6.0 kW · hr / kg) ) And E1 <E2.
The numbers outside the parentheses can be combined with the numbers within the parentheses as appropriate.
(3) The following operating conditions can be further combined with the above operating conditions (1) and / or (2).
The shearing force applied by the upstream side kneader and the downstream side extruder is 100 to 20,000 / second (preferably 150 to 15,000 / second, more preferably 200 to 10,000 / second) in terms of shear rate.
The numbers outside the parentheses can be combined with the numbers within the parentheses as appropriate.
(4) The following operating conditions can be further combined with one or two or more of the above operating conditions (1) to (3).
The thermoplastic resin is a polyolefin-based resin as described above, and its Tm is 60 to 200 ° C, preferably 70 to 200 ° C.
(5) The following operating conditions can be further combined with one or two or more of the above operating conditions (1) to (4).
The crosslinking degree Z of the crosslinked polymer component in the kneaded product at the outlet of the downstream extruder is 80 to 100% (preferably 85 to 100%, particularly preferably 90 to 100%), and at the outlet of the upstream kneader. The degree of crosslinking Z _i of the crosslinked polymer component in the kneaded product is 85% or less (preferably 80% or less, particularly preferably 75% or less) of the degree of crosslinking Z.
The numbers outside the parentheses can be combined with the numbers within the parentheses as appropriate.

  In the method for producing a thermoplastic elastomer composition of the present invention, the thermoplastic elastomer composition obtained is a cross-linked rubber regardless of the phase structure of any of the three types described above at the outlet of the upstream kneader. And the thermoplastic resin have a phase structure that is an island / sea structure. In particular, when the kneaded product at the outlet of the upstream side kneader has a phase structure in which the rubber component including the uncrosslinked rubber and the crosslinked rubber and the thermoplastic resin have a sea / island structure, the phase is inverted. Has extremely excellent performance.

(3) Thermoplastic elastomer composition The thermoplastic elastomer composition of the present invention is obtained by the method for producing a thermoplastic elastomer composition of the present invention. As described above, the thermoplastic elastomer composition of the present invention has a phase structure in which the crosslinked rubber and the thermoplastic resin have an island / sea structure. The thermoplastic elastomer composition of the present invention is excellent in the balance between mechanical properties such as flexibility and elastic recovery and molding processability.

  The thermoplastic elastomer composition of the present invention may contain other additives as required. Examples of the additives include softeners, anti-aging agents, lubricants, fillers, ultraviolet absorbers, fluorine powders, silicone powders, pigments, processing aids, mold release agents, flame retardants, antistatic agents, and antifungal agents. 1 type, or 2 or more types, such as a coloring agent and a heat stabilizer. There is no limitation in particular in the method of making the thermoplastic elastomer composition of this invention contain the said additive. Usually, the said additive can be contained by mix | blending and manufacturing the said additive in the said raw material composition. Moreover, the said additive can be contained by supplying and manufacturing to the said upstream kneading machine or the said downstream extruder separately from the said raw material composition.

  There is no limitation in particular in the kind of said softening agent. Specific examples of the softener include vegetable oil (palm oil, castor oil, linseed oil, rapeseed oil, soybean oil, etc.), esters of fatty acids and higher alcohols (phthalic diesters such as dioctyl phthalate, dioctyl, etc.) Adipate, dioctyl sebacate, etc.), waxes (honey wax, carnauba wax, lanolin, etc.), phosphate triesters, mineral oils (paraffinic mineral oil, naphthenic mineral oil, aromatic mineral oil), polymeric substances ( Petroleum resin, coumarone indene resin, atactic polypropylene, etc.). Examples of the mineral oil include process oil, lubricating oil, petroleum asphalt, and petroleum jelly. The said softener may be used individually by 1 type, and may use 2 or more types together. As the softener, process oil is preferable, and paraffinic (paraffin, liquid paraffin, etc.), naphthenic, and aromatic mineral oil softeners are particularly preferable. In addition, the said paraffin and the said liquid paraffin act also as a lubricant. The mineral oil-based softener is generally a mixture of an aromatic ring, a naphthene ring, and a paraffin chain. Paraffin mineral oil is a mineral oil in which the number of carbon atoms in the paraffin chain accounts for 50% or more of the total carbon number, and naphthenic mineral oil is a mineral oil in which the number of carbons in the naphthenic ring is 30 to 45% of the total carbon number, aromatic The system mineral oil means a mineral oil in which the aromatic ring has 30% or more of carbon atoms in the total number of carbon atoms.

  The blending amount of the softening agent can be 200 parts by mass or less per 100 parts by mass of the uncrosslinked rubber (A), preferably 180 parts by mass or less, more preferably 150 parts by mass or less. When the blending amount of the softening agent is within the above range, bleed out of the softening agent from the obtained thermoplastic elastomer composition can be suppressed, and mechanical properties and rubber elasticity of the thermoplastic elastomer composition can be improved. Therefore, it is preferable.

  As a method of blending the softener, for example, a method of adding the softener to the uncrosslinked rubber (A) to obtain an oil-extended rubber, which is blended with the raw material composition, the uncrosslinked rubber (A) and Includes a method of separately blending (post-addition), a method of combining both, and the like. As the oil-extended rubber, for example, the ethylene / α-olefin copolymer rubber can be used as the uncrosslinked rubber (A), and the softener can be added thereto. Use of such an oil-extended rubber is preferable because it may be easy to handle in producing a thermoplastic elastomer composition. Examples of the method for preparing the oil-extended rubber include a method of adding a softening agent to a polymerization solution such as ethylene / α-olefin copolymer rubber and then removing the solvent; ethylene / α-olefin copolymer rubber and softening And a method of kneading the agent.

  Specific examples of the anti-aging agent include naphthylamine compounds, diphenylamine compounds, p-phenylenediamine compounds, quinoline compounds, hydroquinone derivatives, monophenol compounds, bisphenol compounds, trisphenol compounds, polyphenol compounds. Examples include compounds, thiobisphenol compounds, hindered phenol compounds, and phosphite compounds. The anti-aging agent may be used alone or in combination of two or more. The blending amount of the anti-aging agent is preferably 0.01 to 2 parts by mass, more preferably 0.05 to 100 parts by mass with respect to a total of 100 parts by mass of the uncrosslinked rubber (A) and the thermoplastic resin (B). 1 part by mass.

  Specific examples of the lubricant include silicone oil, modified silicone oil, fatty acid ester (fatty acid lower alcohol ester, fatty acid polyhydric alcohol ester, fatty acid polyglycol ester, etc.), hydrocarbon resin, higher fatty acid, oxy fatty acid, fatty acid amide. , Alkylene bis fatty acid amide, aliphatic ketone, aliphatic alcohol, polyhydric alcohol, polyglycol, polyglycerol, and metal soap. The said lubricant may be used individually by 1 type, and may use 2 or more types together. The blending amount of the lubricant is preferably 0.01 to 3 parts by mass, more preferably 0.05 to 1 part by mass with respect to a total of 100 parts by mass of the uncrosslinked rubber (A) and the thermoplastic resin (B). Parts, more preferably 0.1 to 0.5 parts by mass.

  Specific examples of the filler include carbon black, clay, kaolin, talc, calcium carbonate, wet silica, dry silica, natural silicic acid, synthetic silicic acid, magnesium carbonate, and barium sulfate. The said filler may be used individually by 1 type, and may use 2 or more types together.

  Hereinafter, the present invention will be described more specifically with reference to examples. “Part” and “%” are based on mass unless otherwise specified.

(1) Raw material component (1-1) Uncrosslinked rubber (A)
In this example, as the uncrosslinked rubber (A), an oil-extended rubber obtained by blending a terpolymer rubber with a mineral oil softener was used. Specifically, as terpolymer rubber, ethylene / propylene / 5-ethylidene-2-norbornene terpolymer rubber (ethylene unit amount is 66 mol%, 5-ethylidene-2-norbornene unit amount is 4 mol. 0.5 mol%) was used. A mineral oil-based softener (trade name “Diana Process Oil PW-380”, manufactured by Idemitsu Kosan Co., Ltd.) is added to the polymer solution of the terpolymer rubber, and then the solvent is removed. An oil-extended rubber was prepared. In addition, the oil extension amount of the mineral oil-based softener with respect to 100 parts of the terpolymer rubber is 100 parts. The terpolymer rubber is crumb-like.

(1-2) Thermoplastic resin (B)
Polyolefin resin (PO-1); a mixture of propylene / ethylene random copolymer and propylene / 1-butene copolymer (manufactured by Ube Industries, trade name “Ube CAP350”, density: 0.88 g / cm ³ , MFR ( 230 ° C., 2.16 kg); 12 g / 10 min, melting point 142 ° C. (1 peak))
Polyolefin resin (PO-2); propylene / ethylene block copolymer (manufactured by Nippon Polychem, trade name “Novatech BC5CW”, density: 0.90 g / cm ³ , MFR (230 ° C., 2.16 kg); 5 g / 10 Min, melting point 151 ° C)
Polyolefin resin (PO-3); propylene / ethylene random copolymer (manufactured by Nippon Polychem, trade name “Novatech FL02A”, density: 0.90 g / cm ³ , MFR (230 ° C., 2.16 kg); 20 g / 10 minutes, melting point 145 ° C)
Polyolefin resin (PO-4): 1-butene copolymer (manufactured by Sun Allomer, trade name “PB8640”, density 0.91 g / cm ³ , melt flow rate (230 ° C., 2.16 kg); 4 g / 10 min. Melting point 110 ° C.)

(1-3) Crosslinking agent (C) and crosslinking aid Crosslinking agent: 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (manufactured by NOF Corporation, trade name “Perhexa 25B-40” 40%, 1 minute half-life temperature; 179.8 ° C.)
Crosslinking aid (1); divinylbenzene (manufactured by Sankyo Kasei Co., Ltd., purity: 55%)
Crosslinking aid (2); N, N′-m-phenylenebismaleimide (trade name “Barnock PM”, manufactured by Ouchi Shinsei Chemical Co., Ltd.)

(1-4) Other components As the softener, the mineral oil softener used for the preparation of the uncrosslinked rubber (A) was used. Tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane (Ciba Specialty Chemicals, trade name “Irganox 1010”) was used as an antioxidant. . Silicone oil (manufactured by Toray Dow Corning Silicone, trade name “SH-200, viscosity 100 cSt”) was used as a lubricant.

(2) Production of Thermoplastic Elastomer Composition The production equipment for the thermoplastic elastomer composition is a continuous different-direction rotating twin-screw kneader (made by Kobe Steel, model name “Mixtron LCM50”, different-direction meshing type 2 rotor, L / D = 10, screw diameter 49 mm, cylinder inner diameter 54 mm, motor driving force 37 kW), same direction rotating twin screw extruder (manufactured by Nippon Steel Works, model name “TEX44αII”, same direction non-engagement type screw, L / D D = 52.5, screw diameter 46 mm, cylinder inner diameter 47 mm, motor driving force 132 kW).

  Using the above production apparatus, the thermoplastic elastomer compositions of Examples 1 to 8 and Comparative Examples 1 to 4 were produced by the method described below. Table 1 shows the types and ratios of the raw material components contained in the raw material compositions used in Examples 1 to 8 and Comparative Examples 1 to 4. Table 2 shows the production conditions for the thermoplastic elastomer composition.

[Example 1]
80 parts of oil-extended rubber, 15 parts of polyolefin resin (PO-1), 1 part of crosslinking agent, 1.25 parts of crosslinking aid (1), 0.1 part of anti-aging agent, and 0.2 part of lubricant, Henschel mixer It was thrown into. The above raw material components were mixed for 30 seconds to obtain a raw material composition. Next, the raw material composition was mixed with the above-described continuous different-direction biaxial kneader (upstream kneader) at a discharge rate of 40 kg / h using two weight type feeders (type name “KF-C88” manufactured by Kubota Corporation). From the raw material inlet.

  And the set temperature of the cylinder of the upstream side kneader was set to 80 ° C., the screw rotation speed was 500 rpm, and the specific energy E1 was 0.925 kW · hr / kg, and the raw material composition was mixed and dispersed. . In addition, 11 parts of the mineral oil-based softening agent among the above raw material components was press-fitted from the cylinder of the first kneading rotor part of the upstream kneading machine. The kneading by the upstream kneader proceeded in a state where the thermoplastic resin (B) was melted. Further, the temperature T1 (° C.) of the kneaded material at the outlet of the upstream side kneader was measured using a non-contact thermometer (model name “PT-3LF”) manufactured by Optex. The T1 was 173 ° C.

  Thereafter, the kneaded product is introduced into the same-direction rotating twin-screw extruder (downstream extruder) from the conveying pipe, the set temperature of the cylinder of the downstream extruder is 210 ° C., the screw rotation speed is 400 rpm, And the thermoplastic elastomer composition was obtained by setting so that specific energy E2 might be set to 3.3 kW * hr / kg, and performing the crosslinking reaction by dynamic heat processing. The temperature T2 (° C.) of the kneaded product at the outlet of the downstream kneader was measured using a non-contact thermometer (model name “PT-3LF”) manufactured by Optex. The T2 was 234 ° C.

  In order to see the morphology of the kneaded material at the outlet of the upstream side kneader, a predetermined amount of the kneaded material at the outlet of the upstream side kneader was collected. The collected kneaded material was sliced with a freezing microtome and stained with ruthenium tetroxide. The uncrosslinked rubber, crosslinked rubber, and thermoplastic resin contained in the dyed flakes were observed at a magnification of 2000 using a transmission electron microscope (model name “H-7500”) manufactured by Hitachi, Ltd. (FIG. 2). Moreover, in order to see the morphology of the kneaded material at the outlet of the downstream side extruder, the same pretreatment as described above was performed, and observed using the electron microscope at a magnification of 2000 times (see FIG. 3).

[Example 2]
70 parts of oil-extended rubber, 5 parts of polyolefin resin (PO-1) and 25 parts of (PO-1), 0.5 part of crosslinking agent, 0.5 part of crosslinking aid (2), 0.1 part of anti-aging agent, And 0.2 part of silicone oil was put into a Henschel mixer. The above raw material components were mixed for 30 seconds to obtain a raw material composition. A thermoplastic elastomer composition was produced in the same manner as in Example 1 using the raw material composition. T1 and T2 were measured by the same method as in Example 1. The T1 was 176 ° C., and the T2 was 243 ° C.

Example 3
80 parts of oil-extended rubber, 20 parts of polyolefin resin (PO-2), 1 part of crosslinking agent, 1.25 parts of crosslinking aid (1), 0.1 part of anti-aging agent, and 0.2 part of lubricant, Henschel mixer It was thrown into. The above raw material components were mixed for 30 seconds to obtain a raw material composition. The production conditions of the thermoplastic elastomer composition are as follows: the amount of the raw material composition discharged to the upstream kneader is 30 kg / h, the specific energy E1 is 1.23 kW · hr / kg, and the set temperature of the cylinder of the downstream extruder is The temperature is 230 ° C., the rotational speed of the screw is 400 rpm, and the specific energy E2 is 4.4 kW · hr / kg. And the thermoplastic elastomer composition was manufactured by the method similar to Example 1 using the said raw material composition. T1 and T2 were measured by the same method as in Example 1. The T1 was 167 ° C., and the T2 was 254 ° C.

Example 4
The same raw material composition as in Example 3 was used as the raw material composition. The production conditions of the thermoplastic elastomer composition are the same as those in Example 1 except that the set temperature of the cylinder of the downstream extruder is 230 ° C. And the thermoplastic elastomer composition was manufactured by the method similar to Example 1 using the said raw material composition. T1 and T2 were measured by the same method as in Example 1. The T1 was 163 ° C., and the T2 was 276 ° C.

Example 5
The same raw material composition as in Example 3 was used as the raw material composition. The production conditions of the thermoplastic elastomer composition are as follows: the discharge amount of the raw material composition to the upstream kneader is 50 kg / h, the specific energy E1 is 0.74 kW · hr / kg, and the set temperature of the cylinder of the downstream extruder Is 230 ° C., and the others are the same as those in Example 4. And the thermoplastic elastomer composition was manufactured by the method similar to Example 1 using the said raw material composition. T1 and T2 were measured by the same method as in Example 1. The T1 was 161 ° C., and the T2 was 276 ° C.

Example 6
The same raw material composition as in Example 3 was used as the raw material composition. The production conditions for the thermoplastic elastomer composition are the same as in Example 4 except that the screw speed of the upstream kneader is 350 rpm. And the thermoplastic elastomer composition was manufactured by the method similar to Example 1 using the said raw material composition. T1 and T2 were measured by the same method as in Example 1. The T1 was 168 ° C., and the T2 was 264 ° C.

Example 7
The same raw material composition as in Example 3 was used as the raw material composition. The manufacturing conditions of the thermoplastic elastomer composition are the same as in Example 4 except that the screw speed of the upstream side kneader is 700 rpm. And the thermoplastic elastomer composition was manufactured by the method similar to Example 1 using the said raw material composition. T1 and T2 were measured by the same method as in Example 1. The T1 was 193 ° C., and the T2 was 242 ° C.

Example 8
70 parts of oil-extended rubber, 30 parts of polyolefin resin (PO-4), 1 part of cross-linking agent, 1 part of cross-linking aid (2), 0.1 part of anti-aging agent and 0.2 part of lubricant are put into a Henschel mixer. did. The above raw material components were mixed for 30 seconds to obtain a raw material composition. The manufacturing conditions of the thermoplastic elastomer composition are the same as in Example 4 except that the screw speed of the downstream extruder is 700 rpm. And the thermoplastic elastomer composition was manufactured by the method similar to Example 1 using the said raw material composition. T1 and T2 were measured by the same method as in Example 1. The T1 was 177 ° C., and the T2 was 267 ° C.

[Comparative Example 1]
70 parts of oil-extended rubber, 30 parts of polyolefin resin (PO-2), 1 part of crosslinking agent, 1.25 parts of crosslinking aid (1), 0.1 part of anti-aging agent and 0.2 part of lubricant, Henschel mixer It was thrown into. The above raw material components were mixed for 30 seconds to obtain a raw material composition. The production conditions of the thermoplastic elastomer composition are the same as those in Example 4 except that the screw speed of the upstream kneader is 900 rpm. And the thermoplastic elastomer composition was manufactured by the method similar to Example 1 using the said raw material composition. T1 and T2 were measured by the same method as in Example 1. The T1 was 213 ° C., and the T2 was 256 ° C.

[Comparative Example 2]
As the raw material composition, the same raw material composition as in Comparative Example 1 was used. The production conditions of the thermoplastic elastomer composition were as follows: the discharge amount of the raw material composition to the upstream kneader was 10 kg / h, the specific energy E1 of the upstream kneader was 3.7 kW · hr / kg, and the downstream extruder The specific energy E2 is 13.2 kW · hr / kg, and the others are the same as in the first embodiment. And the thermoplastic elastomer composition was manufactured by the method similar to Example 1 using the said raw material composition. T1 and T2 were measured by the same method as in Example 1. The T1 was 183 ° C., and the T2 was 231 ° C. However, the discharge amount of the kneaded material was not stable at the outlet of the upstream kneader, and a thermoplastic elastomer composition could not be obtained.

[Comparative Example 3]
As the raw material composition, the same raw material composition as in Comparative Example 1 was used. The production conditions for the thermoplastic elastomer composition are the same as in Example 1 except that the cylinder setting temperature of the upstream kneader is 270 ° C. And the thermoplastic elastomer composition was manufactured by the method similar to Example 1 using the said raw material composition. T1 and T2 were measured by the same method as in Example 1. The T1 was 290 ° C., and the T2 was 228 ° C. However, the melt viscosity of the kneaded material supplied from the upstream side kneader was extremely low, and the kneaded material adhered to the periphery of the apparatus. Therefore, the kneaded product could not be stably supplied to the downstream extruder, and a thermoplastic elastomer composition could not be obtained.

[Comparative Example 4]
As the raw material composition, the same raw material composition as in Comparative Example 1 was used. The production conditions of the thermoplastic elastomer composition are the same as in Example 1 except that the screw speed of the upstream kneader is 100 rpm. And the thermoplastic elastomer composition was manufactured by the method similar to Example 1 using the said raw material composition. However, in the upstream kneader, the olefin resin was not melted and the oil-extended rubber was discharged in powder form. The T1 and T2 were measured by the same method as in Example 1. The T1 was 110 ° C. and the T2 was 220 ° C. Therefore, the kneaded product could not be stably supplied to the downstream extruder, and a thermoplastic elastomer composition could not be obtained.

(3) Evaluation Melt flow rate, hardness, tensile breaking strength, tensile breaking elongation, compression set and extrusion processability of each of the thermoplastic elastomer compositions of Examples 1 to 8 and Comparative Example 1 obtained by the above method It measured according to the following method. Moreover, about each thermoplastic elastomer composition of Examples 1-8 and the comparative example 1, the presence or absence of the roughness was investigated according to the following method. Furthermore, in the production of each thermoplastic elastomer composition of Examples 1 to 8 and Comparative Example 1, the degree of crosslinking Z _i of the kneaded product at the outlet of the upstream kneader and the degree of crosslinking Z of the kneaded product at the outlet of the downstream extruder Was measured by the method described in the text. These results are shown in Table 3.
(A) Melt flow rate (MFR)
As a flowability index, measurement was performed at 230 ° C. and a load of 10 kg.
(B) Hardness Duro A hardness was measured according to JIS K6252.
(C) Tensile breaking strength and tensile breaking elongation Measured according to JIS K6251.
(D) Compression set Measured according to JIS K6262.
(E) Extrusion processability Extruder (made by Toyo Seiki Co., Ltd., trade name “Lab Plast Mill”, outer diameter; 20 mm, L / D = 25) is used for flat plate extrusion (die part width 25 mm, The thickness was 1.5 mm), and the appearance was visually evaluated. The case where the surface was smooth and the edge was “◯”, and the others were all “X”.
[Extruder settings]
Cylinder C1; 180 ° C, cylinder C2; 190 ° C, cylinder C3; 210 ° C, die; 205 ° C, screw rotation speed: 40rpm
(F) Presence / absence of protrusions The surface of the (E) extrudable sample was visually observed to examine the presence / absence of protrusions. The case where there was no “bump” on the surface was “◯” and the case where there was a “bump” was all “x”. In addition, the above-mentioned “butsu” is visible when the rubber component is not kneaded well when the thermoplastic elastomer composition is dynamically heat-treated in the presence of a crosslinking agent, or when the crosslinking reaction proceeds rapidly. Huge cross-linked rubber particles.

  From Tables 2 and 3, the thermoplastic elastomer compositions of Examples 1 to 8 obtained by the production method of the present invention have large hardness, tensile breaking strength, tensile breaking elongation and compression set, rubber elasticity and mechanical properties. Excellent mechanical strength. Moreover, each thermoplastic elastomer composition of Examples 1-8 was excellent in extrusion processability, and "buzz" was not recognized by the thermoplastic elastomer composition after an extrusion process. Therefore, it can be seen that the thermoplastic elastomer composition having an excellent balance between mechanical properties and moldability can be obtained by the production method of the present invention.

On the other hand, from Table 2 and Table 3, in Comparative Example 1 in which the degree of crosslinking Z _i exceeds 85% of the degree of crosslinking Z, the tensile elongation at break is lower than in Examples 1 to 8, and the extrusion processability is inferior. In the thermoplastic elastomer composition after the extrusion process, “buzz” was generated. Also, from Tables 2 and 3, a comparative example in which the relationship between the temperature (T1) of the kneaded material at the outlet of the upstream side kneader and the melting point (Tm) of the thermoplastic resin (B) is outside the scope of the present invention. In both Nos. 3 and 4, the mixture could not be stably supplied to the downstream kneader, and a thermoplastic elastomer composition could not be obtained. Furthermore, from Table 2 and Table 3, even in Comparative Example 2 where the specific energy E1 of the continuous different-direction rotating twin-screw kneader and the specific energy E2 of the same-direction rotating twin-screw extruder are high, the discharge amount is not stable, A thermoplastic elastomer composition could not be obtained.

  Further, FIG. 2 shows that in Example 1, the kneaded product at the outlet of the upstream side kneader has a phase structure in which each of the rubber component / thermoplastic resin has a bicontinuous structure. Furthermore, from FIG. 3, in Example 1, the kneaded product at the outlet of the downstream side extruder has a rubber component / thermoplastic resin island / sea structure (a rubber component is an island structure and a thermoplastic resin is a sea structure. ). That is, in Example 1, it can be seen that the rubber component / thermoplastic resin phase inversion occurred.

  The thermoplastic elastomer composition obtained by the production method of the present invention can be used particularly for various composite processed products having an injection fusion part. Further, the thermoplastic elastomer composition obtained by the production method of the present invention can be widely used for general processed products. Examples of the general processed products include automobile bumpers, exterior moldings, wind seal gaskets, door seal gaskets, trunk seal gaskets, roof side rails, emblems, interior / exterior skin materials, weather strips, etc. Sealing materials and interior / exterior skin materials, etc., civil engineering / architecture sealing materials, interior / exterior skin materials or waterproof sheet materials, general machinery / equipment sealing materials, etc., weak electrical components, flat panel displays, liquid crystal panels, fuel cells -Packing or housing for inkjet printer parts, daily miscellaneous goods, sports equipment, etc.

In the production of the thermoplastic elastomer composition of the present invention, it is a schematic diagram showing the phase structure of the kneaded material discharged from the continuous different direction rotating biaxial kneader ((a); rubber component / thermoplastic resin is sea / Island structure, (b); rubber component / thermoplastic resin is island / sea structure, (c); rubber component / thermoplastic resin is bicontinuous structure). In Example 1, it is a figure which shows the TEM image which shows the morphology of the kneaded material of the exit of a continuous different direction rotation biaxial kneader. In Example 1, it is a figure which shows the TEM image which shows the morphology of the kneaded material of the exit of a same direction rotation twin-screw extruder.

Claims (12)

A raw material composition containing an uncrosslinked rubber (A), a thermoplastic resin (B), and a crosslinking agent (C) is converted into a continuous different-direction rotating twin-screw kneader upstream and the same-direction rotating twin-screw extrusion downstream. Is supplied from the raw material introduction part of the continuous different direction rotating biaxial kneader of the extrusion device arranged in series, and the raw material composition is mixed and dispersed by the continuous different direction rotating biaxial kneader, A method for producing a thermoplastic elastomer composition, wherein a kneaded product obtained by the continuous different-direction rotating twin-screw kneader is supplied to the same-direction rotating twin-screw extruder to obtain a dynamically crosslinked thermoplastic elastomer composition. ,
The degree of crosslinking Z of the crosslinked polymer component in the kneaded product at the outlet of the same-direction rotating twin-screw extruder is 80 to 100%, and the crosslinking in the kneaded product at the outlet of the continuous different-direction rotating twin-screw kneader. The method for producing a thermoplastic elastomer composition, wherein the polymer component has a crosslinking degree Z _i of 85% or less of the crosslinking degree Z.   When the melting point of the thermoplastic resin (B) is Tm, the temperature of the kneaded material at the outlet of the continuous different-direction rotating twin-screw kneader is Tm (° C) or more and [Tm + 100] (° C) or less. A process for producing the thermoplastic elastomer composition according to 1. The crosslinking agent (C) contains an organic peroxide,
The melting point of the thermoplastic resin (B) Tm, the temperature of the case of the one minute half-life temperature of the organic peroxide was T _h, the kneaded material at the outlet of the continuous counter-rotating twin screw kneader is, Tm The thermoplastic elastomer composition according to claim 1 or 2, wherein the temperature is not lower than (° C) and not higher than [Tm + 100] (° C), and is not lower than [T _h -30] (° C) and not higher than [T _h +30] (° C). Production method.   The kneaded product at the outlet of the continuous different-direction rotating twin-screw kneader is a phase structure in which the rubber component / thermoplastic resin is an sea / island structure, a phase structure in which the rubber component / thermoplastic resin is an island / sea structure, or The rubber component / thermoplastic resin each has a phase structure having a bicontinuous structure, and the kneaded material at the outlet of the same-direction rotating twin-screw extruder has a cross-linked rubber component / thermoplastic resin as an island / sea structure. The manufacturing method of the thermoplastic-elastomer composition in any one of Claims 1 thru | or 3 provided with a phase structure.   The method for producing a thermoplastic elastomer composition according to any one of claims 1 to 4, wherein a temperature of a cylinder of the continuous different-direction rotating twin-screw kneader is Tm (° C) or less.   The method for producing a thermoplastic elastomer composition according to any one of claims 1 to 5, wherein a temperature of a cylinder of the co-rotating twin screw extruder is [Tm-30] (° C) or more and [Tm + 200] (° C) or less. . The thermoplastic resin (B) is a polyolefin resin,
The temperature of the kneaded material at the outlet of the continuous different-direction rotating twin-screw kneader is Tm (° C.) or more and [Tm + 100] (° C.) or less, and the temperature of the cylinder of the continuous different-direction rotating twin-screw kneader is Tm (° C.). And the difference between the temperature of the kneaded material at the outlet and the temperature of the cylinder is 100 ° C. or less,
The temperature of the kneaded material at the outlet of the co-rotating twin screw extruder is [Tm + 10] (° C.) or more and [Tm + 200] (° C.) or less, and the temperature of the cylinder of the co-rotating twin screw extruder is [Tm-30]. The thermoplastic elastomer according to any one of claims 1 to 6, wherein the temperature is not lower than (° C) and not higher than [Tm + 200] (° C), and the difference between the temperature of the kneaded product at the outlet and the temperature of the cylinder is not higher than 100 ° C. A method for producing the composition. Melting | fusing point of the said polyolefin resin is 60-200 degreeC,
The temperature of the kneaded product at the outlet of the continuous different direction rotating biaxial kneader is 60 to 200 ° C., the temperature of the cylinder of the continuous different direction rotating biaxial kneader is 30 to 100 ° C., and the temperature of the kneaded product at the outlet The difference between the temperature and the temperature of the cylinder is 100 ° C. or less,
The temperature of the kneaded product at the outlet of the same-direction rotating twin-screw extruder is 70 to 400 ° C., the temperature of the cylinder of the same-direction rotating twin-screw extruder is 20 to 400 ° C., and the temperature of the kneaded product at the outlet The method for producing a thermoplastic elastomer composition according to claim 7, wherein a difference from the temperature of the cylinder is 100 ° C or less.   The specific energy E1 of the continuous different-direction rotating twin-screw kneader is 0.01 to 2.0 kW · hr / kg, and the specific energy E2 of the same-direction rotating twin-screw extruder is 0.1 to 10 kW · hr / kg. The method for producing a thermoplastic elastomer composition according to claim 1, wherein E1 <E2.   The shearing force applied by the continuous different-direction rotating twin-screw kneader and the same-direction rotating twin-screw extruder is 100 to 20,000 / second in terms of shear rate. A method for producing the thermoplastic elastomer composition described in 1.   The method for producing a thermoplastic elastomer composition according to any one of claims 1 to 10, wherein the uncrosslinked rubber (A) is crumb-like and / or powdery uncrosslinked rubber.   A thermoplastic elastomer composition obtained by the method according to claim 1.