WO2020045082A1 - Composition d'élastomère thermoplastique et son procédé de production - Google Patents

Composition d'élastomère thermoplastique et son procédé de production Download PDF

Info

Publication number
WO2020045082A1
WO2020045082A1 PCT/JP2019/031875 JP2019031875W WO2020045082A1 WO 2020045082 A1 WO2020045082 A1 WO 2020045082A1 JP 2019031875 W JP2019031875 W JP 2019031875W WO 2020045082 A1 WO2020045082 A1 WO 2020045082A1
Authority
WO
WIPO (PCT)
Prior art keywords
copolymer
thermoplastic elastomer
aromatic vinyl
aromatic
vinyl compound
Prior art date
Application number
PCT/JP2019/031875
Other languages
English (en)
Japanese (ja)
Inventor
亘佑 中村
雄志 熊谷
勝 長谷川
哲央 野口
Original Assignee
デンカ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by デンカ株式会社 filed Critical デンカ株式会社
Priority to JP2020539323A priority Critical patent/JP7348191B2/ja
Publication of WO2020045082A1 publication Critical patent/WO2020045082A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
    • B60R13/02—Internal Trim mouldings ; Internal Ledges; Wall liners for passenger compartments; Roof liners
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

  • the present invention relates to a thermoplastic elastomer composition having excellent heat resistance, oil resistance, and scratch resistance, and a molded article, a sheet, and a skin material using the same, and a method for producing the same.
  • Skin materials covering the surface of various hard machines such as passenger cars and various automobiles, furniture and indoor interiors, and robots are required to have various functions in addition to various levels of softness.
  • interior skin materials for automobiles heat resistance, weather resistance, cold resistance, creasing retention including heat history during molding, scratch resistance to human contact (scratch wear resistance), accompanying humans
  • scratch resistance to human contact scratch wear resistance
  • Oil resistance and chemical resistance to chemical substances are required.
  • a skin material sheet made of soft vinyl chloride (soft PVC) to which a plasticizer is added has been used.
  • Soft PVC has excellent softness, oil resistance, and scratch resistance, and is a material that is advantageous in cost.
  • soft PVC contains problems of management during incineration, that is, volatile organic compounds (VOCs) due to plasticizers contained in large quantities in recent years, concerns that some plasticizers may become environmental hormones, and heavy metal stabilizers. Therefore, there is a demand for materials having better environmental properties. Therefore, skin material sheets made of TPO (thermoplastic olefin resin) or TPS (thermoplastic styrene resin) have been receiving attention. TPO and TPS are characterized by heat resistance, softness, recyclability, and environmental friendliness, and have been widely used.
  • These materials are compounds composed of a soft component and a heat-resistant component, but have the problem that the scratch resistance is reduced to an insufficient level by the PP (isotactic polypropylene) component used as the heat-resistant component.
  • the PP isotactic polypropylene
  • the crosslinked ethylene-propylene rubber or the crosslinked or non-crosslinked styrene-based hydrogenated block copolymer used as a soft component does not have sufficient oil resistance, and may swell or deform in a severe environment. Even if an attempt is made to improve the scratch resistance by reducing the amount of PP added, there is a problem that the heat resistance, in particular, the surface grain retention at the time of sheet molding is reduced and the grain disappears.
  • Patent Literatures 1 and 2 disclose a so-called “method” obtained by a method of copolymerizing a small amount of divinylbenzene with a styrene-ethylene copolymer and introducing a polystyrene chain (cross chain) via a vinyl group of the divinylbenzene unit.
  • Cross copolymers have been proposed.
  • the cross copolymer obtained by this method is a block copolymer having a branched structure having a styrene-ethylene copolymer chain as a soft segment and polystyrene as a hard segment.
  • JP 2009-102515 A International Publication No. 2007/139116 International Publication No. 2009/128444 JP 2010-24215 A
  • Cloth copolymers are thermoplastic elastomers that have excellent properties such as scratch resistance, softness, transparency, and moldability, but depending on the application, heat resistance and oil resistance may be insufficient. However, there is a problem that it is difficult to improve heat resistance and oil resistance while maintaining such characteristics. In order to cope with such a problem, if PP is added to increase the heat resistance, the abrasion resistance with scratches is reduced as in the case of TPO and TPS. Therefore, the addition of PPE (polyphenylene ether) resin (Patent Document 3) and the addition of TPEE (Polyester soft resin) (Patent Document 4) improve the heat resistance.
  • PPE polyphenylene ether
  • TPEE Polyyester soft resin
  • Patent Literature 1 describes in particular a tape base material, an electric wire covering material, and a foamed material using an electron beam crosslinked body of a cross copolymer.
  • Patent Document 2 describes a composition obtained by dynamically cross-linking a cross-copolymer with another polymer, particularly a crystalline polypropylene.
  • thermoplastic elastomer composition using the above-mentioned cross-copolymer according to the conventional technique still cannot be said to have sufficient heat resistance and oil resistance, and does not have sufficient scratch resistance.
  • interior skin materials for automobiles and the like are required to have high heat resistance, oil resistance, and scratch resistance, and are also required to have high-temperature oil resistance, so that a higher-performance thermoplastic elastomer composition has been required. .
  • the present invention can provide a thermoplastic elastomer composition having excellent heat resistance, oil resistance, and scratch resistance, and a molded article, a sheet, and a skin material using the same.
  • the storage elastic modulus E ′ can be measured at 150 ° C. and 190 ° C., and the ratio of the storage elastic modulus E ′ between 190 ° C. and 150 ° C. (E ′ ( 190) / E ′ (150)) is 0.3 or more, the thermoplastic elastomer composition according to [1] or [2].
  • the cross copolymer (A) has a structure in which an olefin-aromatic vinyl compound-aromatic polyene copolymer chain and an aromatic vinyl compound polymer chain are bonded via an aromatic polyene monomer unit.
  • the thermoplastic elastomer composition according to any one of [1] to [3], which is a copolymer satisfying at least one of the following conditions (1) to (3).
  • the content of the aromatic vinyl compound monomer unit of the olefin-aromatic vinyl compound-aromatic polyene copolymer is 10 to 30 mol%, and the content of the aromatic polyene monomer unit is 0.01 mol% or more. 0.5 mol% or less, the balance being the content of olefin monomer units.
  • the olefin-aromatic vinyl compound-aromatic polyene copolymer has a weight average molecular weight of 50,000 or more and 300,000 or less, and a molecular weight distribution (Mw / Mn) of 1.8 or more and 6 or less.
  • the content of the olefin-aromatic vinyl compound-aromatic polyene copolymer contained in the cross copolymer is in the range of 60 to 95% by mass.
  • the cross copolymer (A) has a structure in which an ethylene-aromatic vinyl compound-aromatic polyene copolymer chain and an aromatic vinyl compound polymer chain are bonded via an aromatic polyene monomer unit.
  • the thermoplastic elastomer composition according to any one of [1] to [4], which is a copolymer satisfying at least one of the following conditions (1) to (3).
  • the content of the aromatic vinyl compound monomer unit of the ethylene-aromatic vinyl compound-aromatic polyene copolymer is 10 to 30 mol%, and the content of the aromatic polyene monomer unit is 0.01 mol% or more. 0.5 mol% or less, with the balance being the ethylene monomer unit content.
  • the ethylene-aromatic vinyl compound-aromatic polyene copolymer has a weight average molecular weight of 50,000 or more and 300,000 or less, and a molecular weight distribution (Mw / Mn) of 1.8 or more and 6 or less.
  • the content of the ethylene-aromatic vinyl compound-aromatic polyene copolymer contained in the cross copolymer is in the range of 70 to 95% by mass.
  • the cross copolymer (A) is composed of 70 to 95% by mass of an olefin-aromatic vinyl-aromatic polyene copolymer having an aromatic vinyl monomer unit content of 10 to 30% by mole, and aromatic vinyl monomer. 5 to 30% by mass of an aromatic vinyl polymer comprising monomer units, and the olefin-aromatic vinyl-aromatic polyene copolymer and the aromatic vinyl polymer cannot be substantially separated by solvent separation.
  • the thermoplastic elastomer composition according to any one of [1] to [5].
  • thermoplastic elastomer composition according to any one of [1] to [6], wherein the polyethylene resin (B) is high density polyethylene (HDPE).
  • B polyethylene resin
  • HDPE high density polyethylene
  • thermoplastic elastomer composition further comprising 1 to 40 parts by mass of a polypropylene resin (C) based on 100 parts by mass of the thermoplastic elastomer composition according to any one of [1] to [7].
  • thermoplastic elastomer composition blended by mass.
  • thermoplastic elastomer composition according to any one of [1] to [9].
  • a multilayer sheet including the sheet according to [11].
  • a skin material comprising the sheet according to [11] or the multilayer sheet according to [12].
  • thermoplastic elastomer composition comprising a step of mixing a cross-copolymer (A), a polyethylene-based resin (B), and a crosslinking agent under shear and crosslinking.
  • An aromatic vinyl compound monomer and an anionic polymerization initiator are added to the obtained olefin-aromatic vinyl compound-aromatic polyene copolymer, and anion polymerization is performed to obtain the cross copolymer (A).
  • thermoplastic elastomer composition obtained in [16] or [17].
  • a method for producing a thermoplastic elastomer composition further comprising:
  • thermoplastic elastomer composition having excellent heat resistance, oil resistance, and scratch resistance, and a molded article, a sheet, and a skin material using the same.
  • thermoplastic elastomer composition which concerns on an Example and a comparative example.
  • thermoplastic elastomer composition of the present invention will be described in detail.
  • the present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within a range that does not impair the effects of the present invention.
  • a numerical range includes a lower limit value and an upper limit value unless otherwise specified.
  • thermoplastic elastomer composition contains the cross copolymer (A) and the polyethylene resin (B).
  • Cross-copolymer (A) any one can be used as long as the polymer main chain and another polymer chain are cross-linked.
  • the cross copolymer (A) may have a structure in which an olefin-aromatic vinyl compound-aromatic polyene copolymer chain and an aromatic vinyl compound polymer chain are bonded.
  • the cross-copolymer (A) is composed of an olefin-aromatic vinyl compound-aromatic polyene copolymer chain and an aromatic vinyl compound polymer chain via an aromatic polyene monomer unit. May have a combined structure.
  • the cross copolymer (A) may be a copolymer satisfying at least one, more preferably at least two, and more preferably all of the following conditions (1) to (3).
  • the content of the aromatic vinyl compound monomer unit of the olefin-aromatic vinyl compound-aromatic polyene copolymer is 10 to 30 mol%, more preferably 12 to 28 mol%, and further preferably 15 to 25 mol. %,
  • the content of the aromatic polyene monomer unit is 0.01 mol% or more and 0.5 mol% or less, more preferably 0.01 mol% or more and 0.4 mol% or less, further preferably 0.02 mol% or more.
  • the weight average molecular weight of the olefin-aromatic vinyl compound-aromatic polyene copolymer is from 50,000 to 300,000, and the molecular weight distribution (Mw / Mn) is from 1.8 to 6, more preferably 1.8 or more. 5 or less, more preferably 1.8 or more and 4 or less.
  • the content of the olefin-aromatic vinyl compound-aromatic polyene copolymer contained in the cross copolymer is 60 to 95% by mass, more preferably 65 to 90% by mass, and further preferably 70 to 95% by mass. In the range.
  • the olefin monomer unit examples include ⁇ -olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, vinylcyclohexane, and cyclic olefins, ie, cyclopentene.
  • ⁇ -olefins and cyclic olefins for example, and norbornene.
  • the olefin may include an ethylene monomer, and most preferably is an ethylene monomer.
  • the ethylene monomer unit is preferably used alone.
  • a relatively small amount of an ⁇ -olefin having 3 to 20 carbon atoms is used as long as the effect of the present invention is not impaired.
  • ⁇ -olefin-based monomers and cyclic olefin-based monomers such as propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, vinylcyclohexane, and cyclic olefins such as cyclopentene and norbornene May be copolymerized.
  • aromatic vinyl compound monomer unit examples include styrene and various substituted styrenes such as p-methylstyrene, m-methylstyrene, o-methylstyrene, ot-butylstyrene, mt-butylstyrene, and p-methylstyrene.
  • styrene and various substituted styrenes such as p-methylstyrene, m-methylstyrene, o-methylstyrene, ot-butylstyrene, mt-butylstyrene, and p-methylstyrene.
  • units derived from each styrene monomer such as t-butylstyrene, p-chlorostyrene, and o-chlorostyrene.
  • a styrene unit a p-methylstyrene unit and a p-chlorostyrene unit are preferred, and a styrene unit is particularly preferred.
  • aromatic vinyl compound monomer units may be used alone, or two or more of them may be used in combination.
  • aromatic polyene monomer unit for example, an aromatic polyene having 10 to 30 carbon atoms and having a plurality of double bonds (vinyl groups) and one or more aromatic groups can be used.
  • aromatic polyene monomers such as 1,3-divinyl-4,5,8-tributylnaphthalene, and preferably any one of an orthodivinylbenzene unit, a paradivinylbenzene unit and a metadivinylbenzene unit.
  • One type or a mixture of two or more types is suitably used.
  • the content ratio in the olefin-aromatic vinyl compound-aromatic polyene copolymer is in the range of 10 to 30 mol% of the monomer unit of the aromatic vinyl compound from the viewpoint of improving softness and scratch resistance. Is preferred.
  • the amount of the aromatic vinyl compound monomer unit is 10 mol% or more, sufficient softness and scratch resistance can be obtained.
  • the amount of the aromatic vinyl compound monomer unit is 30 mol% or less, sufficient flexibility at low temperatures is obtained, and the scratch resistance is improved.
  • the content of the aromatic polyene monomer unit may be 0.01 to 0.5 mol%, preferably 0.02 to 0.1 mol%.
  • the aromatic polyene monomer unit is at least 0.01 mol%, the mechanical properties will be improved, and when it is at most 0.5 mol%, the moldability will be improved.
  • the content ratio of the olefin-aromatic vinyl compound-aromatic polyene copolymer chain and the aromatic vinyl compound polymer chain is preferably from the viewpoint of improvement in softness.
  • the amount of the aromatic vinyl compound-aromatic polyene copolymer chain may be 70 to 95% by mass, and the amount of the aromatic vinyl compound polymer chain may be 5 to 30% by mass. Further, from the viewpoint of improving the physical properties of the thermoplastic elastomer composition, from 82 to 92% by mass of the olefin-aromatic vinyl compound-based copolymer, and from 8 to 18% by mass of the polymer comprising the aromatic vinyl compound monomer unit. %.
  • the cross copolymer (A) is obtained by copolymerizing ethylene, an aromatic vinyl compound, and an aromatic polyene monomer using a coordination polymerization catalyst to form an ethylene-aromatic vinyl compound-aromatic
  • a polyene copolymer is synthesized, and in an anion polymerization step, a polymerization method is carried out using an anion polymerization initiator in the coexistence of an ethylene-aromatic vinyl compound-aromatic polyene copolymer and an aromatic vinyl compound monomer.
  • the obtained copolymer may further satisfy all of the following conditions (1) to (3).
  • the content of the aromatic vinyl compound monomer unit of the ethylene-aromatic vinyl compound-aromatic polyene copolymer is 10 to 30 mol%, and the content of the aromatic polyene monomer unit is 0.01 mol% or more. 0.5 mol% or less, with the balance being the ethylene monomer unit content.
  • the ethylene-aromatic vinyl compound-aromatic polyene copolymer has a weight average molecular weight of 50,000 or more and 300,000 or less, and a molecular weight distribution (Mw / Mn) of 1.8 or more and 6 or less.
  • the content of the ethylene-aromatic vinyl compound-aromatic polyene copolymer contained in the cross copolymer is in the range of 60 to 95% by mass.
  • the olefin-aromatic vinyl compound-aromatic polyene copolymer chain and the aromatic vinyl compound polymer chain may be bonded via an aromatic polyene monomer unit.
  • the formation of the bond mediated by the aromatic polyene monomer unit can be proved by the following observable phenomenon.
  • an ethylene-styrene (aromatic vinyl compound) -divinylbenzene (aromatic polyene) copolymer chain and a polystyrene (aromatic vinyl compound) chain are linked via a divinylbenzene unit. The case where they are combined is shown.
  • the peak intensity (area) of the vinyl group hydrogen (proton) of the divinylbenzene unit is ethylene-styrene-
  • the peak intensity is less than 50%, preferably less than 20%.
  • the divinylbenzene unit is copolymerized simultaneously with the polymerization of the styrene unit, and the ethylene-styrene-divinylbenzene copolymer chain and the polystyrene chain are bonded via the divinylbenzene unit. Therefore, in the cross-copolymer after anionic polymerization, the peak intensity of hydrogen (proton) of the vinyl group of the divinylbenzene unit is greatly reduced. Actually, the peak of hydrogen (proton) of the vinyl group of the divinylbenzene unit has substantially disappeared in the cross copolymer after anionic polymerization.
  • an ethylene-aromatic vinyl compound-aromatic polyene copolymer chain and an aromatic vinyl compound polymer chain are bonded via an aromatic polyene monomer unit.
  • an ethylene-styrene-divinylbenzene copolymer chain and a polystyrene chain are bonded via a divinylbenzene unit
  • the cross-copolymer having a bond in which an aromatic polyene monomer unit is interposed therein contains ethylene-styrene- Divinylbenzene copolymer chains and polystyrene chains cannot be separated.
  • Ethylene-styrene-divinylbenzene copolymer and polystyrene having the same composition as the ethylene-styrene-divinylbenzene copolymer chain contained in the ordinary cross-copolymer are subjected to Soxhlet extraction with boiling acetone to form acetone-insoluble parts. Usually, it can be separated into polystyrene as an acetone-soluble part in an ethylene-styrene-divinylbenzene copolymer.
  • the cross copolymer (A) has an ethylene-aromatic vinyl compound-aromatic polyene copolymer chain and an aromatic vinyl compound polymer chain, and is an ethylene-aromatic vinyl compound.
  • substantially as used herein means that the present cross-copolymer may contain a relatively small amount of an aromatic vinyl compound (polystyrene) homopolymer that does not impair the effects of the present invention. I do.
  • the weight average molecular weight Mw of the aromatic vinyl compound polymer chain contained in the cross copolymer (A) is arbitrary, but is generally in the range of 10,000 to 80,000. In the cross copolymer, the molecular weight of the aromatic vinyl compound polymer chain bonded to the main chain olefin-aromatic vinyl compound-aromatic polyene copolymer cannot be determined.
  • the weight average molecular weight Mw of the aromatic vinyl compound polymer homopolymer contained in the copolymer in a relatively small amount is defined as the weight average molecular weight Mw of the aromatic vinyl compound polymer chain contained in the cross copolymer. I have.
  • the amount of the aromatic polyene (eg, divinylbenzene) unit contained was significantly smaller than that of the aromatic vinyl compound (eg, styrene) unit. Since the position overlaps with the aromatic vinyl compound (for example, styrene) unit, the peak cannot be directly confirmed.
  • the peak derived from the olefin-aromatic vinyl compound-aromatic polyene copolymer (ethylene-styrene-divinylbenzene copolymer) and the aromatic A peak derived from a vinyl compound polymer (polystyrene) was observed, and an olefin unit derived from an olefin-aromatic vinyl compound-aromatic polyene copolymer (ethylene-styrene-divinylbenzene copolymer) of a cross-copolymer was observed.
  • aromatic vinyl compound (styrene) unit content aromatic vinyl compound polymer (polystyrene) content.
  • the olefin-aromatic vinyl compound-aromatic polyene copolymer ethylene-styrene-divinylbenzene copolymer
  • the polyene (divinylbenzene) content is determined by including the aromatic vinyl compound (styrene) unit content in which the peak positions overlap with each other.
  • the above-mentioned acetone-insoluble portion which occupies most of the cross-copolymer includes an ethylene-aromatic vinyl compound-aromatic polyene copolymer (ethylene-styrene-divinylbenzene copolymer) and an aromatic vinyl compound polymer ( Polystyrene), which cannot be separated by further fractionation. Therefore, in a preferred cross copolymer, the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain and the aromatic vinyl compound polymer chain have a bond (for example, ethylene-styrene-divinylbenzene copolymer). (A polymer chain and a polystyrene chain have a bond).
  • the cross-copolymer has substantially no gel component despite the bond between the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain and the aromatic vinyl compound polymer chain. And a practical molding processability as a thermoplastic resin, that is, a specific MFR value.
  • the cross copolymer (A) according to a preferred embodiment comprises 70 to 95% by mass of an olefin-aromatic vinyl compound-aromatic polyene copolymer having an aromatic vinyl monomer unit content of 10 to 30 mol%. And 5 to 30% by mass of an aromatic vinyl polymer comprising an aromatic vinyl monomer unit, and the two may be substantially inseparable by solvent separation.
  • the polyethylene resin (B) in which the thermoplastic elastomer composition of the present invention can be used may be a resin containing 50% by mass or more of an ethylene monomer unit.
  • the polyethylene resin (B) may be an ethylene homopolymer, and ethylene and another ⁇ -olefin, for example, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, or a mixture thereof. It may be a copolymer with the above mixture.
  • the polyethylene resin (B) may be high-density polyethylene (hereinafter “HDPE”), low-density polyethylene (hereinafter “LDPE”), linear low-density polyethylene (hereinafter “LLDPE”), or a mixture thereof.
  • HDPE high-density polyethylene
  • LDPE low-density polyethylene
  • LLDPE linear low-density polyethylene
  • HDPE has a density of 0.940 g / cm 3 or more, preferably 0.940 to 0.970 g / cm 3 , more preferably 0.950 to 0.970 g / cm 3 .
  • the melting point thereof is preferably 126 to 136 ° C. as measured by a DSC method (differential scanning calorimeter), the melt flow rate (MFR) is 190 ° C. specified by JIS K-6922-2: 2010, and the load is 2.16 kg. Under the measurement conditions, it is preferably 0 (substantially no flow) to 30 g / 10 min, more preferably 0.05 to 10 g / 10 min.
  • thermoplastic elastomer composition Those having an MFR of 0.05 g / 10 min or more have excellent processability of the thermoplastic elastomer composition, and those having an MFR of 10 g / 10 min or less have high mechanical properties of the obtained thermoplastic elastomer composition. Also, a so-called ultrahigh molecular weight polyethylene having a number average molecular weight of 1,000,000 or more can be suitably used.
  • LDPE and LLDPE preferably have a melting point of 60 to 125 ° C. measured by a DSC method (differential scanning calorimeter), a melt flow rate (MFR) of 190 ° C. specified in JIS @ K-6922-2: 2010, and a load. Under the measurement conditions of 2.16 kg, it is preferably 0.05 to 30 g / 10 min, and more preferably 0.05 to 10 g / 10 min. If the MFR is 0.05 g / 10 min or more, the thermoplastic elastomer composition has excellent processability, and if the MFR is 30 g / 10 min or less, the obtained thermoplastic elastomer composition has high mechanical properties.
  • LDPE is usually produced by a known high-pressure radical polymerization method, and may be produced by any of a tubular method and an autoclave method.
  • LLDPE can be produced by coordination polymerization using a Ziegler-Natta catalyst or a metallocene catalyst, by copolymerizing ethylene and an ⁇ -olefin as a comonomer.
  • HDPE is preferred as the polyethylene resin (B) to be used.
  • thermoplastic elastomer composition contains 50 to 85% by mass of the cross copolymer (A) and 15 to 50% by mass of the polyethylene resin (B). If the cross copolymer (A) is less than 50% by mass, the resulting composition may have insufficient flexibility, and if it is more than 85% by mass, heat resistance and oil resistance may be insufficient.
  • thermoplastic elastomer composition according to the embodiment of the present invention has a gel content of 1.0% by mass or more.
  • the gel fraction can be measured in boiling xylene (140 ° C.) after 8 hours. If the gel content is less than 1.0% by mass, crosslinking is insufficient, and heat resistance and oil resistance may be insufficient.
  • the gel content is from 3.0% by mass to 60% by mass. If it is at most 60% by mass, thermoplasticity and moldability will be good.
  • the MFR (measured based on JIS K7210-1: 2014) of the thermoplastic elastomer composition according to the embodiment of the present invention is preferably 0.3 g / 10 min or more and 10 g / 10 min or less. More preferably, the storage elastic modulus E ′ measured under the conditions of 150 ° C., a frequency of 1 Hz, and a temperature rise of 4 ° C./min is in the range of 1 ⁇ 10 5 to 5 ⁇ 10 6 Pa, and more preferably 1 ⁇ 10 5 to 2 Pa. ⁇ 10 6 Pa, and the gel content after 8 hours in boiling xylene (140 ° C.) is 1.0% by mass or more.
  • the ratio of the storage modulus E ′ (E ′ (190) / E ′ (150)) of the thermoplastic elastomer composition at 190 ° C. and 150 ° C., respectively, may be 0.3 or more. , More preferably 0.3 or more and 1 or less.
  • thermoplastic elastomer composition according to the embodiment of the present invention preferably has an A hardness (measured based on JIS K-6253-3: 2012) of 95 or less, more preferably 90 or less, and 70 or more.
  • a hardness measured based on JIS K-6253-3: 2012
  • the A hardness is in this range, even if a polypropylene-based resin is further compounded as shown below, it is possible to have appropriate softness as a skin material.
  • thermoplastic elastomer composition When the MFR (JIS # K7210: 2014) of the thermoplastic elastomer composition is less than 0.3 g / 10 minutes, there is a possibility that the moldability may be insufficient and economical efficiency may be lost during the production, and if it is higher than 10 g / 10 minutes. , Heat resistance and oil resistance may be reduced.
  • the storage modulus E ′ of the thermoplastic elastomer composition measured at 150 ° C., a frequency of 1 Hz and a temperature rise of 4 ° C./min is less than 1 ⁇ 10 5 , the heat resistance may be reduced.
  • the storage elastic modulus of the thermoplastic elastomer composition according to the embodiment of the present invention can be measured at 150 ° C. and 190 ° C., and even in a temperature range not lower than the melting point (about 130 ° C.) of the polyethylene resin (B). There is no significant drop.
  • the ratio of storage elastic modulus E ′ between 190 ° C. and 150 ° C. is 0.3 or more, more preferably 0.3 or more and 1 or less. This is considered to indicate the presence of a typical crosslinked structure.
  • thermoplastic elastomer composition of the present invention can exhibit good oil resistance. Specifically, the swelling ratio after immersion in liquid paraffin or oleic acid at 70 ° C. for 24 hours can be 120% by mass or less.
  • thermoplastic elastomer composition of the present invention shows good heat resistance.
  • the press sheet with the grain was allowed to stand at 110 ° C. for 24 hours, and then the 60 ° gloss value (gloss value at an incident angle of 60 °) of the grain of the press sheet was measured and compared with the gloss value before the test.
  • the amount is 1.00% or less.
  • the heat resistance is low, the grain changes due to heat, so that the rate of change in gloss becomes a larger value.
  • the thermoplastic elastomer composition of the present invention has good scratch resistance. Specifically, a scratch of 3 cm or more was applied to the mirror surface of the mirror press sheet by using a scratch type hardness meter “318S” manufactured by Eriksen and having a ball tip (ultra-hardness) of 1.0 mm in diameter at a load of 3N. In this case, it is preferable that the scratch depth is 15 ⁇ m or less.
  • the thermoplastic elastomer composition of the present invention can be obtained by a so-called dynamic crosslinking method.
  • Dynamic cross-linking (dynamic vulcanization) is a method in which shearing, dispersion and cross-linking are simultaneously caused by strongly kneading various compounds in a molten state under a temperature condition at which a cross-linking agent reacts.
  • Such a dynamic crosslinking treatment is described, for example, in Reference A. Y. See Coran et al., Rub. Chem. and @Technol. vol. 53.141 to (1980), JSR TECHNICAL REVIEW, No. 112/20050, P20-24.
  • the kneading machine at the time of dynamic crosslinking is usually performed using a closed kneading machine such as a Banbury mixer or a pressure kneader, a single-screw or twin-screw extruder, or the like.
  • the kneading temperature is usually from 130 to 300 ° C, preferably from 150 to 200 ° C.
  • the kneading time is usually 1 to 30 minutes.
  • the crosslinking agent in the case of dynamic crosslinking may include an organic peroxide (F).
  • organic peroxide (F) examples include a phenol resin crosslinking agent, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) -hexane, and 2,5-dimethyl- 2,5-di (tert-butylperoxy) -hexyne-3, di-tert-butyl peroxide and the like.
  • a crosslinking aid a polyfunctional monomer such as a maleimide compound, divinylbenzene, TAIC (trimethallyl isocyanurate), or trimethylolpropane trimethacrylate can also be used.
  • 1 to 40 parts by mass of the polypropylene resin (C) may be further added to 100 parts by mass of the thermoplastic elastomer composition.
  • 1 part by mass or more of the polypropylene resin it becomes possible to further improve oil resistance and heat resistance.
  • the softness can be maintained by blending the polypropylene resin in an amount of 40% by mass or less.
  • the thermoplastic resin composition is based on 100 parts by mass of the thermoplastic elastomer composition containing the cross copolymer (A) and the polyethylene resin (B), or further blended with the polypropylene resin (C). Further, 1 to 50 parts by mass of a plasticizer (D) and / or 1 to 25 parts by mass of a styrene-based thermoplastic elastomer (E) may be further blended with 100 parts by mass.
  • a plasticizer and a styrene-based thermoplastic elastomer in combination, the softness can be improved while preventing the bleed-out of the plasticizer (such as oil).
  • plasticizer (D) examples include paraffin-based (liquid paraffin, etc.), naphthene-based, aroma-based process oil, mineral oil-based softeners such as liquid paraffin, castor oil, linseed oil, olefin-based wax, mineral-based wax, various types Known compounds such as esters can be used.
  • thermoplastic elastomer (E) for example, a thermoplastic elastomer containing a styrene portion can be used.
  • a thermoplastic elastomer containing a styrene portion can be used.
  • the “Septon” series (SEP, SEPS, SEEPS, SEBS, SEEPS-OH) sold by Kuraray can be used.
  • thermoplastic elastomer composition obtained by blending these polypropylene resin (C), plasticizer (D), and / or styrene thermoplastic elastomer (E) also exhibits excellent A hardness and scratch resistance. And exhibit more excellent oil resistance and heat resistance.
  • a method of blending the polypropylene resin (C), the plasticizer (D), and / or the styrene thermoplastic elastomer (E) is optional.
  • a polypropylene resin (C) and a plasticizer (D) are separately added to the thermoplastic elastomer composition containing the cross copolymer (A) and the polyethylene resin (B) obtained by the dynamic crosslinking method.
  • / or a styrene-based thermoplastic elastomer (E) is blended and kneaded by a known method.
  • the same dynamic vulcanization may be performed by using a crosslinking agent or a crosslinking assistant, or the composition may be produced by simply kneading without using these.
  • a crosslinking agent or a crosslinking assistant in particular, in the case of using a polypropylene resin (C), it is finally possible to simply knead the composition without using a cross-linking agent or a cross-linking aid to avoid breaking of the polypropylene chain due to radicals. It is preferable from the viewpoint of heat resistance and oil resistance of the resulting composition.
  • the polypropylene resin (C), the plasticizer (D), and / or the styrene thermoplastic elastomer (E) use one twin feed extruder with side feed economically.
  • the main raw materials including the cross-copolymer (A), the polyethylene resin (B), the cross-linking agent, and the like are charged from the raw material inlet, and the cross-linking agent substantially completes the reaction in the extruder region. Dynamic crosslinking is performed, and when the crosslinking agent has substantially completed the reaction, the polypropylene-based resin (C), the plasticizer (D), and / or the styrene-based thermoplastic elastomer (E) are blended from the side feed.
  • thermoplastic elastomer composition (dynamic vulcanizate) containing the cross copolymer (A) and the polyethylene resin (B) is continuously added to the polypropylene resin (C) and the plasticizer (D). And / or a thermoplastic elastomer composition containing a styrene-based thermoplastic elastomer (E).
  • thermoplastic elastomer composition which comprises a step of mixing at least a cross-copolymer (A), a polyethylene-based resin (B), and a cross-linking agent under shear and further cross-linking the mixture. it can.
  • the thermoplastic elastomer composition obtained above is further blended with a polypropylene resin (C), a plasticizer (D), and / or a styrene thermoplastic elastomer (E),
  • a method for producing a thermoplastic elastomer composition including a step of kneading can also be provided.
  • a molded article using the thermoplastic elastomer composition can be provided.
  • a molded article include synthetic leathers and skin materials described in JP-A-2009-102515, WO09 / 128444, WO13 / 018171, or JP-A-2011-153214. It is suitably used for grips or exterior members, foams, skin materials, tape base materials, wire covering materials, gaskets, sheets, or conductive sheets.
  • the sheet using the thermoplastic elastomer composition according to the embodiment of the present invention may be a single layer or a multilayer. In the case of a multilayer, it may be a multilayer further having a layer composed of another resin component, or a multilayer composed only of a layer composed of the present thermoplastic elastomer composition.
  • a skin material for example, a skin material sheet for an automobile interior having a single-layer or multi-layer sheet containing the thermoplastic elastomer composition
  • a skin material sheet for an automobile interior having a single-layer or multi-layer sheet containing the thermoplastic elastomer composition
  • a sheet of a thermoplastic elastomer composition can be used for a surface layer, and a foamed polypropylene sheet can be used as a base (base) layer.
  • base base
  • thermal adhesiveness to the expanded polypropylene sheet is required.
  • the thermoplastic elastomer composition according to the embodiment of the present invention has thermal adhesion to the expanded polypropylene sheet. The properties are good and suitable.
  • an automobile interior member including the skin material can be provided.
  • thermoplastic elastomer Due to the characteristics of the thermoplastic elastomer according to the embodiment of the present invention, there is little odor to humans and low gloss, so that driving is not hindered by the reflection of light incident from outside the window, and the human feel is comfortable. Therefore, an extremely advantageous effect can be obtained as an automobile interior member.
  • the surface of the single-layer or multi-layer sheet according to the embodiment of the present invention can be subjected to a known surface coating agent treatment in order to further impart texture, scratch resistance, and oil resistance.
  • a known surface coating agent treatment in order to further impart texture, scratch resistance, and oil resistance.
  • Such surface coats include, for example, urethane surface coat agents.
  • Cross copolymer (A) The cross copolymers 1 to 3 shown in Table 1 were used. These cross-copolymers were produced by the production methods of Examples or Comparative Examples described in WO2000 / 37517, WO2007 / 139116 and JP-A-2009-120792. Was similarly determined by the method described in these publications. That is, the composition in the cross-copolymer or ethylene-aromatic vinyl compound-aromatic polyene copolymer, that is, the content of ethylene and aromatic vinyl compound and the content of aromatic vinyl compound polymer are determined by 1 H-NMR (proton NMR).
  • the content of the aromatic polyene in the ethylene-aromatic vinyl compound-aromatic polyene copolymer was determined from the amount of the aromatic polyene charged during the polymerization and gas chromatographic analysis of the polymerization solution sampled after the completion of the coordination polymerization.
  • the amount of the aromatic polyene used in the polymerization was determined from the difference in the amount of the unreacted aromatic polyene, and the amount was calculated by comparing with the amount of the copolymer obtained by the polymerization.
  • the molecular weight in the polymerization solution was determined by GPC measurement.
  • the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polystyrene chain were determined by GPC measurement of an aromatic vinyl compound polymer separated by solvent fractionation.
  • the vinyl group hydrogen (proton) peak intensity (area) of the divinylbenzene unit is the same as that of the divinylbenzene unit of the ethylene-styrene-divinylbenzene copolymer obtained in the coordination polymerization step.
  • the strength (area) was less than 20%.
  • the hydrogen (proton) peak of the vinyl group of the divinylbenzene unit had substantially disappeared in the cross-copolymer after anionic polymerization.
  • the cross copolymer was subjected to Soxhlet extraction using boiling acetone, and the ethylene-styrene-divinylbenzene copolymer chain (essentially, ethylene-styrene copolymer chain) and polystyrene chain included were extracted.
  • the styrene content, divinylbenzene content, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), cross copolymer of the ethylene-styrene-divinylbenzene copolymer used are specified.
  • the content of the ethylene-styrene-divinylbenzene copolymer, the weight average molecular weight (Mw) of the polystyrene chain, the molecular weight distribution (Mw / Mn), and the MFR (JIS # K7210-1, 200 ° C., 49N) are shown.
  • the gel content measured by ASTM-D2765-84 was less than 0.1% by mass (lower detection limit or less) in any of the cross copolymers.
  • GPC gel permeation chromatography
  • Polyethylene resin (B) and other raw materials are as shown in Table 2.
  • thermoplastic elastomer compositions of Examples 1 to 9 were obtained.
  • the evaluation results are shown in Tables 3a and 3b.
  • the cross copolymer (A), the polyethylene resin (B), and the organic peroxide (F) were mixed with a Henschel mixer for 1 minute.
  • the obtained mixture was kneaded using a twin-screw extruder (TEM35B manufactured by Toshiba Machine Co., Ltd.) at a resin temperature of 220 ° C., a screw rotation speed of 170 rpm, and a residence time of 120 seconds, and was extruded into a strand from a die, cut and heated.
  • a plastic elastomer composition was obtained.
  • the sheet was prepared according to the following.
  • a sample for physical property evaluation was a square mirror-surface pressed sheet having a thickness of 1 mm and 0.3 mm formed by a heat press method (200 ° C., time: 5 minutes, pressure: 50 kg / cm 2 ) using a mirror surface mold (manufactured by STAVAX).
  • a press sheet with a single-sided grain a grain mold was used, and a press sheet with a single-sided grain having a thickness of 0.6 mm, in which a crimp pattern was applied to one side of the sheet by the same heating press method, was used.
  • a mirror-finished press sheet with a single-sided grain having a thickness of 0.6 mm and a side of 20 mm is placed in a 60 mL plastic bottle containing 4 g of liquid paraffin, (Hi-Kol K-350 manufactured by Kaneda) or oleic acid (first grade manufactured by Junsei Chemical Co., Ltd.). After being immersed above and left at 70 ° C. for 24 hours, the press sheet was taken out and weighed, and the swelling ratio of the press sheet was calculated by comparing with the weight before the test. In addition, the swelling rate of 120 wt% or less was regarded as a pass level.
  • a scratch-type hardness meter “318S” manufactured by Ericssen having a 1.0 mm-diameter ball tip (ultra-hardness) is used on the specular side. Scratches of 3 cm or more. The depth of the groove at the center of the scratch (the portion intersecting with the center line of the press sheet) was measured using a surface roughness measuring device (Surfcoder ET4000AK manufactured by Kosaka Laboratory Co., Ltd.). In addition, 15 micrometers or less of damage depths were set as the pass level.
  • MFR MFR It measured at 230 degreeC and 10 kg of load based on JIS7210. In addition, 0.3 g / 10 min or more and 10 g / 10 min or less were regarded as acceptable levels.
  • thermoplastic elastomer compositions according to the examples including the cross copolymer (A) and the polyethylene resin (B), and dynamically crosslinked in the presence of a peroxide, has a suitable MFR value and storage elasticity. It shows that the resin composition has good softness and good high-temperature oil resistance, heat resistance, and scratch resistance.
  • the polyethylene-based resin (B) is not used, in the viscoelastic spectrum measurement, the resin melts before reaching the measurement temperature of 150 ° C., and the storage elastic modulus becomes lower than the lower limit of measurement, Heat resistance and high temperature oil resistance were also insufficient (Comparative Example 1).
  • FIG. 1 shows a graph of the temperature change of the storage elastic modulus for Examples 1 to 3 and Comparative Example 3 as typical examples of the examples.
  • the storage elastic modulus of the thermoplastic elastomer composition according to the present example which contains the cross copolymer (A) and the polyethylene resin (B) and is dynamically crosslinked in the presence of a peroxide, is determined by the polyethylene resin ( There is no significant decrease in the temperature range above the melting point of B) (about 130 ° C.).
  • the ratio of storage elastic modulus E ′ between 190 ° C. and 150 ° C. is 0.3 or more, more preferably 0.3 or more and 1 or less.
  • the thermal cross-link according to Comparative Example 3 which included the cross-copolymer (A) and the polypropylene-based resin (C) but did not include the polyethylene-based resin (B), and was dynamically crosslinked in the presence of a peroxide.
  • the plastic elastomer composition melts at a temperature equal to or higher than the melting point (approximately 170 ° C.) of the polypropylene resin (C), and the storage elastic modulus E ′ sharply decreases. At 190 ° C., it is below the lower limit of measurement (1 ⁇ 10 4 Pa). Specifically, the ratio of storage elastic modulus between 190 ° C. and 150 ° C. (E ′ (190) / E ′ (150)) is 0.
  • the cross-linked structure related to the polypropylene-based resin (C) is substantially small. It is considered to indicate.
  • thermoplastic elastomer composition obtained in Example 2 a polypropylene resin, a plasticizer, and a styrene thermoplastic elastomer shown in Table 4 were blended and kneaded, whereby the thermoplastic elastomers of Examples 10 to 14 were mixed. A composition was obtained. Evaluation results of commercially available TPV-based skin materials, TPS-based skin materials, and PVC-based skin materials are also described as Comparative Examples 5 to 7. Table 5 shows the blending of the raw materials and the evaluation results.
  • the thermoplastic elastomer composition of the example exhibited excellent scratch resistance while having the same level of heat resistance and oil resistance as compared with the commercially available TPV and TPS skin materials of the comparative example.
  • the thermoplastic elastomer compositions of the examples exhibited excellent oil resistance and heat resistance as compared with the PVC skin material.
  • thermoplastic elastomer composition obtained in Example 12 was extruded by an extrusion sheet molding machine with a T-die set at a die temperature of 200 ° C., and simultaneously extruded, and a 1.0 mm-thick foamed PP sheet (Toray Pef # 10010AP67 manufactured by Toray Industries, Inc.) ) And a grain roll immediately after the die were subjected to heat fusion to obtain a grained multilayer sheet according to Example 15. The thickness of this multilayer sheet was 1.5 mm.
  • the obtained multilayer sheet was subjected to vacuum forming using an instrument panel mold made of a polypropylene resin at a sheet surface temperature of 110 ° C. to obtain an instrument panel-type automobile interior member. Table 6 shows the evaluation criteria and results.
  • Heat cycle test With respect to the instrument panel-type automobile interior member, a heat cycle test of 10 cycles was carried out with 80 ° C. for 4 hours to ⁇ 30 ° C. for 2 hours as one cycle. After the test, the instrument panel-type automobile interior member was left at room temperature for 1 hour or more, and then, at a part designated at five places at random, L * was measured using a colorimetric colorimeter (ZE-2000 manufactured by Nippon Denshoku Industries Co., Ltd.). , A *, and b * were measured, and the average value was used as a reference value. The color difference ⁇ E was calculated by comparing the average value of L *, a *, and b * before the test. The color difference ⁇ E 2.0 or less was regarded as a pass level.
  • a glass cleaner (HONDA's genuine product number 08CBC-B010L1) was spread on the surface of the instrument panel-type automobile interior member so as to have an application amount of about 0.4 g / 100 cm 2 . After being left at 80 ° C. for 48 hours, the appearance of the instrument panel-type automobile interior member was visually checked, and it was confirmed that there was no deformation, crack, or peeling.
  • the instrument panel-type automobile interior member was left at room temperature for 1 hour or more, and then, at a part designated at five places at random, L * was measured using a colorimetric colorimeter (ZE-2000 manufactured by Nippon Denshoku Industries Co., Ltd.). , A *, and b * were measured, and the average value was used as a reference value.
  • the color difference ⁇ E was calculated by comparing the average value of L *, a *, and b * before the test. The color difference ⁇ E 2.0 or less was regarded as a pass level.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne une composition d'élastomère thermoplastique qui comprend de 50 à 85 % en masse d'un copolymère réticulé (A) et de 15 à 50 % en masse d'une résine à base de polyéthylène (B) et qui présente un indice de fluidité (MFR) (à 230 °C, sous 10 kg de charge) de 0,3 à 10 g/10 min et une teneur en gel supérieure ou égale à 1,0 % en masse.
PCT/JP2019/031875 2018-08-30 2019-08-13 Composition d'élastomère thermoplastique et son procédé de production WO2020045082A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2020539323A JP7348191B2 (ja) 2018-08-30 2019-08-13 熱可塑性エラストマー組成物およびその製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018-161947 2018-08-30
JP2018161947 2018-08-30

Publications (1)

Publication Number Publication Date
WO2020045082A1 true WO2020045082A1 (fr) 2020-03-05

Family

ID=69644929

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/031875 WO2020045082A1 (fr) 2018-08-30 2019-08-13 Composition d'élastomère thermoplastique et son procédé de production

Country Status (2)

Country Link
JP (1) JP7348191B2 (fr)
WO (1) WO2020045082A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022071314A1 (fr) * 2020-09-29 2022-04-07 クラレプラスチックス株式会社 Composition de résine

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001019881A1 (fr) * 1999-09-13 2001-03-22 Denki Kagaku Kogyo Kabushiki Kaisha Copolymere vinyle/diene olefinique/aromatique copolymerise par reticulation, et procede de production associe
JP2008544066A (ja) * 2005-06-22 2008-12-04 エクソンモービル・ケミカル・パテンツ・インク 均質ポリマーブレンド及び均質ポリマーブレンドを生成するプロセス
JP2009102515A (ja) * 2007-10-23 2009-05-14 Denki Kagaku Kogyo Kk 耐傷つき摩耗性エラストマ−
JP2009120792A (ja) * 2007-10-23 2009-06-04 Denki Kagaku Kogyo Kk クロス共重合体の製造方法及び得られるクロス共重合体、その用途
JP2009185208A (ja) * 2008-02-07 2009-08-20 Denki Kagaku Kogyo Kk オレフィン−芳香族ビニル化合物系クロス共重合体を含む樹脂組成物を用いた電線被覆材
JP2011074187A (ja) * 2009-09-30 2011-04-14 Denki Kagaku Kogyo Kk 易架橋性熱可塑性樹脂
WO2013018171A1 (fr) * 2011-07-29 2013-02-07 電気化学工業株式会社 Feuille de matériau de surface
WO2016136534A1 (fr) * 2015-02-25 2016-09-01 デンカ株式会社 Composition de résine à base de polypropylène et objet moulé obtenu à partir de celle-ci
JP2018083885A (ja) * 2016-11-22 2018-05-31 アロン化成株式会社 熱可塑性エラストマー組成物

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001019881A1 (fr) * 1999-09-13 2001-03-22 Denki Kagaku Kogyo Kabushiki Kaisha Copolymere vinyle/diene olefinique/aromatique copolymerise par reticulation, et procede de production associe
JP2008544066A (ja) * 2005-06-22 2008-12-04 エクソンモービル・ケミカル・パテンツ・インク 均質ポリマーブレンド及び均質ポリマーブレンドを生成するプロセス
JP2009102515A (ja) * 2007-10-23 2009-05-14 Denki Kagaku Kogyo Kk 耐傷つき摩耗性エラストマ−
JP2009120792A (ja) * 2007-10-23 2009-06-04 Denki Kagaku Kogyo Kk クロス共重合体の製造方法及び得られるクロス共重合体、その用途
JP2009185208A (ja) * 2008-02-07 2009-08-20 Denki Kagaku Kogyo Kk オレフィン−芳香族ビニル化合物系クロス共重合体を含む樹脂組成物を用いた電線被覆材
JP2011074187A (ja) * 2009-09-30 2011-04-14 Denki Kagaku Kogyo Kk 易架橋性熱可塑性樹脂
WO2013018171A1 (fr) * 2011-07-29 2013-02-07 電気化学工業株式会社 Feuille de matériau de surface
WO2016136534A1 (fr) * 2015-02-25 2016-09-01 デンカ株式会社 Composition de résine à base de polypropylène et objet moulé obtenu à partir de celle-ci
JP2018083885A (ja) * 2016-11-22 2018-05-31 アロン化成株式会社 熱可塑性エラストマー組成物

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022071314A1 (fr) * 2020-09-29 2022-04-07 クラレプラスチックス株式会社 Composition de résine
CN116234870A (zh) * 2020-09-29 2023-06-06 可乐丽塑料株式会社 树脂组合物

Also Published As

Publication number Publication date
JP7348191B2 (ja) 2023-09-20
JPWO2020045082A1 (ja) 2021-08-26

Similar Documents

Publication Publication Date Title
EP2757131B1 (fr) Composition réticulée, son procédé de production, et moulage
TWI612068B (zh) 氫化嵌段共聚物、聚丙烯樹脂組合物以及成形體
NO322848B1 (no) Koblet polymer, fremgangsmate for fremstilling og anvendelse derav.
KR20130020898A (ko) 열가소성 엘라스토머 조성물 및 그 성형품
CN108026201B (zh) 使用了氢化嵌段共聚物的管
JPWO2018143373A1 (ja) 表皮材用多層シ−ト
EP3070123B1 (fr) Composition de résine élastomère thermoplastique
JP3612374B2 (ja) ポリオレフィン系樹脂組成物
JPWO2016136534A1 (ja) ポリプロピレン系樹脂組成物およびそれを用いた成形体
JP2007091974A (ja) 熱可塑性発泡樹脂組成物
WO2020045082A1 (fr) Composition d'élastomère thermoplastique et son procédé de production
JP2009132765A (ja) シームレスインストルメントパネル用樹脂組成物およびその用途
JP2008169316A (ja) プロピレン重合体組成物、該組成物からなるペレット、樹脂用改質剤、熱可塑性樹脂組成物の製造方法、プロピレン系重合体組成物からなる成形体の製造方法、プロピレン系重合体組成物からなる成形体
JP6835069B2 (ja) 熱可塑性樹脂組成物およびその成形体
CN101085848A (zh) 热塑性弹性体组合物和层压材料
JP4732749B2 (ja) 熱可塑性樹脂組成物、成形体およびその用途
JP6666115B2 (ja) 樹脂組成物およびそれからなる成形体
JP4615232B2 (ja) ポリプロピレン系樹脂組成物
JP7166433B2 (ja) 水添ブロック共重合体
JP4048595B2 (ja) ポリプロピレン系樹脂表皮材
JP2006176708A (ja) 樹脂組成物
JPH10279738A (ja) 熱可塑性エラストマー組成物、熱可塑性エラストマー組成物パウダー及びそれよりなる表皮材
JP2020147638A (ja) 光透過性シート、多層シート、照明装置、自動車内装部材
WO2023176810A1 (fr) Composition d'élastomère thermoplastique et procédé de production d'une composition d'élastomère thermoplastique
WO2023013772A1 (fr) Composition d'élastomère thermoplastique, et corps moulé constitué de celle-ci

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19854429

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2020539323

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19854429

Country of ref document: EP

Kind code of ref document: A1