WO2023145927A1 - 熱可塑性エラストマー組成物及びその成形体 - Google Patents

熱可塑性エラストマー組成物及びその成形体 Download PDF

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WO2023145927A1
WO2023145927A1 PCT/JP2023/002812 JP2023002812W WO2023145927A1 WO 2023145927 A1 WO2023145927 A1 WO 2023145927A1 JP 2023002812 W JP2023002812 W JP 2023002812W WO 2023145927 A1 WO2023145927 A1 WO 2023145927A1
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component
elastomer composition
thermoplastic elastomer
mass
composition according
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French (fr)
Japanese (ja)
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洋子 小座間
美結 山岸
真由 佐野
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MCPP Innovation LLC
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MCPP Innovation LLC
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Priority to JP2023561258A priority Critical patent/JP7409582B2/ja
Priority to CN202380019440.9A priority patent/CN118632903A/zh
Priority to EP23747137.0A priority patent/EP4474430A1/en
Publication of WO2023145927A1 publication Critical patent/WO2023145927A1/ja
Priority to JP2023200853A priority patent/JP2024009290A/ja
Priority to US18/788,063 priority patent/US20240384081A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06—Waxes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/01—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods

Definitions

  • the present invention relates to a thermoplastic elastomer composition and a molded article made from it.
  • thermoplastic elastomers have moldability similar to that of thermoplastic resins, and have unique rubber elasticity. Since thermoplastic resins and thermoplastic elastomers can be recycled, they are widely used in automobile parts, building parts, medical parts, wire coating materials, food parts, packaging materials, sundries, clothing items, sporting goods, etc. It is for example, a thermoplastic elastomer composition is known in which a specific hydrogenated block copolymer, a non-aromatic rubber softener having a kinematic viscosity at 40° C. of 100 cSt or more, and a polyolefin resin are mixed in a specific mixing ratio. (Patent Document 1).
  • thermoplastic elastomers As a substitute for vulcanized rubber has also attracted attention, and it is particularly important that they have good rubber elasticity. Furthermore, thermoplastic elastomers, which are used in a wide range of applications, are used in various temperature environments, so there are concerns about weight loss and bleeding out due to volatilization of low-boiling components.
  • thermoplastic elastomer composition described in Patent Document 1 has insufficient bleed-out resistance under certain conditions, and there is room for improvement.
  • the present invention has been made in view of such conventional problems, and has not only good moldability and rubber elasticity, but also allows the weight of the resin to be reduced, and has excellent bleed-out resistance.
  • An object of the present invention is to provide a plastic elastomer composition and a molded article thereof.
  • thermoplastic elastomer composition containing specific components (A), (B) and (C) can solve the above problems.
  • the gist of the present invention is as follows.
  • thermoplastic elastomer composition comprising the following components (A) to (C), wherein the kinematic viscosity of component (C) at 40°C is 20 cSt or more and 8000 cSt or less.
  • thermoplastic elastomer composition containing at least one of
  • thermoplastic elastomer composition which is an isoalkane mixture, containing at least one of compounds represented by C n H 2n (40 ⁇ n ⁇ 60).
  • the component (C) is further identified by the molecular formulas C n H 2n+2 and C n H 2n (30 ⁇ n ⁇ 40) determined from the mass spectrum obtained by measuring the component (C) by FD-MS.
  • the component (C) is further identified by the molecular formulas C n H 2n+2 and C n H 2n (60 ⁇ n ⁇ 80) determined from a mass spectrum obtained by measuring the component (C) by FD-MS.
  • the component (C) is further identified by the molecular formulas C n H 2n+2 and C n H 2n (30 ⁇ n ⁇ 40) determined from the mass spectrum obtained by measuring the component (C) by FD-MS. and at least one of the compounds represented by the molecular formulas C n H 2n+2 and C n H 2n (60 ⁇ n ⁇ 80).
  • a thermoplastic elastomer composition is further identified by the molecular formulas C n H 2n+2 and C n H 2n (30 ⁇ n ⁇ 40) determined from the mass spectrum obtained by measuring the component (C) by FD-MS. and at least one of the compounds represented by the molecular formulas C n H 2n+2 and C n H 2n (60 ⁇ n ⁇ 80).
  • thermoplastic elastomer composition according to any one of [1] to [8], wherein the component (C) is derived from a biomass material.
  • thermoplastic elastomer composition according to [9] which has a biomass content of 1% or more and 100% or less according to ASTM D 6866-22
  • thermoplastic elastomer composition according to any one of [1] to [10], wherein the thermoplastic resin of component (A) contains one or more of an olefin resin and an ester resin.
  • thermoplastic elastomer composition according to any one of [1] to [11], wherein the elastomer of component (B) contains one or more of an olefin elastomer, a styrene elastomer and a polyester elastomer.
  • thermoplastic elastomer composition according to any one of [1] to [12], containing 10 parts by mass or more and 400 parts by mass or less of component (C) with respect to 100 parts by mass of component (B).
  • thermoplastic elastomer composition according to any one of [1] to [13], wherein the component (C) has a pour point of -50°C or higher and 0°C or lower.
  • thermoplastic elastomer composition according to any one of [1] to [14], wherein the component (C) contains an isoalkane having a side chain alkyl group.
  • thermoplastic elastomer composition according to any one of [1] to [17], which further contains a hydrocarbon softener for rubber other than component (C).
  • component (C) is 1% by mass or more and 99% by mass or less with respect to the total content of component (C) and the hydrocarbon softener for rubber.
  • thermoplastic elastomer composition according to any one of [1] to [19].
  • thermoplastic elastomer composition which not only has good moldability and rubber elasticity, but also enables weight reduction of the resin and is excellent in bleed-out resistance, and a molded article thereof.
  • the thermoplastic resin composition and molded article thereof of the present invention are expected to be used in a wide range of applications such as automobile parts, building parts, medical parts, food parts, packaging materials, miscellaneous goods, clothing goods, sporting goods and the like.
  • 4 is a chart showing an example of FD-MS spectra; 4 is a chart showing another example of FD-MS spectra; 4 is a chart showing another example of FD-MS spectra;
  • thermoplastic elastomer composition contains the following components (A) to (C).
  • thermoplastic elastomer composition according to the first embodiment of the present invention is characterized in that the component (C) has a kinematic viscosity at 40° C. of 20 cSt or more and 8000 cSt or less.
  • the main structural units specified by the mass spectrum obtained by measuring the component (C) by FD-MS are the molecular formulas C 16 H 34 and It is characterized by being represented by at least one of C 16 H 32 .
  • the component (C) in the thermoplastic elastomer composition according to the third embodiment of the present invention, has the molecular formulas C n H 2n+2 and C It is characterized by containing at least one of the compounds represented by n H 2n (40 ⁇ n ⁇ 60).
  • the configuration of component (C) in each of the above-described embodiments satisfies the conditions of each embodiment if it is satisfied by itself, and the configurations of other embodiments are preferred. be. That is, the component (C) in the first embodiment preferably satisfies at least one of the conditions in the second embodiment and the conditions in the third embodiment, and more preferably satisfies both of these conditions. preferable. Also, in each of the second embodiment and the third embodiment, the conditions of the other embodiments similarly have the meaning of preferable conditions.
  • thermoplastic elastomer composition of the present invention not only has good moldability, but also allows the weight of the resin to be reduced. According to the thermoplastic elastomer composition of the present invention, a molded article having good rubber elasticity and excellent bleed-out resistance can be obtained. Although the details of why the thermoplastic elastomer composition of the present invention exhibits such effects are not clear, it is speculated as follows.
  • thermoplastic elastomer composition of the present invention together with the thermoplastic resin (A) and the elastomer (B), is an isoalkane mixture (C) having a kinematic viscosity at 40° C. within a specific range, or obtained by measuring with FD-MS.
  • isoalkane mixture (C) having specific characteristics specified from the mass spectrum obtained, the entanglement of the elastomer (B) and the isoalkane mixture (C) causes the entanglement of the elastomer (B) and the isoalkane mixture (C).
  • the affinity is increased, the plasticization of the elastomer (B) is promoted, and a molded article having excellent moldability, bleed-out resistance, and rubber elasticity can be obtained.
  • the isoalkane mixture (C) is an alkane, it has a low specific gravity, making it possible to reduce the specific gravity of the thermoplastic elastomer composition.
  • the isoalkane mixture (C) further has a side chain alkyl group, preferably a side chain alkyl group having 1 to 18 carbon atoms, the effect of entanglement between the elastomer (B) and the isoalkane mixture (C) can be easily obtained. It has stable fluidity and makes it easier to obtain a molded article excellent in heat resistance and other mechanical strength.
  • the fact that the isoalkane mixture (C) has specific characteristics specified from the mass spectrum obtained by measurement with FD-MS means that the content of low-viscosity components is small compared to conventionally known rubber softeners. This means that it is considered that a molded article having excellent bleed-out resistance can be easily obtained. Similarly, it means that the amount of high-viscosity components is less than that of conventionally known rubber softeners, and the affinity between the elastomer (B) and the isoalkane mixture (C) is increased, and the moldability and rubber elasticity are excellent. It can be inferred that a molded body can be obtained.
  • thermoplastic resin As the thermoplastic resin of component (A), known thermoplastic resins can be used. For example, olefin-based resins such as propylene-based polymers and ethylene-based polymers; ester-based resins such as polyethylene terephthalate and polybutylene terephthalate; amide-based resins such as nylon 6 and nylon 66; styrene-based resins such as polystyrene; carbonate-based resins such as polycarbonate; polyoxymethylene-based resins such as polyoxymethylene copolymers; polyphenylene ether-based resins; and polyvinyl chloride-based resins.
  • olefin resins and ester resins are preferable from the viewpoint of lightness and mechanical properties.
  • thermoplastic resins may be used singly or in combination of two or more.
  • thermoplastic resins are not particularly defined, it is preferable to include a resin with a weight average molecular weight of 500 to 1,500,000 as measured by gel permeation chromatography (GPC). This weight average molecular weight is more preferably 1,000 to 1,000,000, and even more preferably 2,000 to 500,000.
  • GPC gel permeation chromatography
  • the propylene-based polymer includes, for example, a propylene homopolymer, and a random or block copolymer of polypropylene and ethylene or an ⁇ -olefin such as butene-1 or hexene-1. Some propylene-based copolymers are mentioned.
  • the melt flow rate (JIS K7210, 230° C., 21.2N load) of the propylene-based polymer is not particularly specified, but is usually 0.05 to 200 g/10 minutes, and 0.05 to 100 g/10 minutes. preferably 0.1 to 80 g/10 minutes.
  • propylene-based polymer it is also possible to use a commercially available corresponding product.
  • Commercially available polypropylene can be procured from the manufacturers listed below, and can be selected as appropriate.
  • Commercially available products include Novatec PP from Nippon Polypropylene, Prime Polypro from Prime Polymer, Sumitomo Noblen from Sumitomo Chemical, polypropylene block copolymer from SunAllomer, LyondellBasell. Circluen from ExxonMobil, ExxonMobil PP from Formosa Plastics, Formolene from Borealis, Borealis PP from LG Chemical, SEETEC PP from LG Chemical.
  • ethylene polymers include, for example, high-density polyethylene, low-density polyethylene, and linear low-density polyethylene.
  • the ethylene polymer preferably has a density of 0.910 g/cm 3 or more and 1.00 g/cm 3 or less as measured by JIS K7112 from the viewpoint of achieving both mechanical strength and rubber elasticity.
  • the melt flow rate of the ethylene polymer (JIS K7210, 190° C., 21.2 N load) is not particularly specified, but is usually 0.05 to 200 g/10 minutes, and 0.05 to 100 g/10 minutes. preferably 0.1 to 80 g/10 minutes.
  • ethylene polymer It is also possible to use a commercially available corresponding product as the ethylene polymer.
  • Commercially available ethylene-based polymers can be procured from the manufacturers listed below, and can be selected as appropriate.
  • Commercially available products include Novatec (registered trademark) from Nippon Polyethylene Co., Ltd., Sumikasen (registered trademark) from Sumitomo Chemical Co., Ltd., Hi-Zex (registered trademark), Neo-Zex (registered trademark), and Ulto-Zex (registered trademark) from Prime Polymer Co., Ltd. , Ube Maruzen Polyethylene Co., Ltd. UBE Polyethylene (registered trademark), Asahi Kasei Corp. Suntech (registered trademark), Creolex (registered trademark), Saudi Petrochemical Company SABIC (registered trademark), Braskem Biopolyethylene, and the like.
  • Elastomers include ethylene-propylene-copolymer rubber (EPM), ethylene-propylene-nonconjugated diene copolymer rubber (EPDM), ethylene-butene copolymer rubber (EBM), ethylene-propylene-butene copolymer rubber, and the like.
  • SBS styrene-butadiene-styrene cop
  • elastomers may be used singly or in combination of two or more.
  • olefin-based elastomers olefin-based elastomers, styrene-based elastomers, and polyester-based elastomers are preferable from the viewpoint of lightness and mechanical properties. Moreover, from the viewpoint of interaction with the component (C), olefin elastomers and styrene elastomers are more preferable.
  • an ethylene/propylene copolymer elastomer having a Mooney viscosity ML 1+4 (125° C.) of 30 to 300 is preferable, and an ethylene/propylene/nonconjugated diene copolymer rubber (EPDM) is particularly preferable.
  • the EPDM may be an oil-extended type containing oil in advance, a non-oil-extended type containing no oil, or a combination thereof. Non-oil-extended EPDM, which does not contain oil beforehand, is economically inexpensive. On the other hand, oil-extended EPDM tends to improve mechanical properties and moldability.
  • any type of EPDM is preferably used when the Mooney viscosity ML 1+4 (125° C.) in the oil-containing state is 30-100, particularly 35-80.
  • non-conjugated dienes examples include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylenenorbornene, ethylidenenorbornene, and the like. Ethylidene norbornene is particularly preferred as the non-conjugated diene.
  • a preferred specific example of the olefinic elastomer is EPDM having an ethylene unit content of 55 to 75% by mass and a non-conjugated diene unit content of 1 to 10% by mass.
  • the ethylene unit content is 55% by mass or more, the extrusion moldability tends to be good, and when it is 75% by mass or less, the flexibility tends to be easily maintained.
  • a commercially available product can be used as such an olefin elastomer.
  • Specific examples of commercially available products include “EP Rubber” manufactured by ENEOS Materials, “Mitsui EPT” manufactured by Mitsui Chemicals, “ESPRENE (registered trademark)” manufactured by Sumitomo Chemical, and “Keltan (registered trademark)” manufactured by ARLANXEO. , “Keltan (registered trademark) Eco”, “NORDEL (registered trademark)” manufactured by DOW CHEMICAL, and “KEP” manufactured by KUMHO POLYCHEM.
  • block P aromatic vinyl compound unit
  • block Q polymer block Q
  • (hydrogenated) block copolymer” a hydrogenated product thereof
  • “mainly” means that the content of monomer units constituting the block is 50 mol% or more.
  • the aromatic vinyl compound constituting block P is not particularly limited, and examples include styrene, ⁇ -methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N,N-dimethyl-p-amino Ethylstyrene, N,N-diethyl-p-aminoethylstyrene can be mentioned. Among these, styrene, ⁇ -methylstyrene and p-methylstyrene are preferably used from the viewpoint of availability and productivity. Styrene is more preferred.
  • the block P may be composed of one type of aromatic vinyl compound unit, or may be composed of two or more types of aromatic vinyl compound units. Block P may contain monomeric units other than vinyl aromatic compound units.
  • the conjugated diene compound constituting the block Q is a diolefin having a pair of conjugated double bonds, and is not limited to the following, but examples include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene ), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, and 1,3-hexadiene. Among these, 1,3-butadiene and isoprene are preferably used from the viewpoint of productivity. 1,3-butadiene is more preferred.
  • Block Q may be composed of one type of conjugated diene compound unit, or may be composed of two or more types of conjugated diene compound units. Block Q may contain monomeric units other than conjugated diene compound units.
  • a commercial item can also be used as such a styrene-type elastomer.
  • Specific examples of commercially available products include "Clayton (registered trademark) G” manufactured by Clayton Polymer Co., Ltd., "Septon (registered trademark)” and “Septon (registered trademark) Bio” manufactured by Kuraray Co., Ltd., and “Tuftec (registered trademark)” manufactured by Asahi Kasei Corporation. )”, “S.O.E (registered trademark)”, “TAIPOL (registered trademark)” manufactured by TSRC, and “GLOBALPRENE” manufactured by LCY.
  • a polyester-based elastomer is generally a block copolymer having a hard segment having crystallinity and a soft segment having flexibility.
  • a dicarboxylic acid or an alkyl ester thereof means a dicarboxylic acid having a cyclic structure or an alkyl ester thereof.
  • a block copolymer having a soft segment (hereinafter sometimes referred to as a "polyalkylene glycol unit") (hereinafter sometimes referred to as a “cyclic polyester-polyalkylene glycol block copolymer”), and A hard segment made of a cyclic polyester and a chain aliphatic polyester (in this specification, the term “chain aliphatic polyester” refers to a dicarboxylic acid or an alkyl ester thereof in which the raw material dicarboxylic acid or its alkyl ester has only a chain structure.
  • a block copolymer having a soft segment hereinafter sometimes referred to as “chain aliphatic polyester unit”
  • chain aliphatic polyester unit hereinafter, "cyclic polyester - chain aliphatic polyester block copolymer may be referred to as “polymer”
  • cyclic polyester-polyalkylene glycol block copolymers are preferred.
  • cyclic polyester-polyalkylene glycol block copolymer for example, a copolymer having a hard segment made of an aromatic polyester (hereinafter sometimes referred to as “aromatic polyester unit”) and a polyalkylene glycol unit (hereinafter , It may be referred to as "aromatic polyester-polyalkylene glycol block copolymer”.) And a hard segment made of alicyclic polyester (hereinafter sometimes referred to as "alicyclic polyester unit”) and polyalkylene and a block copolymer having a glycol unit (hereinafter sometimes referred to as "alicyclic polyester-polyalkylene glycol block copolymer”).
  • aromatic polyester-polyalkylene glycol block copolymers are preferred.
  • the aromatic polyester-polyalkylene glycol block copolymer is a known thermoplastic elastomer as described in JP-A-10-130451 and the like, and if it is a polymer containing a polyalkylene glycol unit, each block may be a homopolymer or a copolymer.
  • the raw material of the aromatic polyester unit will be described in detail below, but it preferably contains polybutylene terephthalate as a hard segment.
  • the raw material of the polyalkylene glycol unit will also be described in detail below, it is preferable to include a soft segment made from polytetramethylene ether glycol (hereinafter sometimes referred to as "polytetramethylene glycol unit").
  • polyester-based elastomer used in the present invention a polybutylene terephthalate-polyalkylene glycol block copolymer is preferable, and a polybutylene terephthalate-polytetramethylene glycol block copolymer is more preferable.
  • the alicyclic polyester-polyalkylene glycol block copolymer includes, for example, alicyclic dicarboxylic acid ("alicyclic dicarboxylic acid” in this specification is a cyclic aliphatic hydrocarbon having two carboxyl groups directly bonded to it. compounds), alicyclic diols and polyalkylene glycols as starting materials.
  • alicyclic dicarboxylic acid in this specification is a cyclic aliphatic hydrocarbon having two carboxyl groups directly bonded to it. compounds
  • alicyclic diols and polyalkylene glycols as starting materials.
  • Each block may be a homopolymer or a copolymer as long as the polymer contains a polyalkylene glycol unit.
  • the alicyclic polyester unit preferably contains a hard segment obtained using cyclohexanedicarboxylic acid and cyclohexanedimethanol as raw materials.
  • the polyalkylene glycol unit of the alicyclic polyester-polyalkylene glycol block copolymer preferably contains a soft segment (polytetramethylene glycol unit) obtained from polytetramethylene ether glycol as a starting material.
  • Examples of the cyclic polyester-chain aliphatic polyester block copolymer include block copolymers having a hard segment made of an aromatic polyester and a soft segment made of a chain aliphatic polyester (hereinafter referred to as "aromatic polyester-chain Sometimes referred to as “aliphatic polyester block copolymer”.) And a block copolymer having a hard segment composed of an alicyclic polyester and a soft segment composed of a chain aliphatic polyester (hereinafter referred to as "alicyclic polyester - chain may be referred to as "similar aliphatic polyester block copolymer").
  • aromatic polyester-chain aliphatic polyester block copolymers are preferred.
  • aromatic polyester-chain aliphatic polyester block copolymers a polybutylene terephthalate-chain aliphatic polyester block copolymer in which the aromatic polyester unit is composed of polybutylene terephthalate is more preferable.
  • Preferred chain aliphatic polyester units are those obtained from chain aliphatic dicarboxylic acids having 4 to 10 carbon atoms, represented by sebacic acid and adipic acid, and chain aliphatic diols.
  • Polyalkylene ether glycol is preferred as the flexible soft segment.
  • Polyalkylene ether glycols include linear and branched fatty acids such as, for example, polymethylene glycol, polyethylene glycol, poly(1,2- and 1,3-)propylene glycol, polytetramethylene glycol and polyhexamethylene glycol.
  • cyclohexanediol condensates and cyclohexanedimethanol condensates homopolymers or copolymers of alicyclic ethers.
  • Soft segments may be random copolymers within these ether units.
  • a block copolymer having a polyalkylene glycol unit can also be used for the soft segment. These may be used individually by 1 type, and may use 2 or more types together.
  • the number average molecular weight of the polyalkylene glycol contained in the cyclic polyester-polyalkylene glycol block copolymer is preferably 600 to 4,000, more preferably 800 to 2,500, and more preferably 900 to 2,100. It is even more preferable to have
  • the number average molecular weight of polyalkylene glycol refers to a value calculated by magnetic resonance spectroscopy (NMR).
  • Only one of these polyalkylene glycols may be contained in the cyclic polyester-polyalkylene glycol block copolymer, or two or more of them having different number average molecular weights or constituent components may be contained.
  • polyester-based elastomer there are no particular restrictions on the method for producing the polyester-based elastomer, and either a batch polymerization method or a continuous polymerization method may be used.
  • aromatic polyester-polyalkylene glycol block copolymers using aromatic polyester and polyalkylene ether glycol are chain aliphatics having 2 to 12 carbon atoms and /
  • it can be obtained by polycondensing an oligomer obtained by subjecting an alicyclic diol, an aromatic dicarboxylic acid or its alkyl ester, and a polyalkylene ether glycol as raw materials to an esterification reaction or a transesterification reaction.
  • chain aliphatic and/or alicyclic diol having 2 to 12 carbon atoms those commonly used as raw materials for polyester can be used.
  • Chain aliphatic diols include, for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butylene glycol, 1,4-butylene glycol and 1,6-hexene glycol. Among them, 1,4-butylene glycol is preferred.
  • Alicyclic diols include, for example, 1,4-cyclohexene glycol and 1,4-cyclohexanedimethanol, with 1,4-cyclohexanedimethanol being preferred.
  • These chain aliphatic and/or alicyclic diols having 2 to 12 carbon atoms may be used singly or in combination of two or more.
  • aromatic dicarboxylic acid or its alkyl ester those generally used as raw materials for polyester can be used.
  • terephthalic acid and its lower (“lower” means having 4 or less carbon atoms in this specification) alkyl esters and isophthalic acid, phthalic acid, 2,5-norbornene dicarboxylic acid, 1,4-naphthalenedicarboxylic acid , 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and lower alkyl esters thereof.
  • terephthalic acid and isophthalic acid are preferred, and terephthalic acid is more preferred.
  • One of these aromatic dicarboxylic acids or alkyl esters thereof may be used alone, or two or more thereof may be used in combination.
  • polyalkylene ether glycol examples include linear and branched polymethylene glycol, polyethylene glycol, poly(1,2- and 1,3-)propylene glycol, polytetramethylene glycol and polyhexanemethylene glycol, as described above.
  • polyalkylene ether glycols examples include linear and branched polymethylene glycol, polyethylene glycol, poly(1,2- and 1,3-)propylene glycol, polytetramethylene glycol and polyhexanemethylene glycol, as described above.
  • aliphatic ether glycols alicyclic ether homopolymers or copolymers such as cyclohexanediol condensates and cyclohexanedimethanol condensates can be used. Moreover, it may be a random copolymer within these ether units.
  • linear and branched aliphatic ether glycols such as polymethylene glycol, polyethylene glycol, poly(1,2- and 1,3-)propylene glycol, polytetramethylene glycol and polyhexamethylene glycol. and more preferred are polymethylene glycol, polyethylene glycol, poly(1,2- and 1,3-)propylene glycol and polytetramethylene glycol, and still more preferred is polytetramethylene glycol. These may be used individually by 1 type, and may use 2 or more types together.
  • the alicyclic polyester-polyalkylene glycol block copolymer comprises a chain aliphatic and/or alicyclic diol having 2 to 12 carbon atoms, an alicyclic dicarboxylic acid or an alkyl ester thereof, and a polyalkylene ether glycol. It can be obtained by polycondensing an oligomer obtained by an esterification reaction or a transesterification reaction as a raw material.
  • alicyclic dicarboxylic acid or its alkyl ester those generally used as raw materials for polyester can be used.
  • examples include cyclohexanedicarboxylic acid and its lower alkyl esters, cyclopentanedicarboxylic acid and its lower alkyl esters.
  • cyclohexanedicarboxylic acid and its lower alkyl ester are preferred, and cyclohexanedicarboxylic acid is more preferred.
  • One of these alicyclic dicarboxylic acids or alkyl esters thereof may be used alone, or two or more thereof may be used in combination.
  • the content of each of the cyclic polyester unit and the polyalkylene glycol unit in the cyclic polyester-polyalkylene glycol block copolymer is not limited. range.
  • the lower limit of the content of the cyclic polyester unit in the cyclic polyester-polyalkylene glycol block copolymer is not limited, it is usually 10% by mass or more, preferably 15% by mass or more.
  • the upper limit of the content of the cyclic polyester unit is not limited, it is usually 95% by mass or less, preferably 90% by mass or less, and more preferably 80% by mass or less.
  • the lower limit of the polyalkylene glycol unit content in the cyclic polyester-polyalkylene glycol block copolymer is not limited, it is usually 5% by mass or more, preferably 10% by mass or more, and more preferably 20% by mass or more.
  • the upper limit of the polyalkylene glycol unit content is not limited, it is usually 90% by mass or less, preferably 85% by mass or less.
  • the content of the cyclic polyester unit in the block copolymer having the cyclic polyester unit can be calculated using nuclear magnetic resonance spectroscopy (NMR) based on the chemical shift of its hydrogen atoms and its content.
  • NMR nuclear magnetic resonance spectroscopy
  • the content of the polyalkylene glycol unit in the block copolymer having a polyalkylene glycol unit is calculated using nuclear magnetic resonance spectroscopy (NMR) based on the chemical shift of its hydrogen atoms and its content. can do.
  • a polybutylene terephthalate-polyalkylene glycol block copolymer is preferable because of its high crystallization rate and excellent moldability.
  • the number of carbon atoms in the alkylene group of the polyalkylene glycol unit is preferably 2 to 12, more preferably 2 to 8, even more preferably 2 to 5, and particularly preferably 4.
  • the cyclic polyester-polyalkylene glycol block copolymer represented by the aromatic polyester-polyalkylene glycol block copolymer according to the present invention contains, in addition to the above components, a trifunctional alcohol or tricarboxylic acid and/or its ester. A small amount of one or more of them may be copolymerized, and a chain aliphatic dicarboxylic acid such as adipic acid or a dialkyl ester thereof may be introduced as a copolymerization component.
  • the above cyclic polyester-polyalkylene glycol block copolymer is also available as a commercial product.
  • Commercial products include "KEYFLEX (registered trademark)” manufactured by LG Chemical Co., Ltd., "TEFABLOC (registered trademark)” manufactured by Mitsubishi Chemical Corporation, "Pelprene (registered trademark)” manufactured by Toyobo Co., Ltd., and “Pelprene (registered trademark)” manufactured by DuPont.
  • thermoplastic elastomer composition of the present invention contains an isoalkane mixture as component (C).
  • Isoalkane means an alkane having a terminal isomethyl group and does not contain double bonds or cyclic substituents.
  • Isoalkane mixture means a mixture of isoalkanes and hydrocarbons that do not have an isoalkane structure.
  • the "isoalkane” according to the present invention may be any alkane having an isomethyl group at the terminal. (In the present invention, this alkyl group is referred to as a "side chain alkyl group”.).
  • isoalkanes having side chain alkyl groups are preferred from the viewpoint of the entanglement effect of the elastomer (B) and isoalkanes. Since many isoalkanes are generally commercially available as isoalkane mixtures, component (C) is referred to as an "isoalkane mixture" in the present invention. good.
  • Examples of side-chain alkyl groups possessed by the isoalkane mixture of component (C) include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. Among these, an alkyl group having 1 to 18 carbon atoms is more preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is particularly preferable.
  • the side chain alkyl group of isoalkane is an alkyl chain branched from the longest linear alkyl chain as the main chain, and the side chain alkyl group is not limited to one in one molecule, but may be two. or more.
  • the number of side chain alkyl groups possessed by the isoalkane is preferably 2 to 16, more preferably 4 to 12, even more preferably 4 to 8.
  • the isoalkane mixture of component (C) preferably has a side chain alkyl group content of 1 to 80% in the molecule, more preferably a side chain alkyl group content of 5 to 70%. It is more preferably ⁇ 60%, particularly preferably 15-50%.
  • the content of the side chain alkyl group is preferably large, and is preferably small from the viewpoint of moldability.
  • the content of the side chain alkyl group is the ratio (percentage) of the molecular weight of the side chain alkyl group (the total molecular weight when there are multiple side chain alkyl groups) to the molecular weight of the entire isoalkane.
  • thermoplastic elastomer composition by containing the isoalkane mixture (C) having a kinematic viscosity at 40° C. of 20 cSt or more and 8,000 cSt or less, the obtained thermoplastic elastomer composition is softened, and the flexibility and rubber elasticity are increased. , the processability, fluidity and bleed-out resistance of the resulting thermoplastic elastomer composition can be improved.
  • the kinematic viscosity at 40° C. of the isoalkane mixture of component (C) is preferably 20 centistokes (cSt) or more, more preferably 25 cSt or more, from the viewpoint of bleed-out resistance and rubber elasticity.
  • the kinematic viscosity of the component (C) isoalkane mixture at 40° C. is preferably 8000 cSt or less, more preferably 3000 cSt or less, and further preferably 1000 cSt or less from the viewpoint of workability and moldability. preferable.
  • the kinematic viscosity is the kinematic viscosity at 40°C measured by a method based on JIS K2283.
  • the flash point (COC method) of the isoalkane mixture of component (C) is preferably the melting point or higher of the thermoplastic resin (A) used or the processing temperature or higher, and is 150° C. or higher. is preferably 180° C. or higher, more preferably 200° C. or higher, and particularly preferably 250° C. or higher.
  • the pour point (measured by ASTM D97) of the isoalkane mixture of component (C) is preferably -60°C or higher, and -50°C or higher because the lower the pour point, the higher the molecular mobility and the lower the bleed-out resistance. is more preferable, and -40°C or higher is even more preferable.
  • the temperature is preferably 0°C or lower, more preferably -10°C or lower, even more preferably -20°C or lower, and -25°C or lower. is particularly preferred.
  • the molecular weight dispersity (PDI) of the isoalkane mixture of component (C) is preferably 1.30 or less, more preferably 1.2 or less, and 1.1 or less from the viewpoint of bleed-out resistance. is more preferred.
  • the weight-average molecular weight of the component (C) isoalkane mixture is preferably 200 or more, more preferably 300 or more, and even more preferably 350 or more as a polystyrene-equivalent value measured by GPC from the viewpoint of bleed-out resistance and rubber elasticity. On the other hand, it is preferably 5,000 or less, more preferably 3,000 or less, and even more preferably 1,500 or less from the viewpoint of workability and moldability.
  • the molecular weight dispersity and weight average molecular weight can be measured by gel permeation chromatography (hereinafter sometimes abbreviated as GPC).
  • the isoalkane mixture of component (C) has a naphthenic carbon ratio (% CN) determined by ring analysis of usually 20% or less, preferably 15% or less, more preferably 10% or less, and still more preferably 5%. It is below.
  • the proportion of aromatic carbon (% CA) determined by ring analysis is preferably 5% or less, more preferably 1% or less.
  • the ring analysis can be specifically carried out by the ndM method defined in ASTM D2140 or ASTM D3238.
  • the obtained thermoplastic elastomer composition can be softened, the flexibility and rubber elasticity can be increased, and the processability, fluidity and bleed-out resistance of the obtained thermoplastic elastomer composition can be improved.
  • the major structural units referred to here are defined as follows.
  • the molecular formula of hydrocarbon represented by the m/z value of the peak is specified based on the atomic weight of carbon: 12 and the atomic weight of hydrogen: 1.00794.
  • the m/z value is, for example, 16.0 for CH4, 420.5 for C30H60 , and 841.0 for C60H120 .
  • the mass spectrum measured by FD-MS from the viewpoint of extracting the peaks representing the molecules themselves, the peaks of m/z with an even first digit are extracted for hydrocarbons having 2 to 118 hydrogen atoms.
  • peaks with odd m/z digits are extracted, and for hydrocarbons with 246 to 370 hydrogen atoms, peaks with even m/z digits are extracted.
  • peaks thus extracted a plurality of peaks having high peak intensities are sequentially extracted.
  • a hydrocarbon molecular formula that can be identified from the difference in m/z represented by the peaks extracted here is called a main structural unit. Peaks having the same number of carbon atoms are not included in the calculation of major structural units.
  • the isoalkane mixture (C) contains at least one of the compounds represented by the molecular formulas C 48 H 96 and C 48 H 98 as a main component in the mass spectrum measured by FD-MS. It is desirable to contain
  • At least one of the compounds represented by the molecular formulas C n H 2n+2 and C n H 2n (40 ⁇ n ⁇ 60) specified by a mass spectrum obtained by FD-MS measurement is By including the isoalkane mixture (C) contained as a main component, the resulting thermoplastic elastomer composition is softened, flexibility and rubber elasticity are increased, and the processability, fluidity and Bleed-out resistance can be improved.
  • the isoalkane mixture (C) may contain raw materials derived from biomass.
  • the biomass degree of the isoalkane mixture (C) is calculated according to ASTM D 6866 based on the 14C content. From the viewpoint of environmental load reduction, the isoalkane mixture (C) preferably has a biomass degree of 40% or more, more preferably 50% or more, and particularly preferably 60% or more.
  • the upper limit of the biomass degree of the isoalkane mixture (C) is not particularly limited, and is 100% or less.
  • the isoalkane mixture of component (C) can also be used in combination with a general hydrocarbon softener for rubber.
  • the general hydrocarbon-based softening agent for rubber means a hydrocarbon-based softening agent for rubber other than the component (C).
  • General hydrocarbon-based softeners for rubber include mineral oil-based softeners and synthetic resin-based softeners, with mineral oil-based softeners being particularly preferred.
  • Mineral oil softeners are generally mixtures of aromatic, naphthenic and paraffinic hydrocarbons, paraffinic oils having 50% or more of the total carbon atoms being paraffinic hydrocarbons, Naphthenic oils in which 30 to 45% of the total carbon atoms are naphthenic hydrocarbons are called naphthenic oils, and those in which 35% or more of the total carbon atoms are aromatic hydrocarbons are called aromatic oils.
  • paraffinic oils are preferred.
  • the kinematic viscosity at 40°C of the hydrocarbon softener for rubber is preferably 20 centistokes (cSt) or more, more preferably 50 cSt or more. On the other hand, it is preferably 800 cSt or less, more preferably 600 cSt or less.
  • the flash point (COC method) of the hydrocarbon-based softening agent for rubber is preferably 200°C or higher, more preferably 250°C or higher.
  • a commercially available hydrocarbon softener for rubber may be used.
  • Commercially available products include, for example, ENEOS "Nisseki Polybutene (registered trademark) HV” series and Idemitsu Kosan Co., Ltd. "Diana (registered trademark) Process Oil PW” series. can do.
  • the hydrocarbon-based softening agent for rubber can be used alone or in any combination and ratio of two or more.
  • the lower limit of the content of component (A) is 100% by mass in total of components (A) to (C) from the viewpoint of stable moldability, heat resistance and other mechanical properties. is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 7% by mass or more, and particularly preferably 10% by mass or more.
  • the upper limit of the content of component (A) is preferably 95% by mass or less, more preferably 90% by mass or less, from the viewpoint of stable rubber elasticity and good moldability, and 85% by mass. % or less, and particularly preferably 80 mass % or less.
  • the lower limit of the content of component (B) is , preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and particularly preferably 15% by mass or more.
  • the upper limit of the content of component (B) is preferably 90% by mass or less, more preferably 80% by mass or less, from the viewpoint of stable workability, moldability, heat resistance and other mechanical properties. More preferably, it is 70% by mass or less, and particularly preferably 60% by mass or less.
  • the lower limit of the content of component (C) is 10 parts by mass or more per 100 parts by mass of component (B) from the viewpoint of stable rubber elasticity and good moldability. It is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and particularly preferably 40 parts by mass or more.
  • the upper limit of the content of component (C) is preferably 400 parts by mass or less, such as 350 parts by mass, relative to 100 parts by mass of component (B), from the viewpoint of handling property and bleed-out resistance during production. It is more preferably 300 parts by mass or less, particularly preferably 200 parts by mass or less.
  • the content of the hydrocarbon softener for rubber is From the viewpoint of good moldability, it is preferably 300 parts by mass or less, more preferably 200 parts by mass or less per 100 parts by mass of component (B). Moreover, it is preferable that the total content of component (C) and the hydrocarbon-based softening agent for rubber is within the content range of component (C).
  • the content of component (C) with respect to the total amount of component (C) and the hydrocarbon softener for rubber such as paraffin oil is preferably 1% by mass or more, and 5% by mass or more. It is more preferable that the content is 10% by mass or more. If the content of component (C) with respect to the total amount of component (C) and a hydrocarbon softener for rubber such as paraffin oil is not less than the above lower limit, moldability and bleed resistance due to the use of component (C) It is possible to effectively obtain the effect of improving out property and rubber elasticity.
  • the content of component (C) with respect to the total amount of component (C) and a hydrocarbon softener for rubber such as paraffin oil is preferably 99% by mass or less, and is 90% by mass or less. is more preferable, and 80% by mass or less is even more preferable. If the content of component (C) with respect to the total amount of component (C) and the hydrocarbon softener for rubber such as paraffin oil is equal to or less than the above upper limit, the hydrocarbon softener for rubber is added together with component (C). By using them together, effects of weight reduction, rubber elasticity, and improvement of moldability can be effectively obtained.
  • thermoplastic elastomer composition of the present invention may contain other components depending on the purpose within a range that does not impair the effects of the present invention.
  • Other components include, for example, fillers, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, neutralizers, lubricants, anti-fogging agents, anti-blocking agents, slip agents, dispersants, colorants, Various additives such as a retardant, a cross-linking agent, a cross-linking aid, an antistatic agent, a conductivity-imparting agent, a metal deactivator, a molecular weight modifier, an antibacterial agent, an antifungal agent, and a fluorescent brightening agent can be mentioned. . Any of these can be used alone or in combination.
  • Fillers include glass fiber, hollow glass spheres, carbon fiber, alumina, talc, calcium carbonate, clay, mica, potassium titanate fiber, silica, zeolite, metallic soap, calcium carbonate, titanium dioxide, carbon black, boron nitride, Cellulose etc. can be mentioned. These fillers may be used alone, or two or more of them may be used in any combination and ratio.
  • Thermal stabilizers include aliphatic, aromatic or alkyl-substituted aromatic esters of phosphoric acid and phosphorous acid, and hypochlorites.
  • Phosphorus compounds such as phosphoric acid derivatives, phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonates, dialkylpentaerythritol diphosphites, dialkylbisphenol A diphosphites; phenol derivatives, especially hindered phenol compounds; thioethers, dithio acids Sulfur-containing compounds such as salts, mercaptobenzimidazoles, thiocarbanilides, and thiodipropionates; and tin compounds such as tin malate and dibutyltin monoxide can be used.
  • hindered phenol compound examples include “Irganox (registered trademark) 1010” and “Irganox (registered trademark) 1520" (both trade names: manufactured by BASF Japan Ltd.).
  • Phosphorus compounds include “PEP-36", “PEP-24G”, “HP-10” (all of which are trade names: manufactured by ADEKA Corporation), and “Irgafos (registered trademark) 168" (trade name: BASF Japan Co., Ltd.) and the like.
  • Compounds containing sulfur include thioether compounds such as dilaurylthiopropionate (DLTP) and distearylthiopropionate (DSTP).
  • thioether compounds such as dilaurylthiopropionate (DLTP) and distearylthiopropionate (DSTP).
  • the lower limit is preferably 0.01 parts by mass, more preferably 0.05 parts by mass
  • the upper limit is preferably 1, as a mass ratio in 100 parts by mass of the thermoplastic elastomer composition. parts by mass, more preferably 0.5 parts by mass.
  • light stabilizers examples include benzotriazole-based and benzophenone-based compounds. Specifically, “TINUVIN622LD”, “TINUVIN765" (both trade names: manufactured by BASF Japan Ltd.), “SANOLLS-2626” and “SANOLLS-765" (both trade names: manufactured by Sankyo Co., Ltd.) is available.
  • TINUVIN328 and "TINUVIN234" (both trade names: manufactured by BASF Japan Ltd.) and the like can be used as ultraviolet absorbers.
  • the amount of these light stabilizers and ultraviolet absorbers to be added is preferably 0.01 parts by mass, more preferably 0.05 parts by mass, as a mass ratio in 100 parts by mass of the thermoplastic elastomer composition.
  • the upper limit is preferably 1 part by mass, more preferably 0.5 part by mass.
  • Colorants include dyes such as direct dyes, acid dyes, basic dyes and metal complex dyes; inorganic pigments such as carbon black, titanium oxide, zinc oxide, iron oxide and mica; Organic pigments such as anthraquinone-based, thioindigo-based, dioxazone-based, and phthalocyanine-based pigments can be used.
  • Flame retardants include phosphorus- and halogen-containing organic compounds, bromine- or chlorine-containing organic compounds, ammonium polyphosphate, aluminum hydroxide, antimony oxide, and other additive and reactive flame retardants.
  • component (E) examples include organic peroxides, phenolic resins, and other cross-linking agents.
  • organic peroxides include di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2 ,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, 1,3-bis(t-butylperoxyisopropyl)benzene, 1,1-di(t-butylperoxy)-3 , 3,5-trimethylcyclohexane and other dialkyl peroxides; t-butyl peroxybenzoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyisopropyl carbonate, 2,5-dimethyl-2, Peroxy esters such as 5-di(benzoylperoxy)hexane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexan
  • a phenolic resin cross-linking agent is usually used together with an activator.
  • Activators that can be used here include, for example, halogen donors such as stannous chloride, ferric chloride, chlorinated paraffin, chlorinated polyethylene, chlorosulfonated polyethylene, and iron oxide, titanium oxide, Acid acceptors such as magnesium oxide, silicon dioxide and zinc oxide are used. Halogen donors may not be used when the phenolic resin is halogenated.
  • crosslinking aids examples include sulfur, p-quinonedioxime, p-dinitrosobenzene, 1,3-diphenylguanidine, and other peroxides.
  • component (F) examples include sulfur, p-quinonedioxime, p-dinitrosobenzene, 1,3-diphenylguanidine, and other peroxides.
  • Auxiliary agent; cross-linking agent for phenolic resin such as stannous chloride/anhydride, stannous chloride/dihydrate, ferric chloride; divinylbenzene, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, etc.
  • polyfunctional vinyl compounds ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate and other polyfunctional (meth) Acrylate compounds include
  • thermoplastic elastomer composition of the present invention contains component (E), a cross-linking agent
  • the content of component (E) is the sum of components (A) to (C) or
  • a hydrocarbon softener for rubber is included, it is preferably 0.01 part by mass or more, more preferably 0, based on a total of 100 parts by mass of components (A) to (C) and the hydrocarbon softener for rubber.
  • this ratio is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 5 parts by mass or less.
  • the cross-linking aid of component (F) is the sum of components (A) to (C), or components (A) to (C) and a hydrocarbon softener for rubber when a hydrocarbon softener for rubber is included. 0.05 to 3 parts by weight, preferably 0.1 to 2 parts by weight, per 100 parts by weight of the total.
  • the content of the cross-linking aid is at least the above lower limit, the use effect of the cross-linking aid can be obtained, and it is preferable from the viewpoint of cost that it is at most the above upper limit.
  • One of the above additives may be used alone, or two or more may be used in any combination and ratio.
  • the method for producing the thermoplastic elastomer composition of the present invention is not particularly limited. It can be produced by dry-blending with other components and then melt-kneading.
  • the mixing device used at that time is not particularly limited, and examples thereof include a kneading device such as a Banbury mixer, a Laboplastomill, a single-screw extruder, and a twin-screw extruder. Among these, the production by the melt-mixing method using an extruder is preferable from the viewpoint of productivity and good kneadability.
  • the melting temperature during kneading can be appropriately set, but is usually in the range of 130 to 300°C, preferably in the range of 150 to 250°C.
  • thermoplastic elastomer composition of the present invention also contains components (A) to (C), and optionally component (D) and other components in a predetermined content ratio, and component (E): a cross-linking agent. and component (F): those obtained by crosslinking by dynamic heat treatment in the presence of a crosslinking aid are also preferred.
  • “Dynamic heat treatment” in the present invention means kneading in a molten or semi-molten state. This dynamic heat treatment is preferably carried out by melt-kneading, and examples of the mixing and kneading apparatus for this purpose include closed Banbury mixers, mixing rolls, kneaders, and twin-screw extruders. Among these, it is preferable to use a twin-screw extruder.
  • a preferred embodiment of this production method using a twin-screw extruder is to supply each component to a raw material supply port (hopper) of a twin-screw extruder having a plurality of raw material supply ports and perform dynamic heat treatment.
  • the temperature for the dynamic heat treatment is usually 80-300°C, preferably 100-250°C.
  • the time for dynamic heat treatment is usually 0.1 to 30 minutes.
  • thermoplastic elastomer composition of the present invention is subjected to dynamic heat treatment using a twin-screw extruder, the barrel radius R (mm) of the twin-screw extruder, the screw rotation speed N (rpm) and the discharge rate Q (kg/hour) ), it is preferable to extrude while maintaining the relationship of the following formula, more preferably while maintaining the relationship of the following formula (2).
  • thermoplastic elastomer composition can be produced efficiently if the relationship among the barrel radius R (mm), screw rotation speed N (rpm) and discharge rate Q (kg/hour) of the twin-screw extruder is greater than the above lower limit. It is preferable to manufacture to On the other hand, it is preferable that the above relationship is smaller than the above upper limit, because heat generation due to shearing is suppressed and foreign matter that causes poor appearance is less likely to occur.
  • the melt measured using a melt indexer (manufactured by Toyo Seiki Seisakusho) at a measurement temperature of 230° C. and a measurement load of 21.18 N with reference to ISO 1133.
  • the flow rate (MFR) is preferably 2 g/10 minutes or more, more preferably 5 g/10 minutes or more, and even more preferably 10 g/10 minutes or more.
  • the melt flow rate (MFR) is preferably 200 g/10 minutes or less, more preferably 185 g/10 minutes or less, and even more preferably 160 g/10 minutes or less. .
  • the rate (MFR) is preferably 0.1 g/10 minutes or more, more preferably 0.5 g/10 minutes or more, and even more preferably 1 g/10 minutes or more. Further, from the viewpoint of formability, the melt flow rate (MFR) is preferably 40 g/10 minutes or less, more preferably 35 g/10 minutes or less, and further preferably 30 g/10 minutes or less. preferable.
  • the thermoplastic elastomer composition of the present invention should have a hardness duro A lower limit of 10 or more, which is measured 15 seconds after a needle is pressed against the test piece, with reference to ISO 7619.
  • it is 20 or more, more preferably 30 or more, and particularly preferably 40 or more.
  • the upper limit is preferably 95 or less, more preferably 90 or less.
  • the thermoplastic elastomer composition of the present invention preferably has a biomass content of 1% or more, more preferably 10% or more, and more preferably 15% or more according to ASTM D 6866-22 from the viewpoint of reducing environmental load. is more preferable, and 20% or more is particularly preferable. On the other hand, the upper limit of the biomass degree is 100% or less.
  • biomass-derived raw materials may be appropriately selected and blended as the raw materials for component (A), component (B), component (C), and the like.
  • the molded article of the present invention can be obtained by molding the thermoplastic elastomer composition of the present invention.
  • thermoplastic elastomer composition of the present invention can be formed into a molded body by various molding methods such as injection molding, extrusion molding, blow molding, compression molding, and vacuum molding. Among these, molded articles obtained by injection molding and extrusion molding are preferred. In addition, it is also possible to obtain a molded body by secondary processing such as lamination molding and thermoforming after performing these moldings.
  • thermoplastic elastomer composition of the present invention and its molded product are not particularly limited.
  • Home appliance parts multilayer hoses
  • medical parts medical multilayer containers, syringe gaskets, rubber stoppers
  • food parts multilayer packaging films, containers, bottles, design packaging, labels, cap liners, packing
  • wire coating materials It can be used in a wide range of fields such as miscellaneous goods and automobile parts (weather strips, ceiling materials, interior sheets, bumper moldings, side moldings, air spoilers, hoses, armrests, door trims, console lids, mats).
  • miscellaneous goods and automobile parts weather strips, ceiling materials, interior sheets, bumper moldings, side moldings, air spoilers, hoses, armrests, door trims, console lids, mats.
  • miscellaneous goods and automobile parts weather strips, ceiling materials, interior sheets, bumper moldings, side moldings, air spoilers, hoses, armrests, door trims, console lids, mats.
  • miscellaneous goods and automobile parts
  • A-1 Propylene homopolymer "Novatec (registered trademark) PP FA3KM” manufactured by Japan Polypro Co., Ltd. MFR (JIS K7210, 230° C., 21.2 N load): 10 g/10 minutes
  • A-2 Propylene homopolymer "Novatec (registered trademark) PP FY6” manufactured by Japan Polypropylene Corporation MFR (JIS K7210, 230° C., 21.2 N load): 2.5 g/10 minutes
  • A-3 Propylene/ethylene random copolymer "Novatec (registered trademark) PP MG03BD” manufactured by Nippon Polypro Co., Ltd.
  • B-1 Styrene/ethylene/butylene/styrene copolymer (SEBS) Asahi Kasei Co., Ltd. "Tuftec (registered trademark) N504"
  • B-2 Ethylene-butene copolymer rubber manufactured by Dow Chemical Company
  • B-3 Ethylene/propylene/ethylidenenorbornene copolymer rubber manufactured by Mitsui Chemicals, Inc.
  • EPT registered trademark 3092PM Mooney viscosity (ML 1+4 , 125°C): 65 Propylene unit content: 29.5% by mass Ethylene unit content: 66% by mass Ethylidene norbornene unit content: 4.5% by mass
  • X-1 Paraffinic oil (not containing isoalkane) Diana (registered trademark) “Process Oil PW-32” manufactured by Idemitsu Kosan Co., Ltd.
  • X-2 Paraffinic oil (not containing isoalkane) Diana (registered trademark) “Process Oil PW-90” manufactured by Idemitsu Kosan Co., Ltd.
  • Main building block CH2 Main component : C49H94 X-4: Isoalkane mixture Nisseki polybutene (registered trademark) "HV-100" manufactured by ENEOS Co., Ltd.
  • X-5 Isoalkane Fujifilm Wako Co., Ltd.
  • thermoplastic elastomer compositions of the following examples and comparative examples are as follows.
  • thermoplastic elastomer compositions obtained in Examples and Comparative Examples were measured for MFR under conditions of 230° C. and 49 N using a melt indexer (manufactured by Toyo Seiki Seisakusho Co., Ltd.) with reference to ISO 1133. The higher the MFR, the higher the fluidity and the better the moldability.
  • Duro A hardness was measured after 15 seconds with reference to ISO7619 to evaluate flexibility. The smaller the Duro A hardness value, the better the flexibility. In terms of flexibility in the thermoplastic elastomer composition of the present invention, the Duro A hardness is equivalent in the range of ⁇ 4.
  • ⁇ Bleed-out resistance> The injection molded bodies (120 mm ⁇ 80 mm ⁇ 2 mm) produced in Examples and Comparative Examples were punched out to prepare test pieces of ⁇ 80 mm, and measured using an air fogging tester at 100 ° C. for 72 hours. The weight change ( ⁇ weight) and the gloss change ( ⁇ gross) of the glass before and after were evaluated. In both cases, the smaller the numerical value, the better the bleed-out resistance.
  • thermoplastic elastomer compositions obtained in Examples and Comparative Examples were measured for 14C concentration using a C-AMS dedicated device (manufactured by NEC Corporation) based on a tandem accelerator, and then subjected to ASTM D6866- 22 to calculate the degree of biomass.
  • C-AMS dedicated device manufactured by NEC Corporation
  • ASTM D6866- 22 ASTM D6866- 22
  • Example/Comparative example ⁇ Example 1> As shown in Table-1, 10 parts by mass of (A-1), 45 parts by mass of (B-1), 45 parts by mass of (C-1), and 0.1 parts by mass of (D-1) are mixed. The resulting mixture was melt-kneaded by a twin-screw kneader (cylinder temperature: 180 to 200° C.) to produce pellets of the thermoplastic elastomer composition.
  • thermoplastic elastomer composition was molded into a shape of 120 mm long x 80 mm wide by an electric injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd.) with a mold clamping force of 180 t at a cylinder temperature of 200°C and a mold temperature of 40°C. Injection filling was performed at an injection speed of 40 mm/sec into a sheet-like mold having a thickness of x 2 mm. After cooling for 30 seconds after completion of filling, the injection molded body was taken out. The obtained injection molded article was evaluated, and the results are shown in Table-1.
  • thermoplastic elastomer composition Pellets of the thermoplastic elastomer composition were obtained in the same manner as in Example 1, except that the composition shown in Table 1 was used. The obtained thermoplastic elastomer composition was evaluated in the same manner as in Example 1, and the evaluation results are shown in Table-1.
  • thermoplastic elastomer composition Pellets of the thermoplastic elastomer composition were obtained in the same manner as in Example 1, except that the composition shown in Table-2 was used. The obtained thermoplastic elastomer composition was evaluated in the same manner as in Example 1, and the evaluation results are shown in Table-2.
  • thermoplastic elastomer compositions of Examples 1 to 3 were excellent in moldability, light weight, rubber elasticity, and bleed-out resistance.
  • a degree of biomass corresponding to the content of component (C) was confirmed.
  • Comparative Examples 1 to 3 and 6 to 7 in which paraffin oil was used instead of the isoalkane mixture of component (C), the MFR was small and the moldability was poor.
  • the bleed-out resistance was also inferior.
  • Comparative Example 4 had a small MFR and poor moldability.
  • Comparative Example 5 was inferior in bleed-out resistance.
  • thermoplastic elastomer composition of the present invention is excellent in moldability, light weight, rubber elasticity and bleed-out resistance, it can be used for civil engineering and building material parts (water stop material, joint material, window frame), sporting goods and industrial parts.
  • multilayer hose tube multilayer hose
  • medical parts multilayer medical containers, syringe gaskets, rubber plugs
  • food parts multilayer packaging films, containers, bottles, design packaging, labels, cap liners, packing ), electric wires, miscellaneous goods, automobile parts (weather strips, ceiling materials, interior sheets, bumper moldings, side moldings, air spoilers, hoses, armrests, door trims, console lids, mats).
  • the thermoplastic elastomer composition of the present invention is suitable for applications such as miscellaneous goods and automobile parts that require excellent moldability due to the diversification of designs.

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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