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WO2018147391A1 - Composition de résine thermoplastique, et corps moulé - Google Patents

Composition de résine thermoplastique, et corps moulé Download PDF

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Publication number
WO2018147391A1
WO2018147391A1 PCT/JP2018/004478 JP2018004478W WO2018147391A1 WO 2018147391 A1 WO2018147391 A1 WO 2018147391A1 JP 2018004478 W JP2018004478 W JP 2018004478W WO 2018147391 A1 WO2018147391 A1 WO 2018147391A1
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Prior art keywords
mass
resin composition
thermoplastic
thermoplastic resin
resin
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PCT/JP2018/004478
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English (en)
Japanese (ja)
Inventor
望 藤井
金丸　正実
南　裕
正憲 世良
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出光興産株式会社
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Priority to JP2018567501A priority Critical patent/JPWO2018147391A1/ja
Publication of WO2018147391A1 publication Critical patent/WO2018147391A1/fr

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • 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
    • 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
    • C08L23/16—Ethene-propene or ethene-propene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene

Definitions

  • the present invention relates to a thermoplastic resin composition and a molded body comprising the thermoplastic resin composition.
  • Thermoplastic elastomers used in various fields such as automobiles, machinery and electrical products are generally blended with process oils in order to improve mechanical properties and processability.
  • This process oil is blended in a synthetic rubber base material such as natural rubber, ethylene-propylene-diene rubber (EPDM), olefin-based thermoplastic elastomer, and styrene-based elastomer.
  • EPDM ethylene-propylene-diene rubber
  • olefin-based thermoplastic elastomer olefin-based thermoplastic elastomer
  • styrene-based elastomer styrene-based elastomer
  • thermoplastic resin composition using the thermoplastic elastomer bleeding out is likely to occur. Moreover, since the viscosity of the thermoplastic elastomer is relatively high, improvement in moldability is required. In contrast, in Patent Document 1, bleeding out is suppressed by mixing silicone oil and / or silicone polymer and silicone powder in the thermoplastic resin composition. Moreover, in patent document 2 and 3, the improvement of a softness
  • JP 2000-109702 A Japanese Patent Laid-Open No. 2002-167481 JP-A-11-315176
  • thermoplastic resin composition described in Patent Document 1 is not sufficient to suppress bleed out.
  • thermoplastic elastomers described in Patent Documents 2 and 3 the viscosity has not been sufficiently reduced, and the improvement in flexibility and workability has not been sufficient.
  • thermoplastic resin composition capable of reducing the amount of oil added to the composition without impairing various physical properties, and the heat It aims at providing the molded object which consists of a plastic resin composition.
  • the present disclosure relates to the following.
  • A thermoplastic elastomer resin
  • DSC differential scanning calorimeter
  • thermoplastic resin composition containing a polyolefin resin (B) having a melting endotherm ( ⁇ HD) obtained from a melting endotherm curve of 0 J / g to 80 J / g,
  • the thermoplastic elastomer resin (A) is contained in an amount of 15% by mass to 99.5% by mass with respect to 100% by mass of the thermoplastic resin composition, and the polyolefin resin (B) is contained in an amount of 0.5% by mass to 50% by mass. % Thermoplastic resin composition.
  • DSC differential scanning calorimeter
  • thermoplastic resin composition comprising a polypropylene resin (C) having a melting point (Tm-D) defined as a peak top observed on the side of more than 120 ° C and not more than 180 ° C.
  • Tm-D melting point
  • thermoplastic resin composition containing a polypropylene-based resin (C) and an oil (D) having a temperature of °C or less, 15 parts by mass of the thermoplastic elastomer resin (A) with respect to 100% by mass in total of the thermoplastic elastomer resin (A), the polyolefin resin (B), the polypropylene resin (C) and the oil (D). % To 99.5% by mass, the polyolefin resin (B) from 0.5% to 50% by mass, the polypropylene resin (C) from 0% to 30% by mass and the oil (D).
  • a thermoplastic resin composition containing 0 mass% or more and 70 mass% or less.
  • the additive is added in an amount of 0.05 to 100 parts by mass in total of the thermoplastic elastomer resin (A), the polyolefin resin (B), the polypropylene resin (C), and the oil (D).
  • the thermoplastic resin composition according to [4] which is contained in an amount of not less than 500 parts by mass.
  • thermoplastic resin composition according to any one of the above [1] to [8], wherein the polyolefin resin (B) has a mesotriad fraction [mm] of 20 mol% to 95 mol%. .
  • thermoplastic resin composition according to any one of [10] to [10].
  • thermoplastic elastomer resin (A) according to any one of the above [1] to [11], wherein the thermoplastic elastomer resin (A) includes at least one selected from the group consisting of styrene, diene, silicon, fluorine, ethylene, and isoprene.
  • the thermoplastic resin composition as described.
  • thermoplastic resin composition according to any one of [1] to [12], wherein the thermoplastic elastomer resin (A) contains styrene.
  • a molded article comprising the thermoplastic resin composition according to any one of [1] to [15] above.
  • thermoplastic resin composition capable of reducing the amount of oil added to the composition without impairing various physical properties
  • a molded article comprising the thermoplastic resin composition.
  • a thermoplastic resin composition having a low viscosity and excellent moldability and capable of suppressing bleed-out in the thermoplastic resin composition, and a molded article comprising the thermoplastic resin composition are provided. Can be provided.
  • thermoplastic resin composition of the present embodiment uses a thermoplastic elastomer resin (A) and a differential scanning calorimeter (DSC), holds the sample at ⁇ 10 ° C. for 5 minutes in a nitrogen atmosphere, and then 10 ° C./min.
  • the thermoplastic elastomer resin (A) is contained in an amount of 15% by mass to 99.5% by mass with respect to 100% by mass of the thermoplastic resin composition
  • the polyolefin resin (B) is contained in an amount of 0.5% by mass or more. It is characterized by containing 50 mass% or less.
  • thermoplastic resin composition of another embodiment uses a thermoplastic elastomer resin (A) and a differential scanning calorimeter (DSC), and after holding the sample at ⁇ 10 ° C. for 5 minutes in a nitrogen atmosphere, 10 Thermoplastic resin composition containing a polyolefin resin (B) having a melting endotherm ( ⁇ HD) obtained from a melting endotherm curve obtained by raising the temperature at a rate of ° C./min of 20 J / g to 80 J / g
  • the thermoplastic elastomer resin (A) is contained in an amount of 50% by mass to 99.5% by mass with respect to 100% by mass of the thermoplastic resin composition, and 0.5% of the polyolefin resin (B) is contained. It is characterized by containing not less than 50% by mass and not more than 50% by mass.
  • thermoplastic resin composition is a thermoplastic resin composition containing a thermoplastic elastomer resin (A), a polyolefin resin (B), a polypropylene resin (C), and an oil (D).
  • the thermoplastic elastomer resin (A), the polyolefin resin (B), the polypropylene resin (C), and the oil (D) with respect to 100% by mass in total. 15 mass% to 99.5 mass%, the polyolefin resin (B) is 0.5 mass% to 50 mass%, the polypropylene resin (C) is 0 mass% to 30 mass%, and the oil. (D) is contained in an amount of 0% by mass to 70% by mass.
  • thermoplastic elastomer resin (A) used in the present embodiment is not particularly limited, but various known olefin rubbers can be used.
  • thermoplastic elastomer resin (A) examples include a copolymer of styrene and a conjugated diene, and a hydrogenated product thereof, ethylene- ⁇ -olefin copolymer rubber, butadiene rubber, and nitrile rubber. Further, an ethylene- ⁇ -olefin-nonconjugated polyene copolymer rubber composed of ethylene, an ⁇ -olefin having 3 to 20 carbon atoms and a nonconjugated polyene can be given, and specific examples thereof include ethylene-propylene-nonconjugated. A diene copolymer rubber is mentioned. As the thermoplastic elastomer resin (A), a copolymer of styrene and a conjugated diene and an ethylene-propylene-nonconjugated diene copolymer rubber are preferable.
  • the ethylene- ⁇ -olefin-nonconjugated polyene copolymer rubber is preferably an amorphous random elastic copolymer composed of ethylene, an ⁇ -olefin having 3 to 20 carbon atoms and a nonconjugated polyene, and is mixed with a peroxide.
  • non-conjugated diene examples include non-conjugated dienes such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, and ethylidene norbornene.
  • non-conjugated diene examples include non-conjugated dienes such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, and ethylidene norbornene.
  • ethylene-propylene-nonconjugated diene copolymer rubber and ethylene / 1-butene / nonconjugated diene copolymer rubber are preferred, and ethylene-propylene-nonconjugated diene copolymer rubber, particularly ethylene-propylene.
  • -Ethylidene norbornene copolymer rubber is particularly preferred.
  • non-conjugated polyenes other than non-conjugated dienes include 6,10-dimethyl-1,5,9-undecatriene, 5,9-dimethyl-1,4,8-decatriene, 6, 9-dimethyl-1,5,8-decatriene, 6,8,9-trimethyl-1,5,8-decatriene, 6-ethyl-10-methyl-1,5,9-undecatriene, 4-ethylidene- 1,6-octadiene, 7-methyl-4-ethylidene-1,6-octadiene, 7-methyl-4-ethylidene-1,6-nonadiene, 7-ethyl-4-ethylidene-1,6-nonadiene, 6, 7-dimethyl-4-ethylidene-1,6-octadiene, 6,7-dimethyl-4-ethylidene-1,6-octadiene, 6,7-dimethyl-4-ethylidene
  • the Mooney viscosity [ML (1 + 4), 100 ° C.] of the ethylene- ⁇ -olefin-nonconjugated polyene copolymer rubber is preferably 10 to 250, and more preferably 50 to 200.
  • the iodine value of the ethylene- ⁇ -olefin-nonconjugated polyene copolymer rubber is preferably 25 or less. When the iodine value is in such a range, a thermoplastic elastomer composition that is partially crosslinked with good balance can be obtained.
  • thermoplastic elastomer resin (A) examples include ethylene-propylene-diene rubber (EPDM), styrene-butadiene rubber (SBR), chloroprene rubber (CR), acrylonitrile-butadiene rubber (NBR), and acrylonitrile-chloroprene rubber (ACR).
  • EPDM ethylene-propylene-diene rubber
  • SBR styrene-butadiene rubber
  • CR chloroprene rubber
  • NBR acrylonitrile-butadiene rubber
  • ACR acrylonitrile-chloroprene rubber
  • SBC Styrene-butadiene copolymer resin
  • SEBS styrene-ethylene-butylene-styrene copolymer
  • SBBS styrene-butadiene-butylene-styrene copolymer
  • SEPS styrene-ethylene-propylene-styrene copolymer
  • SEEPS styrene-ethylene-propylene-styrene copolymer
  • SEPS styrene-ethylene-propylene-styrene copolymer
  • SEPS styrene-isoprene-styrene copolymer
  • SIS Styrene Ethylene - propylene copolymer
  • SEP styrene Ethylene - propylene copolymer
  • thermoplastic elastomer resin (A) examples include natural rubber, butadiene rubber (BR), ethylene-propylene rubber (EPR), acrylonitrile-butadiene rubber (NBR), butyl rubber (IIR), styrene-isoprene- Butadiene rubber (SIBR), ethylene-acrylic rubber (EA), polynorbornene rubber, chlorosulfonated polyethylene (CSM), urethane rubber, epichlorohydrin rubber, propylene oxide rubber, acrylic rubber, chlorinated polyethylene, silicone rubber, fluorine rubber Etc.
  • BR butadiene rubber
  • EPR ethylene-propylene rubber
  • NBR acrylonitrile-butadiene rubber
  • IIR butyl rubber
  • SIBR styrene-isoprene- Butadiene rubber
  • EA ethylene-acrylic rubber
  • CSM chlorosulfonated polyethylene
  • urethane rubber epichlorohydrin rubber
  • thermoplastic elastomer resin (A) in the present invention includes an elastomer composition containing a thermoplastic resin and a softening agent that become a fluid phase in the EPDM or SEBS.
  • the thermoplastic elastomer resin (A) the whole elastomer composition is referred to as the thermoplastic elastomer resin (A), not the EPDM itself or SEBS itself in the elastomer composition.
  • a specific example of the thermoplastic resin to be the fluid phase is polypropylene.
  • a specific example of the softening agent that becomes the fluid phase is oil.
  • Specific examples of the elastomer composition include a dynamically crosslinked thermoplastic elastomer, a styrene thermoplastic elastomer, an olefin thermoplastic elastomer, and the like.
  • Dynamic thermoplastic elastomers are often composed of polypropylene, EPDM, natural rubber and oil, and are thermoplastic elastomers that are formed by cross-linking EPDM and natural rubber by adding and kneading peroxides and sulfur. Yes, sometimes abbreviated as TPV (Thermoplastic Vulcanizates). Styrenic thermoplastic elastomers are often composed of polypropylene, styrene block copolymers and oils.
  • thermoplastic elastomer When the styrene block copolymer itself has thermoplasticity, it may be referred to as a thermoplastic elastomer by itself, but when the styrene block copolymer has a high molecular weight and does not exhibit thermoplasticity, a composition containing polypropylene and oil can be used. It is common to impart thermoplasticity. Sometimes abbreviated as TPS (Thermoplastic Stylastic Elastomer) or TPS compound. Olefin-based thermoplastic elastomers are often composed of olefin-based rubbers such as polypropylene and ethylene-propylene rubber and oils.
  • the components may be mixed while polymerizing in the reactor during polymerization. It may be abbreviated as compounding TPO (Thermoplastic Olefin) or reactor TPO.
  • the polyolefin-based resin (B) By adding the polyolefin-based resin (B) to these elastomer compositions, it is possible to improve fluidity and improve physical properties such as compression set, tear strength, and resilience. .
  • the reason is not clear, but it is presumed as follows. That is, the polyolefin resin (B) has high compatibility with polypropylene and exhibits selective compatibility with polypropylene, so that the fluidity of polypropylene in the elastomer composition is improved and the degree of crystallinity is lowered to be soft. It is thought that it works.
  • the oil retention of the polypropylene of the elastomer composition is increased, and in order to suppress embrittlement due to the addition of oil as a softening agent, compression set, tear strength, It is considered that physical properties such as impact resilience are improved.
  • the polyolefin resin (B) also serves as a softening agent, the amount of oil added can be reduced when the hardness of the elastomer composition is constant. As a result, the content of volatile organic compounds (VOC: Volatile Organic Compounds) can be reduced, and the swelling of the rubber component due to oil is suppressed and the crosslink density of the rubber is improved. In addition, physical properties such as tear strength and impact resilience are improved, and the amount of oil bleed is suppressed.
  • VOC Volatile Organic Compounds
  • the crystallization speed is also reduced, so that the fluidity of the resin surface is prevented from abruptly decreasing during molding, resulting in the transfer of a mold or roll. Property is improved, and as a result, the surface appearance of the molded body is improved.
  • the fluidity can be improved while maintaining the physical properties that do not cause brittle fracture. A thermoplastic resin composition having improved tear strength and compression set can be obtained.
  • the polyolefin resin (B) When the polyolefin resin (B) is added to the elastomer composition, it may be produced by adding the polyolefin resin (B) when producing the TPV, TPS, TPO, etc.
  • the polyolefin resin (B) may be added to and kneaded with TPS and TPO.
  • thermoplastic elastomer resin (A) is an elastomer composition
  • EPDM, natural rubber, isoprene rubber, bradiene rubber, etc. in the elastomer composition may be crosslinked.
  • EPDM, natural rubber, isoprene rubber, bradiene rubber and the like are known to be cross-linked with a double bond of a main chain or a side chain by a peroxide or sulfur. Even if it is contained, it is sufficient that the elastomer composition as a whole has thermoplasticity.
  • the content of the thermoplastic elastomer resin (A) in the thermoplastic resin composition is 15% by mass or more and 99.5% by mass or less with respect to 100% by mass of the thermoplastic resin composition. If it is less than 15% by mass, the tensile modulus of the thermoplastic resin composition may be reduced, and if it exceeds 99.5% by mass, the fluidity of the thermoplastic resin composition may be reduced. From such a viewpoint, the content of the thermoplastic elastomer resin (A) is preferably 20% by mass or more, more preferably 25% by mass or more, and further preferably 30% by mass with respect to 100% by mass of the thermoplastic resin composition.
  • % preferably 99.0% by mass or less, more preferably 98.0% by mass or less, and still more preferably 95.0% by mass or less. From the same point of view, 15% by mass or more and 99.5% by mass with respect to 100% by mass in total of the thermoplastic elastomer resin (A), the polyolefin resin (B), the polypropylene resin (C) and the oil (D).
  • % Preferably 20% by mass or more, more preferably 25% by mass or more, still more preferably 30% by mass or more, and preferably 99.0% by mass or less, more preferably 98.0% by mass or less. More preferably, it is 95.0 mass% or less.
  • thermoplastic resin composition when the thermoplastic resin composition is composed of two components, a thermoplastic elastomer resin (A) and a polyolefin-based resin (B), the content of the thermoplastic elastomer resin (A) is preferably 50% by mass or more. Preferably it is 70.0 mass% or more, More preferably, it is 75.0 mass% or more, More preferably, it is 85.0 mass% or more, Preferably it is 99.0 mass% or less, More preferably, it is 98.0 mass. % Or less, more preferably 95.0 mass% or less.
  • the polyolefin resin (B) used in the present embodiment is obtained by using a differential scanning calorimeter (DSC), holding the sample at ⁇ 10 ° C. for 5 minutes in a nitrogen atmosphere, and then raising the temperature at 10 ° C./min.
  • the melting endotherm ( ⁇ HD) obtained from the melting endotherm curve is 0 J / g or more and 80 J / g or less.
  • the melting endotherm ( ⁇ HD) is less than 0 J / g, the occurrence of bleeding out cannot be suppressed in the thermoplastic resin composition, and when it exceeds 80 J / g, the flexibility of the thermoplastic resin composition May be reduced.
  • the melting endotherm ( ⁇ HD) is preferably 20 J / g or more, more preferably 25 J / g or more, still more preferably 27 J / g or more, and even more preferably 30 J / g or more. And preferably it is 50 J / g or less, More preferably, it is 45 J / g or less, More preferably, it is 40 J / g or less.
  • the melting endotherm ( ⁇ H ⁇ D) is the highest temperature in the melting endotherm curve obtained by DSC measurement, with the line connecting the point on the low temperature side where there is no change in calorie and the point on the high temperature side where there is no change in calorie as the baseline. It is calculated by calculating the area surrounded by the line portion including the peak observed on the side and the base line. Note that the melting endotherm ( ⁇ HD) can be controlled by appropriately adjusting the monomer concentration and reaction pressure.
  • the polyolefin resin (B) preferably satisfies the following (1).
  • (1) Using a differential scanning calorimeter (DSC), hold the sample at ⁇ 10 ° C. for 5 minutes in a nitrogen atmosphere, and then raise the temperature at 10 ° C./min.
  • the melting point (Tm-D) defined as the observed peak top is not observed or is 0 ° C. or higher and 120 ° C. or lower.
  • the melting point (Tm-D) of the polyolefin resin (B) is not observed or is 0 ° C. or higher and 120 ° C. or lower from the viewpoint of enhancing the flexibility of the thermoplastic resin composition and suppressing the occurrence of bleed out. preferable.
  • the melting point is observed, from the same viewpoint, it is more preferably 30 ° C or higher, further preferably 35 ° C or higher, still more preferably 40 ° C or higher, and more preferably 90 ° C or lower, still more preferably 80 ° C. or lower, more preferably 70 ° C. or lower, and still more preferably 60 ° C. or lower.
  • the melting point can be controlled by appropriately adjusting the monomer concentration and reaction pressure.
  • the intrinsic viscosity [ ⁇ ] of the polyolefin resin (B) is preferably 0.01 dL / g or more, more preferably 0.10 dL / g or more, still more preferably 0.30 dL / g or more, and still more preferably 0. .40 dL / g or more, and preferably 2.50 dL / g or less, more preferably 2.00 dL / g or less, still more preferably 1.80 dL / g or less, still more preferably 1.70 dL / g or less, More preferably, it is 1.00 dL / g or less.
  • the mixing property of the thermoplastic elastomer resin (A) and the polyolefin resin (B) can be further improved.
  • a viscosity can be reduced more by setting it as 2.50 dL / g or less.
  • the intrinsic viscosity [ ⁇ ] is calculated by measuring the reduced viscosity ( ⁇ SP / c) in tetralin at 135 ° C. with an Ubbelohde viscometer and using the following formula (Huggins formula).
  • the polyolefin resin (B) is not particularly limited as long as the melting endotherm ( ⁇ H ⁇ D) satisfies the above range.
  • a propylene resin or an ethylene resin is preferable.
  • propylene resins include propylene homopolymers, propylene-ethylene block copolymers, propylene-butene block copolymers, propylene- ⁇ -olefin block copolymers, propylene-ethylene random copolymers, propylene-butene random copolymers.
  • propylene polymer selected from a polymer, a propylene-ethylene-butene ternary random copolymer, a propylene- ⁇ -olefin random copolymer, a propylene- ⁇ -olefin graft copolymer, and the like.
  • Propylene homopolymer is more preferable because it does not crosslink by radicals generated by peroxide, light, heat, etc.
  • ethylene-based resin low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE) and the like are preferable.
  • copolymer containing ethylene as a main component for example, a random copolymer of ethylene and an ⁇ -olefin other than ethylene, and a block copolymer of ethylene and an ⁇ -olefin other than ethylene are preferable.
  • the mesotriad fraction [mm] is preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 40 mol% or more, and still more preferably. 50 mol% or more, more preferably 60 mol% or more, and preferably 95 mol% or less, more preferably 80 mol% or less, still more preferably 75 mol% or less, and even more preferably 71 mol% or less. is there.
  • the mesotriad fraction [mm] is a stereoregularity index indicating isotacticity. If the mesotriad fraction [mm] is within the above range, the flexibility of the thermoplastic resin composition is further increased, and bleeding out Generation
  • the mesopentad fraction [mmmm] when the polyolefin resin (B) is a propylene homopolymer is preferably 10 mol% or more, more preferably 16 mol% or more, still more preferably 25 mol% or more, and still more preferably. 35 mol% or more, and preferably 90 mol% or less, more preferably 70 mol% or less, still more preferably 64 mol% or less, still more preferably 60 mol% or less, and even more preferably 51 mol% or less. is there.
  • the mesopentad fraction [mmmm] is an index representing the stereoregularity of the polypropylene resin, and the stereoregularity increases as the mesopentad fraction [mmmm] increases.
  • the mesopentad fraction [mmmm] of the polyolefin resin (B) within the above range, it is possible to further increase the flexibility of the thermoplastic resin composition and further suppress the occurrence of bleed out. it can.
  • mesotriad fraction [mm], the mesopentad fraction [mmmm], and the racemic pentad fraction [rrrr], which will be described later, are described in “Macromolecules, 6, 925 (1973)” by A. Zambelli.
  • the meso fraction in triad units and the meso fraction and racemic fraction in pentad units in the polypropylene molecular chain measured by the methyl group signal in the 13 C-NMR spectrum in accordance with the method proposed in . [Rr] and [mr] described later are also calculated by the above method.
  • the molecular weight distribution (Mw / Mn) of the polyolefin resin (B) is preferably 3.0 or less, more preferably 2.8 or less, still more preferably 2.6 or less, and even more preferably 2.5 or less, And it is preferably 1.5 or more, more preferably 1.6 or more, still more preferably 1.7 or more, and still more preferably 1.8 or more.
  • molecular weight distribution (Mw / Mn) is the value computed from the weight average molecular weight Mw and number average molecular weight Mn of polystyrene conversion measured by the gel permeation chromatography (GPC) method.
  • the polyolefin resin (B) is a propylene homopolymer
  • the value of [rrrr] / (100- [mmmm]) in the polyolefin resin (B) is preferably 0.1 or less from the viewpoint of suppressing stickiness.
  • the upper limit value is more preferably 0.075 or less, still more preferably 0.05 or less, and the lower limit value is more preferably 0.025 or more, and further preferably 0.035 or more.
  • the polyolefin resin (B) is a copolymer
  • it contains at least one structural unit selected from the group consisting of ethylene and an ⁇ -olefin having 4 to 30 carbon atoms, exceeding 0 mol% and not more than 20 mol%. It is preferable from the viewpoint of suppressing the occurrence of brittleness due to crosslinking and increasing the flexibility of the thermoplastic resin composition. From such a viewpoint, more preferably 0.5 mol% or more, still more preferably 1.0 mol% or more, and more preferably 18.5 mol% or less, still more preferably 15.0 mol% or less, More preferably, it is 10.0 mol% or less.
  • the constituent unit of the olefin having 2 carbon atoms is preferably 0 mol%. More than 20 mol%, more preferably more than 0 mol% and 18 mol% or less, still more preferably more than 0 mol% and 16 mol% or less, still more preferably more than 0 mol% and 14 mol% or less.
  • the content of the ⁇ -olefin having 4 or more carbon atoms is preferably more than 0 mol% and 30 mol% or less, more preferably 0 More than mol% and 25 mol% or less, more preferably more than 0 mol% and 20 mol% or less.
  • the content of the polyolefin resin (B) in the thermoplastic resin composition is 0.5% by mass or more and 50.0% by mass or less with respect to 100% by mass of the thermoplastic resin composition. If it is less than 0.5% by mass, the fluidity of the thermoplastic resin composition may be lowered or the hardness may be too high, and if it exceeds 50% by mass, the elastic recovery of the thermoplastic resin composition may be reduced. There is. From such a viewpoint, the content of the polyolefin-based resin (B) is preferably 1.0% by mass or more, more preferably 2.0% by mass or more, further preferably 100% by mass with respect to 100% by mass of the thermoplastic resin composition.
  • 0% by mass or less preferably 1.0% by mass or more, more preferably 2.0% by mass or more, further preferably 5.0% by mass or more, and preferably 30.0% by mass or less, more Preferably it is 25.0 mass% or less, More preferably, it is 22.0 mass% or less. If it is in the said range, it will become possible to lower the kneading
  • the polyolefin resin (B) can be produced using, for example, a metallocene catalyst as described in WO2003 / 087172.
  • a metallocene catalyst as described in WO2003 / 087172.
  • those using a transition metal compound in which a ligand forms a cross-linked structure via a cross-linking group are preferred, and in particular, a transition metal compound that forms a cross-linked structure via two cross-linking groups and Metallocene catalysts obtained by combining promoters are preferred.
  • (I) General formula (I) [In the formula, M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid series, and E 1 and E 2 represent a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, respectively.
  • a ligand selected from a substituted heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group, and a silicon-containing group, which forms a cross-linked structure through A 1 and A 2 They may be the same or different from each other, X represents a sigma-binding ligand, and when there are a plurality of X, the plurality of X may be the same or different, and other X, E 1 , It may be cross-linked with E 2 or Y.
  • Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and may be cross-linked with other Y, E 1 , E 2 or X, and A 1 and A 2 are A divalent bridging group that binds two ligands, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group , -O -, - CO -, - S -, - SO 2 -, - Se -, - NR 1 -, - PR 1 -, - P (O) R 1 -, - BR 1 - or -AlR 1 - R 1 represents a hydrogen atom, a halogen atom, or a carbon number of 1 to 20 Or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms
  • q is an integer of 1 to 5 and represents [(valence of M) -2], and r represents an integer of 0 to 3.
  • a ligand (1,2 ′) (2,1 ′) double-bridged transition metal compound is preferable.
  • the compound of component (ii-1) include triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl tetraphenylborate (tri- n-butyl) ammonium, benzyl tetraphenylborate (tri-n-butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, tetra Benzylpyridinium phenylborate, methyl tetraphenylborate (2-cyanopyridinium), tetrakis (p
  • Examples of the aluminoxane as the component (ii-2) include known chain aluminoxanes and cyclic aluminoxanes.
  • a polyolefin-based resin (B) may be produced using a combination of these organoaluminum compounds.
  • propylene resins corresponding to the polyolefin resin (B) include “El Modu” manufactured by Idemitsu Kosan Co., Ltd., “Tough Selenium” manufactured by Sumitomo Chemical Co., Ltd., “Tuffmer XM” manufactured by Mitsui Chemicals, Inc. "Wintech” manufactured by ExxonMobil, "Verstamaxx” manufactured by Dow, “Licocene” manufactured by Clariant, "REXtac” manufactured by REXtac, “Vestplast” manufactured by Evonik, "Eastoflex” manufactured by Eastman, Or the like.
  • polyethylene resin corresponding to the polyolefin resin (B)
  • various polyethylene resins “Hi-Zex”, “Neo-Zex”, “Ult-Zex”, “Moretech”, “Evolue” manufactured by Prime Polymer Co., Ltd.
  • Each series for example, high-density polyethylene resin “Hi-Zex 2200J”), low-density polyethylene (for example, “Petrocene 190”) manufactured by Tosoh Corporation, “Engage”, “Affinity” manufactured by Dow, and the like.
  • thermoplastic resin composition of the present embodiment is further obtained by using a differential scanning calorimeter (DSC), holding the sample at ⁇ 10 ° C. for 5 minutes in a nitrogen atmosphere, and then raising the temperature at 10 ° C./min. From the viewpoint of strength, it contains a polypropylene resin (C) whose melting point (Tm-D) defined as the peak top observed on the highest temperature side of the obtained melting endotherm curve is higher than 120 ° C. and lower than or equal to 180 ° C. To preferred.
  • the melting point (Tm-D) of the polypropylene resin (C) is preferably 130 ° C. or higher, more preferably 140 ° C. or higher, and preferably 170 ° C. or lower, more preferably 165 ° C. or lower.
  • polypropylene resin (C) examples include propylene homopolymer, propylene-ethylene block copolymer, propylene-butene block copolymer, propylene- ⁇ -olefin block copolymer, propylene-ethylene random copolymer, propylene- A propylene-based polymer (C ′) selected from a butene random copolymer, a propylene- ⁇ -olefin random copolymer, a propylene- ⁇ -olefin graft copolymer, and the like is preferable.
  • the propylene-based polymer (C ′) preferably has an ethylene structural unit content of 1 mol% or less, and contains an ethylene structural unit. More preferred are propylene homopolymers.
  • the polymer using the monomer derived from petroleum or coal may be sufficient as said polymer, and the polymer using the monomer derived from biomass may be sufficient as it.
  • the content thereof is preferably 5% by mass or more, more preferably 8% by mass with respect to 100% by mass of the thermoplastic resin composition. % Or more, more preferably 11% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass or less. If it is 5 mass% or more, the strength improvement of the composition can be expected, and if it is 30 mass% or less, flexibility is not impaired. Further, from the same viewpoint, the total mass of the thermoplastic elastomer resin (A), polyolefin resin (B), polypropylene resin (C) and oil (D) is preferably 5% by mass or more. Preferably it is 8 mass% or more, More preferably, it is 11 mass% or more, Preferably it is 30 mass% or less, More preferably, it is 20 mass% or less.
  • the thermoplastic resin composition of the present embodiment preferably further contains oil (D) from the viewpoint of moldability.
  • the oil (D) is not particularly limited, and mineral oils such as paraffinic process oil, naphthenic process oil, isoparaffinic oil, aromatic mineral oil hydrocarbons, polybutene, polybutadiene, poly ( ⁇ -olefin) Synthetic resin hydrocarbons such as low molecular weight materials such as alkylbenzene, castor oil, tanse oil, rapeseed oil, coconut oil and other fatty oil softeners, dibutyl phthalate, dioctyl phthalate, dioctyl adipate, dioctyl sebacate and other ester systems A plasticizer etc. can be illustrated.
  • mineral oil hydrocarbons, paraffin process oils, and naphthenic process oils are preferably used.
  • paraffinic oil in which the carbon number of the paraffinic hydrocarbon occupies 50% of the total carbon number is preferable.
  • the weight average molecular weight of the mineral oil-based hydrocarbon is preferably 50 to 2,000, particularly preferably 100 to 1,500, and the kinematic viscosity at 40 ° C. is preferably 3 to 800 cSt, particularly 5 to 600 cSt.
  • the pour point is preferably ⁇ 40 to 0 ° C., particularly preferably ⁇ 30 to 0 ° C.
  • the flash point (COC method) is preferably 200 to 400 ° C., particularly preferably 250 to 350 ° C.
  • the kinematic viscosity is a value measured according to ISO 3104
  • the pour point is a value measured according to JIS K2269
  • the flash point is a value measured according to JIS K2265.
  • oils include “Diana Process Oil PW-32”, “Diana Process Oil PW-90”, “Diana Process Oil PW-150”, “Diana Process Oil PW-” manufactured by Idemitsu Kosan Co., Ltd. "380", “Diana Process Oil PS-32”, “Diana Process Oil PS-90”, “Diana Process Oil PS-430”; “Kaydol Oil”, “ParaLux Oil”, “Synfluid”, ExxonMobil made by Chevron USA "AP / E Core”, “SpectraSyn”, Mitsui Chemicals "Lucanto”, “Tough Selenium” and Ineos "Durasyn”, “Indopol”, JXTG Energy's "Te Tracks "etc. (all are Name).
  • the content is preferably 10% by mass or more, more preferably 20% by mass or more, with respect to 100% by mass of the thermoplastic resin composition. More preferably, it is 25% by mass or more, and preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less. If it is 10% by mass or more, it can be expected to improve moldability and have an appropriate hardness, and if it is 70% by mass or less, reduction of oil bleed-out can be expected.
  • the total mass of the thermoplastic elastomer resin (A), polyolefin resin (B), polypropylene resin (C) and oil (D) is preferably 10% by mass or more, more preferably Preferably it is 20 mass% or more, More preferably, it is 25 mass% or more, Preferably it is 70 mass% or less, More preferably, it is 60 mass% or less, More preferably, it is 50 mass% or less.
  • oil (D) content for setting it as appropriate hardness Can be reduced.
  • the thermoplastic resin composition is preferably a total of the thermoplastic elastomer resin (A), the polyolefin resin (B), the polypropylene resin (C) and the oil (D) with respect to 100% by mass of the thermoplastic resin composition. Is 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more.
  • the thermoplastic resin composition may contain other thermoplastic resins and additives as long as the effects of the present invention are not impaired.
  • thermoplastic resin composition of the present embodiment depending on the purpose, a part or all of the thermoplastic elastomer resin (A) and / or the polypropylene resin (C) may be part of the thermoplastic elastomer resin (A) and Other thermoplastic resins other than the polypropylene resin (C) can be substituted.
  • specific examples of other thermoplastic resins are not particularly limited, and include acrylic resins such as polymethyl acrylate, polymethyl methacrylate, and ethylene-ethyl acrylate copolymer, polystyrene resins, nylon 6, nylon 66, nylon 12, and the like.
  • Polyamide resins polyimide resins, acetate resins, polyether sulfonic acid resins, saturated ester resins such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate, thermoplastic urethane resins, thermoplastic elastomers, vinyl chloride resins, polyfluoride Examples thereof include vinyl fluoride resins such as vinyl and polyvinylidene fluoride, and silicone resins.
  • the thermoplastic resin composition may further contain an optional additive as necessary within a range not impairing the object of the present embodiment.
  • additives include radical generators; polyolefins; slip agents; anti-blocking agents; heat stabilizers; antioxidants such as phenolic antioxidants, phosphite antioxidants, and thioether antioxidants; UV absorbers; Crystal nucleating agents; Antiblocking agents; Sealability improvers; Release agents such as stearic acid and silicone oil; Lubricants such as polyethylene wax; Colorants; Ceramics, carbon black, amber, senna, kaolin, Pigments such as nickel titanium yellow, cobalt blue, plaster gray, quinophthalone, diketopyrrolopyrrole, quinacridone, dioxazine, phthalocyanine blue, phthalocyanine green; talc, silica, calcium carbonate, magnesium carbonate, aluminum hydroxide, barium sulfate, Inorganic hollow fillers such as glass fiber, glass
  • Antioxidants include trisnonylphenyl phosphite, distearyl pentaerythritol diphosphite, “ADK STAB 1178” (manufactured by ADEKA, “ADEKA STAB” is a registered trademark), “Smilizer TNP” (manufactured by Sumitomo Chemical Co., Ltd.) , “Smilizer” is a registered trademark), “Irgafos 168” (manufactured by BASF, “Irgaphos” is a registered trademark), “Sandostab P-EPQ” (manufactured by Sand, “Sandostab” is a registered trademark), etc.
  • the content can be appropriately determined according to the type of the additive.
  • the content can be appropriately determined according to the type of the additive.
  • the content can be 10 parts by mass or less, more preferably 5 parts by mass or less, preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.2 parts by mass. Part or more, more preferably 0.5 part by mass or more.
  • thermoplastic resin composition of the present embodiment it is also possible to partially crosslink by adding a crosslinking agent or a crosslinking aid.
  • the cross-linking agent include organic peroxides, sulfur, sulfur compounds, phenolic vulcanizing agents such as phenol resins, and the like. In these, an organic peroxide is preferable. Specific examples of the organic peroxide include 2,5-dimethyl-2,5-di (t-butylperoxy) -hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) -3.
  • crosslinking aid examples include N-methyl-N, 4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, divinylbenzene, trimethylolpropane tri (meth) acrylate, ethylene di (meth) acrylate, diethylene glycol di (meth).
  • thermoplastic elastomer resin (A) which is the main component of the cross-linked product
  • polyolefin resin (B) are capable of using organic peroxides. Since it has a solubilizing action and functions as a dispersant for organic peroxide, a thermoplastic resin composition having a uniform crosslinking effect by heat treatment and having a balance between fluidity and physical properties can be obtained.
  • crosslinking agent and the crosslinking assistant may be used alone or in combination of two or more.
  • the crosslinking degree is adjusted by arbitrarily using 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of components (A) to (D). be able to.
  • an unsaturated silane compound is used as a crosslinking aid, the crosslinking can be further advanced by contacting with moisture in the presence of a silanol condensation catalyst.
  • the thermoplastic resin composition of the present embodiment includes the thermoplastic elastomer resin (A) and the polyolefin resin (B), and further, if necessary, a polypropylene resin (C), an oil (D), and additives. It is obtained by blending and melt-kneading.
  • the thermoplastic elastomer resin (A) and the polyolefin resin (B) pellets can be dry blended and then charged into a hopper of an extruder and melt-kneaded.
  • the pellet of thermoplastic elastomer resin (A) may be added, and it may melt-knead using the extruder connected with the superposition
  • thermoplastic elastomer resin (A) is polymerized
  • the polyolefin resin (B) is mixed and desolvated before solvent degassing to obtain a composition of the thermoplastic elastomer (A) and the polyolefin resin (B). It may be manufactured. Thereafter, pelletization can be performed as necessary. Kneading the composition after kneading composed of the thermoplastic elastomer (A) and the polyolefin resin (B) with the polypropylene resin (C) and / or the oil (D) regardless of the presence or absence of the pelletizing process. You can also.
  • thermoplastic elastomer resin (A) and the oil (D) are kneaded, both of them can be easily kneaded without immersing the thermoplastic elastomer resin (A) in the oil (D) in advance. It becomes possible.
  • the kneading can be performed using a commonly used apparatus such as a high-speed mixer, a Banbury mixer, a continuous kneader, a single or twin screw extruder, a roll, a Brabender plastograph, or the like. You may pelletize using an extruder after kneading
  • the viscosity ( ⁇ 1 ) at an angular frequency of 1 rad / s of the thermoplastic resin composition of the present embodiment is preferably 25,000 mPa ⁇ s or less, more preferably 21,000 mPa ⁇ s or less, and preferably 800 mPa ⁇ s or more. , More preferably 1,000 mPa ⁇ s or more, and still more preferably 1,200 mPa ⁇ s or more.
  • the viscosity ( ⁇ 100 ) at an angular frequency of 100 rad / s of the thermoplastic resin composition is preferably 1,500 mPa ⁇ s or less, more preferably 1,000 mPa ⁇ s or less, and preferably 100 mPa ⁇ s or more. More preferably, it is 150 mPa * s or more, More preferably, it can be 200 mPa * s or more. If it is in the said range, sufficient moldability will be ensured.
  • the viscosity of the thermoplastic resin composition at each predetermined speed can be measured by the method described in Examples.
  • the thermoplastic resin composition preferably has a viscosity ratio ( ⁇ 1 / ⁇ 100 ) of a viscosity ( ⁇ 1 ) having an angular frequency of 1 rad / s and a viscosity ( ⁇ 100 ) having an angular frequency of 100 rad / s. Or more, more preferably 5.0 or more, still more preferably 7.0 or more, and preferably 60 or less, more preferably 50 or less, still more preferably 40 or less, still more preferably 15 or less. Can do. By setting the viscosity ratio ( ⁇ 1 / ⁇ 100 ) to 3.0 or more, the viscosity is lowered by shearing, and the fluidity at the time of injection is improved. By setting the viscosity ratio to 60 or less, uneven injection is suppressed and defective injection is reduced. Can do.
  • the melt flow rate (MFR) of the thermoplastic resin composition is preferably 2.0 g / 10 min or more, more preferably 2.5 g / 10 min or more, still more preferably 3.0 g / 10 min or more from the viewpoint of fluidity. Yes, and preferably 20.0 g / 10 min or less, more preferably 15.0 g / 10 min or less, still more preferably 10.0 g / 10 min or less.
  • the MFR is measured by a measurement method defined in JIS K7210, and is measured under conditions of a temperature of 230 ° C. and a load of 21.18N.
  • the tensile elastic modulus of the thermoplastic resin composition is preferably 0.5 MPa ⁇ s or more, more preferably 1.0 MPa ⁇ s or more, still more preferably 5.0 MPa ⁇ s or more, and preferably 200 MPa ⁇ s. Hereinafter, it is more preferably 100 MPa ⁇ s or less, and still more preferably 80 MPa ⁇ s or less.
  • the tensile elastic modulus can be measured by the method described in the examples.
  • the molded object of this invention is a molded object which consists of the said resin composition.
  • the resin composition can obtain a molded body having a desired shape by a known molding method such as injection molding, extrusion molding, blow molding, inflation molding, compression molding, or vacuum molding.
  • the polymerization temperature was set to 58 ° C., and propylene and hydrogen were continuously supplied so that the hydrogen partial pressure in the gas phase part of the reactor was maintained at 50 kPa and the total pressure in the reactor was maintained at 1.0 MPaG. went.
  • “Irganox 1010” manufactured by BASF Japan Ltd.
  • a polypropylene resin (B-2) was obtained.
  • Propylene and hydrogen were continuously supplied at a polymerization temperature of 75 ° C. so that the gas phase hydrogen concentration was 24 mol% and the total pressure in the reactor was maintained at 1.0 MPa ⁇ G.
  • the propylene polymer (B-3) was obtained by adding an antioxidant to the resulting polymerization solution so that the content thereof was 1000 ppm by mass, and then removing n-heptane as a solvent. .
  • Propylene and hydrogen were continuously supplied at a polymerization temperature of 70 ° C. so that the gas phase hydrogen concentration was 15 mol% and the total pressure in the reactor was maintained at 1.0 MPa ⁇ G.
  • the propylene polymer (B-4) was obtained by adding an antioxidant to the obtained polymerization solution so that the content thereof was 1000 ppm by mass, and then removing n-heptane as a solvent. .
  • the melting endotherm ( ⁇ H ⁇ D) is a differential scanning calorimeter (manufactured by Perkin Elmer Co., Ltd.) with the line connecting the low temperature side point where there is no change in heat amount and the high temperature side point where there is no change in heat amount as the baseline. , “DSC-7”), and calculating the area surrounded by the line portion including the peak of the melting endothermic curve obtained by DSC measurement and the base line.
  • Weight average molecular weight (Mw), molecular weight distribution (Mw / Mn) measurement The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) method to determine the molecular weight distribution (Mw / Mn). For the measurement, the following equipment and conditions were used, and polystyrene-reduced weight average molecular weight and number average molecular weight were obtained.
  • the molecular weight distribution (Mw / Mn) is a value calculated from these weight average molecular weight (Mw) and number average molecular weight (Mn).
  • ⁇ GPC measurement device Column: “TOSO GMHHR-H (S) HT” manufactured by Tosoh Corporation Detector: RI detection for liquid chromatogram "WATERS 150C” manufactured by Waters Corporation ⁇ Measurement conditions> Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C Flow rate: 1.0 mL / min Sample concentration: 2.2 mg / mL Injection volume: 160 ⁇ L Calibration curve: Universal Calibration Analysis program: HT-GPC (Ver.1.0)
  • the mesopentad fraction [mmmm], the racemic pentad fraction [rrrr] and the racemic mesoracemi mesopentad fraction [rmrm] are described in “Macromolecules, 6, 925 (1973)” by A. Zambelli et al.
  • the meso fraction, the racemic fraction, and the racemic meso-racemic meso in the pentad unit in the polypropylene molecular chain measured by the methyl group signal in the 13 C-NMR spectrum were obtained according to the proposed method. It is a fraction.
  • the mesopentad fraction [mmmm] increases, the stereoregularity increases.
  • the triad fractions [mm], [rr] and [mr] were also calculated by the above method.
  • MFR Melt flow rate
  • Crystallinity (%) ⁇ H / ⁇ Hm 0 ⁇ 100
  • ⁇ Hm 0 represents a melting heat capacity of a complete crystal
  • thermoplastic resin composition [Reference Examples 1 and 2, Examples 1 to 3, and Comparative Examples 1 to 3] Each component of the types and blending amounts shown in Table 2 was melt kneaded at 230 ° C. for 3 minutes using a lab plast mill to prepare a thermoplastic resin composition. The obtained thermoplastic resin composition was molded using a press machine at 200 ° C. for 4 minutes to obtain a press sheet having a thickness of 1 mm. In Table 2, a blank represents no blending.
  • Examples 4 and 5 and Comparative Examples 4 to 6 Each component of the types and blending amounts shown in Table 3 was melt kneaded at 230 ° C. for 3 minutes using a lab plast mill to prepare a thermoplastic resin composition. The obtained thermoplastic resin composition was molded using a press machine at 200 ° C. for 4 minutes to obtain a press sheet having a thickness of 1 mm.
  • Examples 6 to 8 and Comparative Example 7 Among the components of the types and blending amounts shown in Table 4, components other than the crosslinking agent and the crosslinking aid are melt-kneaded at 200 ° C. for 10 minutes using a lab plast mill, and then the crosslinking agent and the crosslinking aid are added. In addition, it was further melt-kneaded for 10 minutes to prepare a thermoplastic resin composition. The obtained thermoplastic resin composition was molded using a press machine at 200 ° C. for 4 minutes to obtain a press sheet having a thickness of 1 mm. In Table 4, blanks indicate no blending. Further, the contents of the antioxidant, the crosslinking agent and the crosslinking aid are the contents relative to 100 parts by mass of the total amount of the components (A) to (D).
  • Examples 9 to 21 and Comparative Example 8 Among the components of the types and blending amounts shown in Table 5, components other than the crosslinking agent and the colorant are melt-kneaded for 10 minutes at 200 ° C. using a lab plast mill, and then the crosslinking agent and the colorant are added. Further, the mixture was melt-kneaded for 10 minutes to prepare a thermoplastic resin composition. The obtained thermoplastic resin composition was molded using a press machine at 200 ° C. for 4 minutes to obtain a press sheet having a thickness of 1 mm. In Table 5, blanks indicate no blending. Further, the content of the crosslinking agent and the colorant is the content based on 100 parts by mass of the total amount of the components (A) to (D).
  • Examples 22 to 25 and Comparative Examples 9 to 10 Each component of the types and blending amounts shown in Table 6 was melt kneaded at 230 ° C. for 3 minutes using a lab plast mill to prepare a thermoplastic resin composition. The obtained thermoplastic resin composition was molded using a press machine at 200 ° C. for 4 minutes to obtain a press sheet having a thickness of 1 mm. In Table 6, a blank represents no blending.
  • Examples 26 to 34 and Comparative Example 11 Among the components of the types and blending amounts shown in Table 7, components other than the crosslinking agent and the colorant are melt-kneaded for 10 minutes at 200 ° C. using a lab plast mill, and then the crosslinking agent and the colorant are added. Further, the mixture was melt-kneaded for 10 minutes to prepare a thermoplastic resin composition. The obtained thermoplastic resin composition was molded using a press machine at 200 ° C. for 4 minutes to obtain a press sheet having a thickness of 1 mm. In Table 7, a blank represents no blending.
  • the raw materials used in Examples, Reference Examples and Comparative Examples are as follows.
  • Kraton (registered trademark) G1651 Styrene-ethylene-butylene-styrene copolymer, manufactured by Kraton Polymer Japan Co., Ltd., styrene content: 33% by weight, solution viscosity: 1.5 Pa ⁇ s (type B (Viscometer, 10wt% toluene solution, 25 ° C) (A-3) Nordel (registered trademark) IP 4760P: ethylene-propylene-ethylidene norbornene copoly
  • Santoprene 101-55 Dynamically cross-linked thermoplastic elastomer, manufactured by ExxonMobil, Shore A hardness: 94 (A-6) Santoprene 101-87: Dynamically cross-linked thermoplastic elastomer, manufactured by ExxonMobil, Shore A hardness: 60
  • Vestplast 708 propylene-butene-ethylene copolymer, manufactured by Evonik, melting point (Tm-D): 105 ° C.
  • Vistamaxx 8780 propylene-ethylene copolymer, manufactured by ExxonMobil, melting point (Tm-D): 105 ° C.
  • Affinity GA 1950 ethylene-octene copolymer, manufactured by Dow, melting point (Tm-D): 60 ° C.
  • Licocene 1602 Propylene-ethylene copolymer, manufactured by Clariant, melting point (Tm-D): 70 ° C.
  • PW-90 Oil, manufactured by Idemitsu Kosan Co., Ltd., trade name, kinematic viscosity at 40 ° C. 90 cSt, pour point ⁇ 17.5 ° C., flash point 266 ° C.
  • D-2 Amorphous propylene homopolymer (D) produced in Production Example 5 ⁇
  • D-3 Polybutene LV-100: Polybutene (PB), manufactured by JX Energy Corporation, trade name ⁇
  • PW-32 Oil, manufactured by Idemitsu Kosan Co., Ltd., trade name at 40 ° C. Kinematic viscosity 30.6mm 2 / s, pour point -17.5 ° C, flash point 222 ° C
  • Viscosity A disk-shaped test piece having a diameter of 25 mm and a thickness of 1 mm was produced by press molding. Using a rheometer MCR301 manufactured by Anton Paar, one of the above test pieces was subjected to dynamic viscoelasticity at a gap distance of 1.0 mm, a strain of 5%, a temperature of 230 ° C., and a shear rate of 600 s ⁇ 1 to 1 s ⁇ 1. Was measured. From the measurement results, the viscosities at shear rates of 1 s ⁇ 1 and 100 s ⁇ 1 were determined, and the viscosity ratio ( ⁇ 1 / ⁇ 100 ) was calculated. In Examples 4 to 8 and Comparative Examples 4 to 7, dynamic viscoelasticity was measured by changing the measurement temperature to 220 ° C.
  • Viscosity reduction rate at an angular frequency of 100 rad / s per 1% mixing rate (R 100-1% )
  • the ratio of the addition amount of the polyolefin resin (B) to the sum of the addition amount of the polyolefin resin (B) and the addition amount of the thermoplastic elastomer resin (A) is c (mass%), and the viscosity reduction rate (R 100-1% ) was calculated by the following formula (2).
  • R 100-1% R 100 / c (%) (2)
  • melt flow rate Measurement was performed under conditions of a temperature of 230 ° C. and a load of 2.16 kg according to JIS K7210.
  • thermoplastic resin composition was placed in a silicone mold having a diameter of 35 mm and a height of 20 mm, dissolved in a vacuum dryer (180 ° C.), and then cooled to obtain a test sample. This sample was placed on a filter paper and allowed to stand in a thermostatic bath at 65 ° C. for 7 days, and then the bleeding out property was evaluated according to the following criteria to the extent that the exudation component was absorbed by the filter paper.
  • thermoplastic resin composition was press-molded under the following conditions to produce a 1 mm thick sheet-like test piece (press sheet).
  • the press sheet of the produced thermoplastic resin composition was stored at room temperature for 1 day and conditioned. Press molding conditions: molding temperature 200 ° C., preheating time 10 minutes, pressurization time 5 minutes, cooling time 5 minutes (water cooling)
  • Oil bleed ⁇ 2> samples of 30 mm ⁇ 30 mm ⁇ 1 mm were produced by hot press molding. After sandwiching the sample with the oil removing paper (65 mm ⁇ 97 mm) whose weight was measured in advance, the upper and lower sides of the sample sandwiched between the oil removing paper were further sandwiched between aluminum plates (45 mm ⁇ 45 mm). This was placed on a bat, a weight of 1 kg was placed on it, and it was placed in a thermostat set at 60 ° C. in advance. After 24 hours, the sample was taken out from the thermostatic chamber and allowed to stand at room temperature for 24 hours. Then, the weight of the oil removing paper was measured, and the increased weight was taken as the weight of the bleed oil.
  • the amount of oil bleed out depends on the amount of oil in the compound.
  • the breaking strength and elongation depend on the amount of oil when the content of the component (A) and the total content of the components (B) and (C) are not reversed.
  • the reason why the breaking strength and the elongation change depending on the amount of oil is considered to be that the component (A) swells and becomes brittle when oil is added.
  • it contributes to lowering the viscosity and elastic modulus of the component (C), but has no effect of swelling the component (A) and does not lower the physical properties of the component (A). This is considered to be because the component (B) is selectively compatible with the component (C).
  • thermoplastic resin composition of the present invention has a low viscosity, excellent moldability, and bleed out in the thermoplastic resin composition even when it contains an additive such as an antioxidant. It can be seen that this can be suppressed.
  • Tables 5 to 7 show material properties other than those described above. [Measuring method] Under the measurement conditions shown below, the properties of the thermoplastic resin compositions obtained in the Examples and Comparative Examples in Tables 5 to 7 and the test pieces comprising the same were measured and evaluated. The results are shown in Tables 5-7.
  • thermoplastic resin composition was press-molded under the following conditions to produce a 2 mm thick press sheet and a 15 mm thick block test piece.
  • the test piece of the produced thermoplastic resin composition was stored at room temperature for 1 day and conditioned. Press molding conditions: molding temperature 175 ° C., preheating time 5 minutes (sheet), 10 minutes (block), pressurization time 3 minutes, cooling time 10 minutes (water cooling)
  • Test piece preparation method After sheet preparation by press molding, punching test piece shape: Dumbbell shape No. 3 Measurement temperature: 23 ° C Test speed: 500 mm / min Test machine: Precision universal testing machine Autograph EZ-LX 1kN manufactured by Shimadzu Corporation Test machine capacity: Load cell type 1kN
  • Test piece production method After producing a sheet by press molding, punching test piece shape: no cut angle type test temperature: 23 ° C Test speed: 500 mm / min Test machine: Precision universal testing machine Autograph EZ-LX 1kN manufactured by Shimadzu Corporation Test machine capacity: Load cell type 1kN
  • melt flow rate Based on JIS K7210, it measured on condition of temperature 230 degreeC and load 2.16kg.
  • thermoplastic resin composition of the present invention is excellent in compression set and can suppress bleed out.
  • Example 9 when comparing Comparative Example 8 and Example 9, in Example 9, by replacing half of the hard polypropylene resin (C) in Comparative Example 8 with the polyolefin resin (B), the system becomes soft, The oil (D) that is a softening agent can be reduced accordingly. And by reducing the amount of oil (D), the swelling rate of the thermoplastic elastomer resin (A) can be reduced, compression set can be reduced, and the amount of oil bleed can also be reduced.
  • Example 10 Comparing Examples 9 and 10, in Example 10, the polypropylene resin (C) in Example 9 was changed to a high fluid grade polypropylene (C-4) and the amount of polyolefin resin (B) was increased. Further, the compression set can be further reduced as compared with Example 9, and the amount of oil bleed can also be reduced. Comparing Comparative Example 8 and Example 11, in Example 11, by adding the polyolefin resin (B) to the composition of Comparative Example 8, the system becomes soft and compression set can be reduced. And the amount of oil bleed can be reduced.
  • thermoplastic resin composition of the present invention can reduce the amount of oil added to the composition without impairing various physical properties.
  • the thermoplastic resin composition of the present invention has a viscosity. It is low and excellent in moldability, and can suppress bleed-out in the thermoplastic resin composition. Therefore, the thermoplastic resin composition of the present invention is used for automobile exterior materials such as moldings, wipers, and bumpers; automotive interiors such as instrument panels, center panels, center console boxes, door trims, pillars, assist grips, handles, and airbag covers.
  • Automotive functional parts such as rack and pinion boots, suspension boots, constant velocity joint boots, etc .; remote control switches, various key tops for OA equipment, home appliance parts such as TVs, stereos, vacuum cleaners; electrical appliances; underwater glasses, underwater cameras, etc. Covers; Various packings; Sealing materials, Adhesives; Rollers; Sheets and films for daily goods, industrial materials, foods, etc .; Food containers; Infants and infants; Wire covering materials, Silence gears; Sports shoes, fashion sandals Footwear such as; skin material; bell Suitable for medical supplies such as medical supplies such as medical casts, catheters, infusion bags, and medical syringe gaskets. Can be used.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention fournit une composition de résine thermoplastique permettant une réduction de la quantité d'addition d'huile qu'elle contient, sans perte de ses propriétés physiques diverses, et un corps moulé constitué de cette composition de résine thermoplastique. Plus précisément, l'invention concerne une composition de résine thermoplastique qui comprend une résine élastomère thermoplastique (A), et une résine à base de polyoléfine (B) de quantité d'endotherme de fusion （ΔＨ－Ｄ） supérieure ou égale à ０Ｊ／ｇ et inférieure ou égale à ８０Ｊ／ｇ. Pour 100% en masse de composition, ladite composition de résine thermoplastique contient 15% en masse ou plus à 99,5% en masse ou moins de ladite résine élastomère thermoplastique (A), et 0,5% en masse ou plus à 50% en masse ou moins de ladite résine à base de polyoléfine (B).
PCT/JP2018/004478 2017-02-13 2018-02-08 Composition de résine thermoplastique, et corps moulé WO2018147391A1 (fr)

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WO2019077989A1 (fr) * 2017-10-19 2019-04-25 出光興産株式会社 Composition de résine élastomère, et corps moulé
JPWO2020085502A1 (ja) * 2018-10-25 2021-09-24 三井化学株式会社 不織布積層体、並びに、伸縮性不織布積層体、繊維製品、吸収性物品及び衛生マスク
CN113999535A (zh) * 2022-01-04 2022-02-01 浙江金仪盛世生物工程有限公司 热塑性弹性体材料及热塑性弹性体管路
WO2022270572A1 (fr) 2021-06-24 2022-12-29 三井化学株式会社 Composition d'élastomère thermoplastique, corps moulé de celle-ci et utilisation associée
CN116113668A (zh) * 2020-09-23 2023-05-12 安姆希比创新咨询有限公司 热塑性弹性体组合物及复合成型体

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WO2015095987A1 (fr) * 2013-12-24 2015-07-02 Exxonmobil Chemical Patents Inc. Compositions comprenant un vulcanisat thermoplastique, matériau alvéolaire et articles fabriqués à partir desdites compositions
JP2015193821A (ja) * 2014-03-19 2015-11-05 三菱化学株式会社 熱可塑性エラストマー組成物、成形体及びエアバッグ収納カバー

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WO2015095987A1 (fr) * 2013-12-24 2015-07-02 Exxonmobil Chemical Patents Inc. Compositions comprenant un vulcanisat thermoplastique, matériau alvéolaire et articles fabriqués à partir desdites compositions
JP2015193821A (ja) * 2014-03-19 2015-11-05 三菱化学株式会社 熱可塑性エラストマー組成物、成形体及びエアバッグ収納カバー

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Publication number Priority date Publication date Assignee Title
WO2019077989A1 (fr) * 2017-10-19 2019-04-25 出光興産株式会社 Composition de résine élastomère, et corps moulé
JPWO2020085502A1 (ja) * 2018-10-25 2021-09-24 三井化学株式会社 不織布積層体、並びに、伸縮性不織布積層体、繊維製品、吸収性物品及び衛生マスク
JP7308223B2 (ja) 2018-10-25 2023-07-13 三井化学株式会社 不織布積層体、並びに、伸縮性不織布積層体、繊維製品、吸収性物品及び衛生マスク
CN116113668A (zh) * 2020-09-23 2023-05-12 安姆希比创新咨询有限公司 热塑性弹性体组合物及复合成型体
EP4219619A4 (fr) * 2020-09-23 2024-03-27 MCPP Innovation LLC Composition d'élastomère thermoplastique et objet moulé composite
WO2022270572A1 (fr) 2021-06-24 2022-12-29 三井化学株式会社 Composition d'élastomère thermoplastique, corps moulé de celle-ci et utilisation associée
KR20240009507A (ko) 2021-06-24 2024-01-22 미쓰이 가가쿠 가부시키가이샤 열가소성 엘라스토머 조성물, 그의 성형체, 및 그의 용도
CN113999535A (zh) * 2022-01-04 2022-02-01 浙江金仪盛世生物工程有限公司 热塑性弹性体材料及热塑性弹性体管路

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