WO2017073695A1 - Composition élastomère thermoplastique, élément, joint d'étanchéité aux intempéries et élément de coin pour joint d'étanchéité aux intempéries - Google Patents

Composition élastomère thermoplastique, élément, joint d'étanchéité aux intempéries et élément de coin pour joint d'étanchéité aux intempéries Download PDF

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WO2017073695A1
WO2017073695A1 PCT/JP2016/081960 JP2016081960W WO2017073695A1 WO 2017073695 A1 WO2017073695 A1 WO 2017073695A1 JP 2016081960 W JP2016081960 W JP 2016081960W WO 2017073695 A1 WO2017073695 A1 WO 2017073695A1
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thermoplastic elastomer
elastomer composition
block copolymer
mass
hydrogenated
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PCT/JP2016/081960
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English (en)
Japanese (ja)
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小西　大輔
佐々木　啓光
陽介 上原
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株式会社クラレ
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Priority to JP2017547868A priority Critical patent/JP6867034B2/ja
Publication of WO2017073695A1 publication Critical patent/WO2017073695A1/fr

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    • 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
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • 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
    • C08L23/08—Copolymers of ethene
    • 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—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

Definitions

  • the present invention relates to a thermoplastic elastomer composition, a member, a weather seal, and a weather seal corner member.
  • thermoplastic elastomers In addition to vulcanized rubber that has been used for automotive parts, dynamic crosslinked thermoplastic elastomers (TPV) are also attracting attention, and are currently widely used in automotive applications and the like.
  • TPV dynamic crosslinked thermoplastic elastomers
  • One of the parts for automobiles is a weather seal.
  • As a material for the weather seal vulcanized rubber having a small compression set and excellent flexibility has been used so far.
  • a weather seal for an automobile usually has a straight portion and a corner portion. Industrially, the straight part is manufactured by extrusion molding, but the corner part is manufactured by injection molding.
  • a material capable of injection molding as the material of the corner part.
  • a TPV having better moldability than vulcanized rubber cannot be said to have sufficient moldability, and there is room for further improvement.
  • vulcanized rubber or TPV is used as the material for the straight portion of the weather seal, but it is desirable to use another material that is excellent in molding processability while maintaining various characteristics as the material for the corner portion. .
  • thermoplastic elastomer composition having excellent agent retention is known (Patent Document 1).
  • the thermoplastic elastomer composition described in Patent Document 1 is derived from olefin rubber (I), a polymer block (A) composed of structural units derived from an aromatic vinyl compound, and isoprene or a mixture of isoprene and butadiene.
  • a hydrogenated block copolymer having a structural unit and a polymer block (B) having a total content of 3,4-bond units and 1,2-bond units of 45% or more A hydrogenated block copolymer (II) having a peak top molecular weight (Mp) of 250,000 to 500,000 determined by gel permeation chromatography in terms of standard polystyrene, a polyolefin resin other than the above (I) (III ) And a softening agent (IV) comprising a olefinic rubber (I) and a hydrogenated block co-polymer
  • thermoplastic elastomer composition described in Patent Document 1 has room for further improvement in molding processability, and as a material for the corner portion of the weather seal, a better material has been developed. It has been demanded. Furthermore, when the material of the straight part of the weather seal is TPV, if the thermoplastic elastomer composition described in Patent Document 1 is used as the material of the corner part, there is room for further improvement in the adhesion with the straight part. It has been found.
  • an object of the present invention is to provide a thermoplastic elastomer having high adhesive strength to vulcanized rubber and dynamically cross-linked thermoplastic elastomer (TPV), and being excellent in moldability as well as flexibility and weather resistance. It is to provide a composition. Furthermore, it is providing the member which has a site
  • the inventors of the present invention made extensive studies to solve the above-mentioned problems.
  • the olefin rubber (I), the specific hydrogenated block copolymer (II), the polyolefin resin (III), and the softener ( IV) a thermoplastic elastomer composition comprising the olefin rubber (I) and the hydrogenated block copolymer (II) in a specific range, and a polyolefin resin (III). It has been found that the above-mentioned problems can be solved if the thermoplastic elastomer composition has a content of the softening agent (IV) within a specific range, and the present invention has been achieved.
  • the present invention relates to the following [1] to [18].
  • Olefin rubber (I) The following hydrogenated block copolymer (II), Polyolefin resin (III) and softener (IV)
  • a thermoplastic elastomer composition comprising: The content ratio [(I) / (II)] of the olefin rubber (I) and the hydrogenated block copolymer (II) is 90/10 to 10/90 by mass ratio, The content of polyolefin resin (III) is 10 to 200 parts by mass and the content of softener (IV) is 100 parts by mass in total of olefin rubber (I) and hydrogenated block copolymer (II).
  • thermoplastic elastomer composition having a content of 15 to 300 parts by mass.
  • Hydrogenated block copolymer (II) mainly from a polymer block (A) mainly composed of a structural unit derived from an aromatic vinyl compound and a structural unit derived from at least one selected from the group consisting of isoprene and butadiene. And a hydrogenated product of a block copolymer having a polymer block (B) having a total content of 3,4-bond units and 1,2-bond units of 45% or more, Water having a peak top molecular weight of 50,000 to 200,000 determined by standard polystyrene conversion by an association chromatography and hydrogenated 70 mol% or more of the carbon-carbon double bonds in the polymer block (B).
  • thermoplastic elastomer composition according to the above [1], wherein the hydrogenated block copolymer (II) has a glass transition temperature of ⁇ 45 to 0 ° C.
  • thermoplastic elastomer composition according to any one of the above [1] to [4], which is a hydrogenated product of the triblock copolymer [A1-B-A2].
  • thermoplastic elastomer composition according to the above [5], wherein the ratio [Mp (A1) / Mp (A2)] of the Mp (A1) to the Mp (A2) satisfies 1/10 to 8/10.
  • thermoplastic elastomer according to any one of [1] to [6] above, wherein the olefin rubber (I) and the polymer block (B) of the hydrogenated block copolymer (II) are crosslinked. Composition.
  • the olefin rubber (I) is a copolymer rubber of (I-1) ethylene and one or more ⁇ -olefins having 3 to 20 carbon atoms, or a crosslinked product thereof, and (I-2) ethylene. And at least one selected from the group consisting of a copolymer rubber of at least one ⁇ -olefin having 3 to 20 carbon atoms and at least one non-conjugated polyene or a crosslinked product thereof [1]
  • the thermoplastic elastomer composition according to any of [7].
  • the polyolefin resin (III) is at least one selected from the group consisting of polyethylene resin, polypropylene resin, poly (1-butene) and poly (4-methyl-1-pentene).
  • the thermoplastic elastomer composition according to any one of the above [1] to [8].
  • the member according to the above [10] which has a portion (Y1) made of a material different from the thermoplastic elastomer composition according to any one of the above [1] to [9] in addition to the portion (X1).
  • thermoplastic elastomer composition according to any one of the above [1] to [9] (provided that the thermoplastic elastomer composition is the same as the thermoplastic elastomer composition forming the part (X1)).
  • thermoplastic elastomer composition which has a portion (X2) consisting of the same.
  • [15] A weather seal containing the member according to any one of [10] to [14].
  • It has a portion (X1) made of the thermoplastic elastomer composition according to any one of [1] to [9], and In addition to the part (X1), it has a part (Y1) made of a material different from the thermoplastic elastomer composition of any one of the above [1] to [9], or in addition to the part (X1) A part comprising the thermoplastic elastomer composition according to any one of the above [1] to [9] (however, it may be the same as or different from the thermoplastic elastomer composition forming the part (X1)).
  • thermoplastic elastomer composition having high adhesive strength to vulcanized rubber and dynamically cross-linked thermoplastic elastomer (TPV), and having excellent flexibility and weather resistance as well as excellent moldability. can do. Furthermore, the member which has a site
  • thermoplastic elastomer composition comprises: Olefin rubber (I), The following hydrogenated block copolymer (II), Polyolefin resin (III) and softener (IV)
  • a thermoplastic elastomer composition comprising: The content ratio [(I) / (II)] of the olefin rubber (I) and the hydrogenated block copolymer (II) is 90/10 to 10/90 by mass ratio, The content of polyolefin resin (III) is 10 to 200 parts by mass and the content of softener (IV) is 100 parts by mass in total of olefin rubber (I) and hydrogenated block copolymer (II).
  • Hydrogenated block copolymer (II) mainly from a polymer block (A) mainly composed of a structural unit derived from an aromatic vinyl compound and a structural unit derived from at least one selected from the group consisting of isoprene and butadiene. And a hydrogenated product of a block copolymer having a polymer block (B) having a total content of 3,4-bond units and 1,2-bond units of 45% or more, Water having a peak top molecular weight of 50,000 to 200,000 determined by standard polystyrene conversion by an association chromatography and hydrogenated 70 mol% or more of the carbon-carbon double bonds in the polymer block (B).
  • a block copolymer mainly from a polymer block (A) mainly composed of a structural unit derived from an aromatic vinyl compound and a structural unit derived from at least one selected from the group consisting of isoprene and butadiene.
  • (Olefin rubber (I)) As the olefin rubber (I), (I-1) a copolymer rubber of ethylene and one or more ⁇ -olefins having 3 to 20 carbon atoms (hereinafter sometimes referred to as “ethylene / ⁇ -olefin copolymer rubber”) or a cross-linked product thereof; (I-2) Copolymer rubber of ethylene, one or more ⁇ -olefins having 3 to 20 carbon atoms and one or more non-conjugated polyenes (hereinafter referred to as “ethylene / ⁇ -olefin / non-conjugated polyene copolymer”) Rubber ”) or cross-linked products thereof. Etc.
  • Olefin rubber (I) may be used individually by 1 type, and may use 2 or more types together. When two or more kinds are used in combination, it is preferable to use a cross-linked product of the ethylene / ⁇ -olefin copolymer rubber and a cross-linked product of the ethylene / ⁇ -olefin / non-conjugated polyene copolymer rubber together.
  • the olefin rubber (I) is preferably an ethylene / ⁇ -olefin / non-conjugated polyene copolymer rubber or a cross-linked product thereof from the viewpoint of better strain recovery at high temperatures.
  • An ⁇ -olefin / non-conjugated polyene copolymer rubber or a cross-linked product of ethylene / ⁇ -olefin / non-conjugated polyene copolymer rubber may be used.
  • Examples of the ⁇ -olefin having 3 to 20 carbon atoms constituting the copolymer rubber or a crosslinked product thereof include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-octene, and the like. Examples include decene. These ⁇ -olefins may be used alone or in combination of two or more. Among these, at least one selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene is preferable, and at least one selected from the group consisting of propylene and 1-butene is preferable. More preferably, it is propylene.
  • the molar ratio of ethylene to ⁇ -olefin having 3 to 20 carbon atoms is high in mechanical strength and strain recovery at high temperature. From the viewpoint that the properties are maintained in a well-balanced manner, 40/60 to 93/7 is preferable, 50/50 to 85/15 is more preferable, and 60/40 to 80/20 is more preferable.
  • non-conjugated polyene constituting the ethylene / ⁇ -olefin / non-conjugated polyene copolymer rubber examples include, for example, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-propylidene-2-norbornene, 5-vinyl- Cyclic polyenes such as 2-norbornene, 2,5-norbornadiene, 1,4-cyclohexadiene, 1,4-cyclooctadiene, 1,5-cyclooctadiene; 1,4-hexadiene, 4-methyl-1,4 -Hexadiene, 5-methyl-1,4-hexadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6 -Octadiene, 5,7-dimethyl-1,6-octadiene, 7-methyl
  • cyclic polyenes and chain polyenes having 6 to 15 carbon atoms having an internal unsaturated bond are preferable.
  • 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methyl-1,4 -At least one selected from the group consisting of hexadiene and 7-methyl-1,6-octadiene is more preferable, and 5-ethylidene-2-norbornene, dicyclopentadiene and More preferred is at least one selected from the group consisting of 5-vinyl-2-norbornene.
  • the molar ratio of ethylene to the ⁇ -olefin having 3 to 20 carbon atoms and the non-conjugated polyene is preferably 90/10 to 40/60, particularly 80/20 to 50/50 from the viewpoint of flexibility and rubber elasticity.
  • the iodine value (iodine value before crosslinking) of the ethylene / ⁇ -olefin / non-conjugated polyene copolymer rubber is preferably 3 to 40, more preferably 5 to 25, from the viewpoint of mechanical strength and rubber elasticity. More preferably, it is 5-15. If the iodine value is 3 or more, the mechanical strength of the molded product obtained from the thermoplastic elastomer composition tends to be good, and if the iodine value is 40 or less, the rubber elasticity of the thermoplastic elastomer composition is impaired. It tends to be difficult.
  • “iodine value” refers to the iodine value measured by the method described in JIS K1525 (2005).
  • the Mooney viscosity (ML 1 + 4 , 100 ° C.) of the olefin rubber (I) is preferably 25 to 350, more preferably 40 to 300, and more preferably 60 to 150 from the viewpoint of moldability and mechanical strength. Further preferred.
  • Mooney viscosity (ML 1 + 4 , 100 ° C.) refers to a viscosity measured by the method described in JIS K6300-1 (2013).
  • the olefin rubber (I) may be pre-crosslinked, and the degree of crosslinking is not particularly limited, but when the crosslinked olefin rubber (I) is subjected to Soxhlet extraction treatment with cyclohexane for 10 hours.
  • the degree of crosslinking is such that the mass ratio (gel fraction) of the gel remaining without being dissolved in cyclohexane is 80% or more, particularly 95% or more with respect to the mass of the olefin rubber after crosslinking before the extraction treatment. Is preferable from the viewpoint of strain recovery at high temperatures.
  • the crosslinking agent and crosslinking adjuvant which can be used for the said crosslinking reaction can use the same thing as the crosslinking agent and crosslinking adjuvant which are mentioned later.
  • thermoplastic elastomer composition of the present invention needs to contain a hydrogenated block copolymer (II).
  • TPV dynamically cross-linked thermoplastic elastomer
  • the hydrogenated block copolymer (II) includes a polymer block (A) mainly composed of a structural unit derived from an aromatic vinyl compound, and a structural unit derived from at least one selected from the group consisting of isoprene and butadiene.
  • the peak top molecular weight determined by standard polystyrene conversion by permeation chromatography is 50,000 to 200,000, and 70 mol% or more of the carbon-carbon double bonds in the polymer block (B) are hydrogenated. It is a hydrogenated block copolymer.
  • vinyl bond units 3,4-bond units and 1,2-bond units in structural units derived from isoprene and 1,2-bond units in structural units derived from butadiene are collectively referred to as “vinyl bond units”.
  • the total amount may be referred to as “vinyl bond content”.
  • the polymer block (A) of the hydrogenated block copolymer (II) mainly comprises a structural unit derived from an aromatic vinyl compound (hereinafter sometimes abbreviated as an aromatic vinyl compound unit).
  • aromatic vinyl compound unit a structural unit derived from an aromatic vinyl compound (hereinafter sometimes abbreviated as an aromatic vinyl compound unit).
  • aromatic vinyl compound unit is preferably 90% by mass or more, more preferably 95% by mass or more, and further preferably 100% by mass based on the mass of the polymer block (A).
  • Examples of the aromatic vinyl compound constituting the polymer block (A) include styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, Examples include 2,4-dimethylstyrene, 2,4,6-trimethylstyrene, monofluorostyrene, difluorostyrene, monochlorostyrene, dichlorostyrene, methoxystyrene, vinylnaphthalene, and vinylanthracene.
  • the polymer block (A) may contain only a structural unit derived from one kind of the above-described aromatic vinyl compound, or may contain a structural unit derived from two or more kinds. Especially, it is preferable that a polymer block (A) mainly consists of the structural unit derived from styrene.
  • the polymer block (A) may contain a small amount of a structural unit derived from another copolymerizable monomer together with a structural unit derived from an aromatic vinyl compound.
  • the proportion of the structural unit derived from the other copolymerizable monomer is preferably 10% by mass or less based on the mass of the polymer block (A), and more preferably 5% by mass or less. preferable.
  • examples of such other copolymerizable monomers include copolymerizable monomers capable of ion polymerization such as 1-butene, pentene, hexene, butadiene, isoprene, and methyl vinyl ether.
  • the content of the polymer block (A) is preferably 5 to 40% by mass, more preferably 5 to 30% by mass with respect to the hydrogenated block copolymer (II). 5 to 20% by mass is more preferable, and 5 to 18% by mass is particularly preferable. If the content of the polymer block (A) is 5% by mass or more, mechanical properties and flexibility tend to be good, and good strain recovery at high temperatures is obtained, and heat resistance is also good. It tends to be excellent. If the content of the polymer block (A) is 40% by mass or less, the melt viscosity of the hydrogenated block copolymer (II) does not become too high and melt mixing with other components tends to be easy. Furthermore, flexibility and adhesion to TPV and vulcanized rubber tend to be excellent. In addition, content of the polymer block (A) in hydrogenated block copolymer (II) is the value calculated
  • the polymer block (B) contained in the hydrogenated block copolymer (II) mainly comprises structural units derived from at least one selected from the group consisting of isoprene and butadiene.
  • the term “mainly” as used herein means that the structural unit derived from at least one selected from the group consisting of isoprene and butadiene based on the mass of the polymer block (B) is preferably 70% by mass or more, more preferably It means 90% by mass or more.
  • the polymer block (B) preferably mainly comprises a structural unit derived from isoprene or a structural unit derived from a mixture of isoprene and butadiene.
  • the vinyl bond content is more preferably 47% or more, and further preferably 50% or more. Although there is no restriction
  • the polymer block (B) is composed of a structural unit derived from a mixture of isoprene and butadiene
  • the structural unit is a 2-methyl-2-butene-1,4-diyl group, isopropenyl derived from isoprene.
  • the vinyl bond content is more preferably 47% or more, and further preferably 50% or more. Although there is no restriction
  • the bonding form of the structural unit derived from isoprene and the structural unit derived from butadiene may be random, block, or tapered.
  • the polymer block (B) is composed of a structural unit derived from a mixture of isoprene and butadiene
  • the structural unit derived from isoprene / the structural unit derived from butadiene (molar ratio) is 10 from the viewpoint of adhesive strength and flexibility.
  • / 90 to 99/1 is preferable, 30/70 to 99/1 is more preferable, 40/60 to 99/1 is further preferable, and 40/60 to 70/30 is preferable. Is particularly preferred, with 40/60 to 55/45 being most preferred.
  • the polymer block (B) may have a small amount of structural units derived from other copolymerizable monomers together with structural units derived from isoprene or structural units derived from isoprene and butadiene.
  • the proportion of the structural unit derived from the other copolymerizable monomer is preferably 30% by mass or less based on the mass of the polymer block (B), and more preferably 10% by mass or less. Preferably, it is 5 mass% or less.
  • copolymerizable monomers examples include styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, diphenylethylene, 1-vinylnaphthalene, Copolymerizable monomers capable of anion polymerization such as aromatic vinyl compounds such as 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene Is mentioned.
  • aromatic vinyl compounds such as 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene Is
  • copolymerizable monomers may be used individually by 1 type, and may use 2 or more types together.
  • the bonding form thereof May be either random or tapered.
  • the hydrogenated block copolymer (II) has one or more functional groups such as a carboxyl group, a hydroxyl group, an acid anhydride group, an amino group, and an epoxy group in the molecular chain and / or at the molecular end. It may be.
  • the hydrogenated block copolymer (II) particularly from the viewpoint of heat resistance and weather resistance, 70 mol% or more of unsaturated double bonds (carbon-carbon double bonds) in the polymer block (B) are hydrogenated. Need to be. From the same viewpoint, 80 mol% or more is more preferably hydrogenated, and 85 mol% or more is more preferably hydrogenated.
  • the hydrogenation rate of the carbon-carbon double bond in the polymer block (B) is determined by the content of the carbon-carbon double bond in the polymer block (B) before and after the hydrogenation. It can be determined from the iodine value measurement described in the examples.
  • the hydrogenated block copolymer (II) is a hydrogenated product of a block copolymer containing at least one polymer block (A) and each polymer block (B).
  • the hydrogenated block copolymer (II) is a hydrogenated product of a block copolymer containing two or more polymer blocks (A) and one or more polymer blocks (B).
  • the bonding form of the polymer block (A) and the polymer block (B) is not particularly limited, and may be linear, branched, radial, or a combination of two or more of these. In addition, a linearly bonded form is preferable.
  • each polymer block (A) and each polymer block (A) may be a block having the same configuration or a block having a different configuration.
  • the two polymer blocks (A) in the triblock structure represented by [ABA] may have the same or different types of aromatic vinyl compounds constituting them. Good.
  • the peak top molecular weight (Mp) of the polymer block (A) is preferably 2,000 to 60,000, more preferably 2,500 to 30,000, still more preferably. 3,000 to 20,000.
  • the peak top molecular weight of the polymer block (B) is preferably 130,000 to 190,000, more preferably 50,000 to 180,000 in the state before hydrogenation.
  • the polymer block (A) in the hydrogenated block copolymer (II) has two polymer blocks (A1) and (A2) having the same or different peak top molecular weights determined in terms of standard polystyrene by gel permeation chromatography.
  • the hydrogenated block copolymer (II) is composed of the polymer block (A1), the polymer block (B), and the polymer block (A2).
  • a hydrogenated product of the polymer [A1-B-A2] is preferable.
  • the hydrogenated block copolymer (II) is a peak obtained by converting the polymer block (A) mainly from a structural unit derived from an aromatic vinyl compound, and in terms of standard polystyrene by gel permeation chromatography.
  • a peak top molecular weight mainly composed of a polymer block (A1) having a top molecular weight of Mp (A1) and a structural unit derived from an aromatic vinyl compound and determined in terms of standard polystyrene by gel permeation chromatography is Mp (A2
  • Mp (A1) / Mp (A2)] satisfies 1/10 to 8/10.
  • the ratio [Mp (A1) / Mp (A2)] indicates that Mp (A1) is smaller than Mp (A2). From the same viewpoint, it is more preferably 3/10 to 7/10.
  • the hydrogenated product of the triblock copolymer [A1-B-A2] is an apparently asymmetric triblock copolymer because Mp (A1) and Mp (A2) are different as described above. It can be said.
  • a hydrogenated block copolymer (II) in which Mp (A1) and Mp (A2) are substantially equal is also preferable.
  • “substantially equal” means that [Mp (A1) / Mp (A2)] is approximately 1/1 or close to 1/1, and more specifically, 9/10 to 11 / It means being in the range of 10.
  • Mp (A1) and Mp (A2) are each preferably 1,000 to 30,000, more preferably 2,000 to 20,000, and still more preferably 2,000 to 15,000.
  • Mp (A1) is particularly preferably 3,000 to 10,000
  • Mp (A2) is particularly preferably 4,000 to 14,000.
  • the total peak top molecular weight (Mp) of the hydrogenated block copolymer (II) is 50,000 to 200,000, preferably 70,000 to 200,000, after hydrogenation. Preferably, it is 100,000 to 200,000. If the peak top molecular weight (Mp) of the hydrogenated block copolymer (II) is within the above range, the powdered hydrogenated block copolymer (II) having a bulk density of 0.10 to 0.40 g / ml is obtained. It tends to be easily obtained, and tends to be excellent in moldability, flexibility and strain recovery at high temperatures. In addition, this peak top molecular weight (Mp) is the value calculated
  • the glass transition temperature (Tg) of the hydrogenated block copolymer (II) is preferably ⁇ 45 to 0 ° C., more preferably ⁇ 45 to ⁇ 5 ° C., and further preferably ⁇ 45 to ⁇ from the viewpoint of vibration damping properties. It is 10 ° C., particularly preferably ⁇ 40 to ⁇ 10 ° C.
  • Examples of the method for producing the hydrogenated block copolymer (II) include ionic polymerization methods such as anionic polymerization and cation polymerization, polymerization methods such as single site polymerization method and radical polymerization method.
  • anionic polymerization method for example, an alkyl lithium compound or the like is used as a polymerization initiator and is selected from the group consisting of an aromatic vinyl compound, isoprene and butadiene in an inert organic solvent such as n-hexane or cyclohexane.
  • the block copolymer is produced by sequentially polymerizing at least one of the above to produce a block copolymer having a desired molecular structure and molecular weight, and then adding an active hydrogen compound such as alcohols, carboxylic acids and water to stop the polymerization. Copolymers can be produced.
  • the hydrogenated block copolymer (II) can be obtained by conducting a hydrogenation reaction in the presence of a hydrogenation catalyst in an inert organic solvent without preferably isolating the obtained block copolymer. it can.
  • alkyl lithium compound examples include alkyl lithium compounds having 1 to 10 carbon atoms in the alkyl residue, and methyl lithium, ethyl lithium, butyl lithium, and pentyl lithium are particularly preferable.
  • the amount of the initiator such as an alkyl lithium compound is appropriately determined depending on the peak top molecular weight (Mp) of the hydrogenated block copolymer (II). On the other hand, 0.01 to 0.2 parts by mass are preferably used.
  • the polymerization is usually preferably carried out at 0 to 80 ° C., preferably 0.5 to 50 hours.
  • the structural unit derived from at least one selected from the group consisting of isoprene and butadiene has a vinyl bond content of 45% or more.
  • a Lewis base as a cocatalyst during the polymerization.
  • the Lewis base include ethers such as dimethyl ether, diethyl ether, and tetrahydrofuran; glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; triethylamine, N, N, N ′, N′-tetramethylenediamine, and N-methylmorpholine.
  • amine compounds such as The amount of the Lewis base used is preferably 0.1 to 1000 moles per 1 mole of lithium atoms in the alkyllithium compound used as the initiator.
  • an unhydrogenated block copolymer is dissolved in an inert organic solvent such as n-hexane or cyclohexane which is inert to the reaction and the hydrogenation catalyst in the presence of a hydrogenation catalyst.
  • an inert organic solvent such as n-hexane or cyclohexane which is inert to the reaction and the hydrogenation catalyst in the presence of a hydrogenation catalyst.
  • a method of reacting molecular hydrogen is preferably used.
  • hydrogenation catalysts examples include Raney nickel; heterogeneous catalysts such as Pt, Pd, Ru, Rh, Ni and other metals supported on carbon, alumina, diatomaceous earth, etc .; transition metal compounds and alkylaluminum compounds, alkyllithiums
  • a Ziegler-based catalyst composed of a combination of compounds is used.
  • the reaction is usually carried out under conditions of a hydrogen pressure of preferably 0.1 to 20 MPa, a reaction temperature of preferably 20 ° C. to 250 ° C., and a reaction time of preferably 0.1 to 100 hours.
  • the hydrogenated block copolymer (II) in the form of powder having a bulk density of 0.10 to 0.40 g / ml can be produced by the following method.
  • the bulk density referred to in this specification is a value calculated by putting a weighed powdered hydrogenated block polymer (II) into a graduated cylinder and measuring its volume, and dividing the mass of the polymer by the volume. is there.
  • the reaction solution from which the hydrogenation catalyst has been removed by filtration after the above hydrogenation reaction is heated to 40 to 150 ° C., preferably 60 to 150 ° C., and a surfactant such as a fatty acid salt or a polyoxyalkylene derivative is mixed as necessary.
  • a desired moisture content of 0.1% by mass / WB or less is obtained by drying at 60 to 100 ° C. using a screw extruder type dryer, an expander dryer, a conduction heat transfer type dryer, a hot air dryer or the like.
  • a powdered hydrogenated block copolymer (II) can be produced.
  • the content ratio [(I) / (II)] of the olefin rubber (I) and the hydrogenated block copolymer (II) is 90/10 to 10 by mass ratio. / 90, preferably 90/10 to 50/50, more preferably 80/20 to 20/80, and still more preferably 80/20 to 60/40. Within this range, the moldability, flexibility and strain recovery at high temperatures are excellent.
  • Polyolefin resin (III) examples of the polyolefin resin (III) used in the present invention include polyethylene resin, polypropylene resin, poly (1-butene), poly (4-methyl-1-pentene) and the like.
  • Polyolefin resin (III) may be used individually by 1 type, and may use 2 or more types together. Among these, from the viewpoint of moldability, at least one selected from the group consisting of polyethylene resins and polypropylene resins is preferable, and polypropylene resins are more preferable.
  • the polyethylene-based resin refers to a polymer having a content of structural units derived from ethylene (hereinafter sometimes abbreviated as ethylene content) of 60 mol% or more, and the ethylene content is Preferably it is 70 mol% or more, More preferably, it is 80 mol% or more.
  • the polypropylene resin refers to a polymer in which the content of structural units derived from propylene (hereinafter sometimes abbreviated as propylene content) is 60 mol% or more, and the propylene content is preferably Is 70 mol% or more, more preferably 80 mol% or more, and particularly preferably 90 mol% or more.
  • the polyolefin resin (III) is distinguished from the olefin rubber (I) which is “rubber”.
  • polyethylene resins include ethylene homopolymers such as high density polyethylene, medium density polyethylene, and low density polyethylene; ethylene / butene-1 copolymer, ethylene / hexene copolymer, ethylene / heptene copolymer, Ethylene / octene copolymer, ethylene / 4-methylpentene-1 copolymer, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / acrylic acid ester copolymer, ethylene / methacrylic acid copolymer And ethylene-based copolymers such as ethylene / methacrylic acid ester copolymers.
  • at least one selected from the group consisting of high density polyethylene, medium density polyethylene, and low density polyethylene is preferable.
  • polypropylene resins examples include propylene homopolymer, ethylene / propylene random copolymer, ethylene / propylene block copolymer, propylene / butene-1 copolymer, propylene / ethylene / butene-1 copolymer, propylene / 4-methylpentene-1 copolymer and the like.
  • propylene homopolymer ethylene / propylene random copolymer
  • ethylene / propylene block copolymer examples include polypropylene resins.
  • propylene homopolymer ethylene / propylene random copolymer, ethylene / propylene block copolymer, propylene / butene-1 copolymer, propylene / 4-methylpentene-1 copolymer and the like.
  • the melt flow rate (MFR) measured under the conditions of 230 ° C. and 2.16 kg of the polyolefin resin (III) is preferably 0.1 g / 10 min or more from the viewpoint of moldability. It is more preferably 1 to 50 g / 10 minutes, further preferably 1 to 40 g / 10 minutes, and particularly preferably 5 to 40 g / 10 minutes.
  • the MFR is a value measured according to JIS K7210-1 (2014).
  • the content of the polyolefin resin (III) is 10 to 200 parts by weight, preferably 10 to 100 parts by weight, based on a total of 100 parts by weight of the olefin rubber (I) and the hydrogenated block copolymer (II). 15 to 100 parts by mass is more preferable, 20 to 80 parts by mass is more preferable, and 30 to 70 parts by mass is still more preferable. If it is less than 10 parts by mass with respect to 100 parts by mass in total of the olefin rubber (I) and the hydrogenated block copolymer (II), molding processability is poor, whereas if it exceeds 200 parts by mass, flexibility and rubber Elasticity decreases.
  • the polyolefin resin (III) forms a continuous phase in the thermoplastic elastomer composition by adjusting the content of the polyolefin resin (III) in the above range.
  • the olefin rubber (I) and the hydrogenated block copolymer (II) have a dispersed morphology in the form of fine particles, and this is an adhesive force, flexibility, and flexibility to the vulcanized rubber and the dynamically crosslinked thermoplastic elastomer (TPV). It is presumed to have a good influence on the weather resistance and molding processability.
  • Softener (IV) examples include petroleum-based process oils such as paraffinic process oil and naphthenic process oil; aromatic process oils; phthalic acid derivatives such as dioctyl phthalate and dibutyl phthalate; white oil; mineral oil; Vegetable oil-based softeners such as oil and rosin; liquid paraffin; liquid co-oligomer of ethylene and ⁇ -olefin, liquid polybutene, liquid polybutadiene, liquid polyisoprene, liquid polyisoprene / butadiene copolymer, liquid styrene / butadiene copolymer And synthetic softeners such as liquid styrene / isoprene copolymer.
  • petroleum-based process oils such as paraffinic process oil and naphthenic process oil; aromatic process oils; phthalic acid derivatives such as dioctyl phthalate and dibutyl phthalate; white oil; mineral oil; Vegetable oil-based softeners such as
  • the kinematic viscosity at 40 ° C. is 20 to 800 mm 2 / s (preferably 40 to 600 mm 2 / s, more preferably 60 to 400 mm 2 / s, and further preferably 60 to 200 mm 2 / s. Particularly preferred is a softening agent of 70 to 120 mm 2 / s).
  • the kinematic viscosity is a value measured according to JIS K2283 (2000).
  • the pour point of the softening agent (IV) is preferably ⁇ 40 to 0 ° C., more preferably ⁇ 30 to 0 ° C.
  • the flash point (COC method) of the softening agent (IV) is preferably 200 to 400 ° C., more preferably 250 to 350 ° C.
  • softening agent (IV) petroleum process oil, liquid co-oligomer of ethylene and ⁇ -olefin, and liquid paraffin are preferable, petroleum process oil is more preferable, and paraffin process oil is more preferable.
  • the softener (IV) may be used alone or in combination of two or more. Examples of commercially available softeners (IV) include paraffinic process oil and naphthenic process oil (preferably paraffinic process oil) in the “Diana Process Oil” series marketed by Idemitsu Kosan Co., Ltd. it can.
  • the content of the softening agent (IV) is 15 to 300 parts by weight, preferably 15 to 150 parts by weight, based on 100 parts by weight in total of the olefin rubber (I) and the hydrogenated block copolymer (II). It is more preferably 20 to 120 parts by mass, and further preferably 20 to 100 parts by mass.
  • the total amount of the olefin rubber (I) and the hydrogenated block copolymer (II) exceeds 100 parts by mass, the mechanical properties are deteriorated and the molded product obtained from the thermoplastic elastomer composition is used.
  • the softening agent (IV) tends to bleed out and the mechanical strength is lowered.
  • thermoplastic elastomer composition of the present invention has the advantage of having sufficient flexibility and moldability even if the content of the softening agent (IV) is reduced.
  • the content of the softening agent (IV) for imparting the same or higher flexibility and molding processability is small. .
  • the upper limit of the content of the softening agent (IV) may be 60 parts by mass or 50 parts by mass in any of the above numerical ranges. It may be 40 parts by mass or 30 parts by mass.
  • thermoplastic elastomer composition of the present invention may be obtained by crosslinking the olefin rubber (I) and the polymer block (B) of the hydrogenated block copolymer (II). By crosslinking in this way, the morphology tends to be easily formed.
  • Crosslinking agent (V) examples include radical generators, sulfur and sulfur compounds.
  • the radical generator include dialkyl monoperoxides such as dicumyl peroxide, di-t-butyl peroxide, and t-butylcumyl peroxide; 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, , 5-Dimethyl-2,5-di (t-butylperoxy) hexyne-3, 1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) -3,3 Diperoxides such as 5-trimethylcyclohexane and n-butyl-4,4-bis (t-butylperoxy) valerate; Diacyl peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide and 2,4-dichloro
  • the content thereof is preferably 0.01 to 15 parts by mass, more preferably 100 parts by mass relative to the total of 100 parts by mass of the olefin rubber (I) and the hydrogenated block copolymer (II). 0.05 to 10 parts by mass.
  • sulfur compound examples include sulfur monochloride and sulfur dichloride.
  • sulfur or a sulfur compound the content thereof is preferably 0.1 to 20 parts by mass, more preferably 100 parts by mass relative to the total of 100 parts by mass of the olefin rubber (I) and the hydrogenated block copolymer (II). Is 0.5 to 10 parts by mass, more preferably 1 to 10 parts by mass.
  • crosslinking agents (V) include phenolic resins such as alkylphenol resins and brominated alkylphenol resins; combinations of p-quinonedioxime and lead dioxide, p, p'-dibenzoylquinonedioxime and trilead tetroxide Etc. can also be used.
  • Crosslinking aid (VI) As the crosslinking aid (VI), a known crosslinking aid can be used. For example, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, trimellitic acid triallyl ester, 1,2,4-benzenetricarboxylic acid triallyl ester, triallyl isocyanurate, 1,6-hexanediol dimethacrylate, 1, 9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, divinylbenzene, glycerol dimethacrylate, 2-hydroxy-3-acryloyl Polyfunctional monomers such as oxypropyl methacrylate; stannous chloride, ferric chloride, organic sulfonic acid, polychloropropyl E
  • the crosslinking aid (VI) may be used by impregnating diatomaceous earth, white carbon or the like.
  • the polyfunctional monomer (and triallyl isocyanurate) is preferably impregnated in diatomaceous earth or white carbon, and more preferably impregnated in white carbon.
  • the crosslinking aid (VI) one kind may be used alone, or two or more kinds may be used in combination.
  • the content thereof is preferably 0.1 to 40 parts by mass with respect to a total of 100 parts by mass of the olefin rubber (I) and the hydrogenated block copolymer (II). More preferred is 0.5 to 20 parts by mass, and further preferred is 2 to 20 parts by mass.
  • Crosslinking accelerator (VII) examples include thiazoles such as N, N-diisopropyl-2-benzothiazole-sulfenamide, 2-mercaptobenzothiazole, 2- (4-morpholinodithio) benzothiazole; diphenylguanidine, Guanidines such as triphenylguanidine; aldehyde-amine reactants such as butyraldehyde-aniline reactant, hexamethylenetetramine-acetaldehyde reactant or aldehyde-ammonia reactants; imidazolines such as 2-mercaptoimidazoline; thiocarbanilide, diethyl Thioureas such as urea, dibutylthiourea, trimethylthiourea, diorthotolylthiourea; dibenzothiazyl disulfide; tetramethylthiuram monosulfide, tetra
  • thermoplastic elastomer composition of the present invention may further contain another thermoplastic polymer.
  • Other thermoplastic polymers include, for example, polyphenylene ether resins; polyamide 6, polyamide 6 ⁇ 6, polyamide 6 ⁇ 10, polyamide 11, polyamide 12, polyamide 6 ⁇ 12, polyhexamethylenediamine terephthalamide, polyhexamethylene Polyamide resins such as diamine isophthalamide and xylene group-containing polyamide; Polyester resins such as polyethylene terephthalate and polybutylene terephthalate; Acrylic resins such as polymethyl acrylate and polymethyl methacrylate; Polyoxymethylene homopolymer, Polyoxymethylene Polyoxymethylene resins such as copolymers; Styrene resins such as styrene homopolymers, acrylonitrile-styrene resins, acrylonitrile-butadiene-styrene resins; Bonate resin; Styrenic elastomers such as styrene
  • the content when other thermoplastic polymers are contained, the content may be used within a range that does not impair the flexibility and mechanical strength of the thermoplastic elastomer composition, and before adding the other thermoplastic polymers.
  • the amount is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, and still more preferably 50 parts by mass or less with respect to 100 parts by mass of the thermoplastic elastomer composition.
  • thermoplastic elastomer composition of the present invention may further contain various additives as long as the effects of the present invention are not impaired.
  • additives include lubricants, foaming agents, nucleating agents, antioxidants, heat stabilizers, light resistance agents, weathering agents, metal deactivators, ultraviolet absorbers, light stabilizers, copper damage prevention agents, and fillers.
  • Reinforcing agents, antistatic agents, antibacterial agents, fungicides, dispersants, coloring agents and the like One of these may be contained alone, or two or more may be contained.
  • a lubricant is preferable because it improves the fluidity of the thermoplastic elastomer composition and suppresses thermal degradation.
  • the lubricant include silicone oils; hydrocarbon lubricants such as paraffin wax, microwax and polyethylene wax; butyl stearate, stearic acid monoglyceride, pentaerythritol tetrastearate, stearyl stearate, unsaturated fatty acid monoamide, and the like. It is done. These may be used individually by 1 type and may use 2 or more types together.
  • the content thereof is preferably 0.01 to 3 parts by weight, more preferably 0.05 to 1 part by weight, and still more preferably 100 parts by weight of the thermoplastic elastomer composition excluding the lubricant. 0.1 to 0.8 part by mass.
  • the foaming agent may be used in the production of a weather seal.
  • the foaming agent include inorganic foaming agents such as ammonium carbonate, ammonium hydrogen carbonate, sodium hydrogen carbonate, ammonium nitrite, sodium borohydride, and azides; N, N′-dinitrosopentamethylenetetramine, N, N ′ -N-nitroso compounds such as dimethyl-N, N'-dinitrosotephthalamide; azo compounds such as azobisisobutyronitrile, azodicarbonamide, barium azodicarboxylate; trichloromonofluoromethane, dichloromonofluoro Fluorinated alkanes such as methane; sulfonylhydrazine compounds such as paratoluenesulfonyl hydrazide, diphenylsulfone-3,3′-disulfonylhydrazide, 4,4′-oxybis (benzenes
  • Sulfonyl semicarbazide compounds such as p-toluylenesulfonyl semicarbazide and 4,4′-oxybis (benzenesulfonyl semicarbazide); organic foams such as triazole compounds such as 5-morpholyl-1,2,3,4-thiatriazole Agents: Thermally expandable fine particles encapsulated in microcapsules in which a heat-expandable compound such as isobutane and pentane is made of a thermoplastic resin such as vinylidene chloride, acrylonitrile, acrylic acid ester, and methacrylic acid ester. These may be used individually by 1 type and may use 2 or more types together.
  • nucleating agent when making a weather seal into a foam, you may contain a nucleating agent as needed.
  • the nucleating agent include metal oxides, composite oxides, metal carbonates such as talc, silica, alumina, mica, titania, zinc oxide, zeolite, calcium carbonate, magnesium carbonate, barium sulfate, and aluminum hydroxide.
  • a metal sulfate, a metal hydroxide, etc. can be used.
  • Crosslinking method As described above, the polymer block (B) portion of the olefin rubber (I) and the hydrogenated block copolymer (II) may be crosslinked.
  • a crosslinking method a method in which a crosslinking agent (V), a crosslinking assistant (VI) and a crosslinking accelerator (VII) are appropriately added to the olefin rubber (I) and the hydrogenated block copolymer (II) and kneaded.
  • Crosslinking method 1 resin crosslinking method
  • crosslinking method 3 quinoid crosslinking method
  • methods using active energy rays crosslinking method 4
  • thermoplastic elastomer composition of the present invention a crosslinking agent (V), a crosslinking assistant (VI) and a crosslinking accelerator (VII) are appropriately added to the olefin rubber (I) and the hydrogenated block copolymer (II). Then, the polymer block (B) of the olefin rubber (I) and the hydrogenated block copolymer (II) can be crosslinked.
  • a crosslinking aid (VI) such as the polyfunctional monomer, dibenzothiazyl disulfide and tetramethylthiuram disulfide (so-called disulfide type) as necessary together with the crosslinking agent (V) such as the radical generator.
  • a crosslinking accelerator (VII) such as a compound
  • a method of melt-kneading a thermoplastic elastomer composition containing a radical generator and, if necessary, another thermoplastic resin, under heating can be mentioned.
  • the heating temperature is preferably 140 to 230 ° C.
  • Melt-kneading can be carried out batchwise or continuously with an apparatus such as an extruder, kneader, roll, plastograph or the like.
  • the crosslinking reaction proceeds by such a melt-kneading process.
  • crosslinking agent (V) When sulfur or a sulfur compound is used as the crosslinking agent (V), crosslinking accelerators such as thiazoles, guanidines, butyraldehyde-aniline reactants, hexamethylenetetramine-acetaldehyde reactants, aldehyde-amine reactants ( It is highly preferred to use VII) together.
  • the cross-linking agent (V), the cross-linking accelerator (VII) and the like are preferably used at 50 to 250 ° C. (more preferably 80 to 200 ° C.) using a mixer such as a roll or a Banbury mixer. After kneading, crosslinking can be formed by maintaining the temperature at 60 ° C. or higher (more preferably 90 to 250 ° C.), usually for 1 minute to 2 hours (more preferably 5 minutes to 1 hour).
  • phenolic resins such as alkylphenol resins and brominated alkylphenol resins are used as the crosslinking agent (V), and stannous chloride, ferric chloride, organic sulfonic acid, Polychloroprene or chlorosulfonated polyethylene is used.
  • the crosslinking temperature is preferably 100 to 250 ° C, more preferably 130 to 220 ° C.
  • a crosslinking accelerator (VII) in combination.
  • ⁇ About crosslinking method 3> In the crosslinking method by the quinoid crosslinking method, a combination of p-quinonedioxime and lead dioxide, p, p′-dibenzoylquinonedioxime and trilead tetroxide, or the like is used as the crosslinking agent (V).
  • the crosslinking temperature is preferably 90 to 250 ° C, more preferably 110 to 220 ° C.
  • a crosslinking accelerator (VII) in combination.
  • Examples of active energy rays that can be used in the crosslinking method using active energy rays include particle rays, electromagnetic waves, and combinations thereof.
  • Examples of the particle beam include an electron beam (EB) and an ⁇ ray
  • examples of the electromagnetic wave include an ultraviolet ray (UV), a visible ray, an infrared ray, a ⁇ ray, and an X ray.
  • an electron beam (EB) or an ultraviolet ray (UV) is preferable.
  • thermoplastic elastomer composition containing olefin rubber (I), hydrogenated block copolymer (II), polyolefin resin (III) and softener (IV) in specific proportions.
  • a mixture of olefin rubber (I), polyolefin resin (III) and softening agent (IV) which has been previously cross-linked is prepared, to which hydrogenated block copolymer (II) and polyolefin resin (III) are prepared.
  • any of melt-kneading devices capable of uniformly mixing each component can be used, for example, a single screw extruder, a twin screw extruder, or the like.
  • a twin screw extruder that has a large shearing force during kneading and can be operated continuously.
  • a weather seal can be obtained from the obtained thermoplastic elastomer composition by a known molding method, preferably extrusion molding or injection molding. In particular, when forming a corner portion of a weather seal, injection molding is used.
  • extrusion molding is preferably used.
  • foam molding is performed.
  • the foam molding method includes a chemical method of foaming by decomposition or reaction of the foaming agent, the chemical method and supercritical foaming. Or the method of using together with physical methods, such as water foaming, is mentioned.
  • foam molding can be performed by a method usually used for foam molding, such as injection foam molding and extrusion foam molding.
  • a foam for forming a corner portion of a weather seal is obtained by injection-foaming a thermoplastic elastomer composition dry blended with a foaming agent into a mold having a cavity having a desired shape. It is done.
  • thermoplastic elastomer composition of the present invention has a hardness (JIS-A) measured according to the method described in the examples of 30 to 90, specifically 40 to 80, and has a flexibility suitable as a weather seal.
  • the upper limit of hardness is preferably 80 or less, more preferably 76 or less, and for a door seal corner, the upper limit of hardness is preferably 57 or less, more preferably 52 or less. preferable.
  • the adhesive strength to vulcanized rubber measured according to the method described in the examples is 100 to 300 N / cm 2 and the adhesive strength to TPV is 100 to 400 N / cm 2 , the adhesive strength to vulcanized rubber and TPV Excellent power.
  • adhesion to TPV is preferably 250 N / cm 2 or more, more preferably 310N / cm 2 or more, adhesion to vulcanized EPDM is 220 N / cm 2 or more, 240 N / cm 2 or more is more preferable (see Table 3).
  • adhesion to TPV is preferably 110N / cm 2 or more, more preferably 140 N / cm 2 or more, adhesion to vulcanized EPDM is 100 N / cm 2 or more, 115 N / cm 2 or more is more preferable (see Table 4).
  • the thermoplastic elastomer composition of the present invention is also excellent in weather resistance and moldability.
  • This invention provides the member which has the site
  • Part (X1) may be a part of the member or the whole. That is, this invention also provides the member which has the site
  • site (Y1) There are no particular restrictions on the material of the site (Y1), but in the case of weather seal applications, vulcanized rubber, dynamic cross-linked thermoplastic elastomer (TPV), and the like can be mentioned.
  • the vulcanized rubber includes (1) a cross-linked product of ethylene and one or more ⁇ -olefins having 3 to 20 carbon atoms, and (2) ethylene and one ⁇ -olefin having 3 to 20 carbon atoms.
  • examples thereof include a cross-linked product of a copolymer of the above and one or more non-conjugated polyenes.
  • the vulcanized rubber is preferably a cross-linked product of a copolymer of ethylene, one or more ⁇ -olefins having 3 to 20 carbon atoms and one or more nonconjugated polyenes. More preferred is a crosslinked product of the above copolymer.
  • the TPV is preferably an olefinic TPV containing an olefinic resin and an olefinic rubber, and more preferably an olefinic TPV containing a polypropylene resin and an olefinic rubber.
  • the olefin-based rubber is preferably a cross-linked product of ethylene, one or more ⁇ -olefins having 3 to 20 carbon atoms and one or more nonconjugated polyenes, and includes ethylene, propylene and nonconjugated polyenes.
  • a cross-linked product of a copolymer (EPDM) is more preferred.
  • TPV TPV
  • commercially available products such as “Excellink 1303B” and “Excellink 1703B” (both manufactured by JSR Corporation) can also be used.
  • the “alpha-olefin having 3 to 20 carbon atoms” and “non-conjugated polyene” are the same as those described in the olefin rubber (I), and the preferred ones are also the same.
  • Vulcanized rubber and TPV contain various additives such as vulcanization aids, vulcanization accelerators, softeners, anti-aging agents, carbon black, zinc oxide, and lubricants as necessary. May be.
  • the present invention also provides a member having a part (X2) made of the thermoplastic elastomer composition of the present invention in addition to the part (X1).
  • the material of the part (X2) may be the same as or different from the thermoplastic elastomer composition forming the part (X1).
  • the material of the part (X2) is different from the thermoplastic elastomer composition forming the part (X1), it becomes a member using two or more thermoplastic elastomer compositions of the present invention.
  • the part (X1) made of the thermoplastic elastomer composition of the present invention is preferably a part obtained by injection molding.
  • the present invention also provides a weather seal containing the member. More specifically, a weather seal having a corner portion made of the portion (X1) and a straight portion made of the portion (X2) or (Y1) is provided.
  • the weather seal is useful for automobiles, ships or aircraft. Since the part (X1) is excellent in flexibility and molding processability, it is particularly useful as a corner member and is useful as a weather seal corner member. For example, if it is used for automobiles, it is useful as a corner member of a glass run, a corner member of a door seal or the like.
  • Peak top molecular weight (Mp) According to gel permeation chromatography (GPC) measurement under the following conditions, peaks in terms of polystyrene in the polymer blocks (A1) and (A2) before hydrogenation and in the hydrogenated block copolymer (II) after hydrogenation The top molecular weight (Mp) was determined.
  • the Mp (A2) of the polymer block (A2) is obtained by subtracting the Mp of the polymer block [A1-B] before hydrogenation from the Mp of the hydrogenated block copolymer (II) after hydrogenation. Asked.
  • Mw / Mn The weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were determined by gel permeation chromatography (GPC) in terms of standard polystyrene. The measurement apparatus and conditions were the same as the GPC measurement apparatus and measurement conditions in the measurement of the peak top molecular weight (Mp).
  • a reaction solution containing a styrene- (butadiene / isoprene) -styrene block copolymer was obtained.
  • 5% by mass of palladium carbon (palladium supported amount: 5% by mass) as a hydrogenation catalyst was added to the block copolymer, and the reaction was performed for 10 hours under conditions of a hydrogen pressure of 2 MPa and 150 ° C. .
  • the palladium carbon is removed by filtration, the filtrate is concentrated, and further dried under vacuum to obtain a hydrogenated styrene- (butadiene / isoprene) -styrene block copolymer (hydrogenated block copolymer).
  • Compound (II) -1) was obtained.
  • the amount of each component used and the measurement results of the physical properties of the hydrogenated block copolymer (II) -1 are shown in Table 1.
  • thermoplastic elastomer composition obtained in each example were injection molded at a cylinder temperature of 230 ° C. with an injection molding machine “EC75SX” (manufactured by Toshiba Machine Co., Ltd.), 100 mm long, 35 mm wide, A sheet having a thickness of 2 mm was prepared, and the sheet was cut into a length of 50 mm and a width of 35 mm to prepare a test piece. The presence or absence of a flow mark in the test piece was visually observed, and molding processability was evaluated according to the following criteria. A: No flow mark B: Low flow mark C: Many flow marks
  • Adhesive strength with an adherend made of a dynamically crosslinked thermoplastic elastomer (TPV) or an adherend made of vulcanized rubber was measured by the following method.
  • Adherent consisting of TPV TPV-1: Using a pellet of “Excelin 1703B” (manufactured by JSR Corporation), a test piece having a length of 50 mm, a width of 35 mm, and a thickness of 2 mm was prepared according to the method described in “(8) Moldability”, This was designated as an adherend “TPV-1.” The hardness of the TPV-1 measured according to the method described in “(7) Hardness” was 71.
  • TPV-2 A test piece was prepared in the same manner as TPV-1 except that pellets of “Excelin 1303B” (manufactured by JSR Corporation) were used, and this was used as an adherend “TPV-2”.
  • the hardness of the TPV-2 measured according to the method described in “(7) Hardness” was 42.
  • Vulcanized EPDM-3 Ethylene / propylene / diene copolymer rubber “EPT4045” (Mitsui Chemicals Co., Ltd.), carbon black “Diablack H” (Mitsubishi Chemical Co., Ltd.) in the blending amounts shown in Table 2 below.
  • Anti-aging agent “NOCRACK 6C” (manufactured by Ouchi Shinko Chemical Co., Ltd.), stearic acid “LUNAC S-20” (manufactured by Kao Corporation) and zinc white “Zinc Oxide” (manufactured by Sakai Chemical Industry Co., Ltd.)
  • the mixture was kneaded for 6 minutes at 150 ° C. using a Banbury mixer (first kneading stage).
  • a vulcanizing agent “sulfur” fine sulfur, 200 mesh, manufactured by Tsurumi Chemical Co., Ltd.
  • a vulcanization accelerator (1) were blended in the amounts shown in Table 2 below.
  • a test piece was prepared by punching out 50 mm in length, 35 mm in width, and 2 mm in thickness from this sheet, and this was used as an adherend “vulcanized EPDM-3”.
  • the hardness of this vulcanized EPDM-3 measured according to the method described in “(7) Hardness” was 70.
  • ⁇ Measurement method of adhesive strength> Each adherend (50 mm long ⁇ 35 mm wide ⁇ 2 mm thick) obtained as described above is mounted in a cavity of 100 mm long ⁇ 35 mm wide ⁇ 2 mm thick, and injection molding machine “EC75SX” is provided there. (Manufactured by Toshiba Machine Co., Ltd.), a thermoplastic elastomer was injection molded at 230 ° C.
  • thermoplastic elastomer composition a thermoplastic elastomer composition.
  • a thing is the state which adhere
  • the obtained composite molded sheet (length 100 mm ⁇ width 35 mm ⁇ thickness 2 mm) was cut into length 100 mm ⁇ width 10 mm ⁇ thickness 2 mm, and Instron universal under a temperature condition of 23 ° C. and a tensile speed condition of 200 mm / min.
  • the adhesion between the thermoplastic elastomer composition and the adherend was measured using a tester “Instron 5566” (manufactured by Instron Japan).
  • thermoplastic elastomer compositions of the examples all have high adhesion to TPV-1, TPV-2 and vulcanized EPDM-3, and have flexibility and weather resistance. It can be seen that the moldability is also excellent. Further, when Example 6 and Example 8 are compared, the ratio of the peak top molecular weight (Mp) in the polymer blocks (A1) and (A2) in the hydrogenated block copolymer (II) [Mp (A1) / It can be seen that Example 8 in which Mp (A2)] satisfies 1/10 to 8/10 is more excellent in moldability.
  • the thermoplastic elastomer compositions obtained in Examples 1 to 8 are particularly useful for glass run corners in automobiles.
  • thermoplastic elastomer compositions obtained in Examples 9 to 16 are particularly useful for corner portions of door seals in automobiles.
  • Comparative Examples 1, 2, 8 and 9 using a hydrogenated block copolymer having a low hydrogenation rate the adhesive strength to TPV may be insufficient (see Comparative Example 2), and the weather resistance is also low. It turns out that it is insufficient (refer comparative examples 1, 2, 8, and 9).
  • Comparative Examples 3, 4, 10 and 11 using a hydrogenated block copolymer in which the vinyl bond content of the polymer block (B) is less than 45% the flexibility may be insufficient (Comparative Example). 3 and 10), and the adhesive strength to TPV and vulcanized rubber may be poor (see Comparative Examples 4 and 11).
  • thermoplastic elastomer composition of the present invention has high adhesion to vulcanized rubber and dynamically cross-linked thermoplastic elastomer (TPV), and is excellent in molding processability as well as flexibility and weather resistance. It is useful for weather seals, particularly for corners of weather seals.
  • TPV dynamically cross-linked thermoplastic elastomer

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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)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Sealing Material Composition (AREA)

Abstract

L'invention concerne une composition élastomère thermoplastique qui présente une forte adhérence au caoutchouc vulcanisé et aux élastomères thermoplastiques réticulés dynamiquement (TPV) et présente une excellente souplesse, une excellente résistance aux intempéries et une excellente aptitude au moulage. L'invention concerne en outre un élément présentant une partie constituée par la composition élastomère thermoplastique, un joint d'étanchéité aux intempéries comprenant l'élément et un élément d'angle pour un joint d'étanchéité aux intempéries comprenant une partie constituée par la composition d'élastomère thermoplastique. La composition élastomère thermoplastique est, particulièrement, une composition élastomère thermoplastique comprenant un caoutchouc à base d'oléfine (I), un copolymère séquencé hydrogéné (II) décrit ci-dessous, une résine à base de polyoléfine (III) et un agent assouplissant (IV). Le rapport de la teneur en caoutchouc à base d'oléfine (I) et du copolymère séquencé hydrogéné (II) [(I)/(II)] est de 90/10 à 10/90 (rapport en masse). Par rapport à un total de 100 parties en masse du caoutchouc à base d'oléfine (I) et du copolymère séquencé hydrogéné (II), la teneur en résine à base de polyoléfine (III) est de 10 à 200 parties en masse et la teneur en agent assouplissant (IV) est de 15 à 300 parties en masse. Le copolymère séquencé hydrogéné (II) comprend : un bloc polymère (A) comprenant principalement des motifs structuraux dérivés d'un composé aromatique de vinyle; et un bloc polymère (B) comprenant principalement des motifs structuraux dérivés d'au moins une substance choisie dans le groupe constitué par l'isoprène et le butadiène, dans lequel la teneur totale en motifs à liaison 3,4 et en motifs à liaison 1,2 est de 45 % ou plus. Le poids moléculaire du sommet du pic du copolymère séquencé hydrogéné (II) est de 50.000 à 200.000 et 70 % en mole ou plus des doubles liaisons carbone-carbone dans le bloc polymère (B) sont hydrogénées.
PCT/JP2016/081960 2015-10-30 2016-10-27 Composition élastomère thermoplastique, élément, joint d'étanchéité aux intempéries et élément de coin pour joint d'étanchéité aux intempéries WO2017073695A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109206550A (zh) * 2017-06-30 2019-01-15 翁秋梅 一种杂化超分子作用动态聚合物
WO2019230872A1 (fr) * 2018-05-31 2019-12-05 株式会社クラレ Copolymère séquencé hydrogéné, composition de résine et différentes applications associées
JP2022187476A (ja) * 2021-06-07 2022-12-19 李長榮化學工業股▲ふん▼有限公司 架橋性及び発泡性組成物、それによって得られる発泡体、発泡のための組成物並びにその使用

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11566129B2 (en) * 2019-11-06 2023-01-31 Kuraray Co., Ltd. Thermoplastic elastomer composition
US11458677B2 (en) 2019-12-26 2022-10-04 Industrial Technology Research Institute Selective laser sintering composition and selective laser sintering 3D printing method employing the same

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63112649A (ja) * 1986-10-30 1988-05-17 Asahi Chem Ind Co Ltd 動加硫された水添ブロツク共重合体組成物
JPH03292342A (ja) * 1990-04-09 1991-12-24 Sumitomo Chem Co Ltd 熱可塑性エラストマー組成物
JPH0726105A (ja) * 1993-07-08 1995-01-27 Mitsui Petrochem Ind Ltd オレフィン系熱可塑性エラストマー
JPH07286078A (ja) * 1994-04-18 1995-10-31 Japan Synthetic Rubber Co Ltd 熱可塑性エラストマー組成物
JPH09316286A (ja) * 1996-05-24 1997-12-09 Sumitomo Chem Co Ltd 熱可塑性エラストマー組成物および複合成形体
JP2001131360A (ja) * 1999-11-02 2001-05-15 Mitsubishi Chemicals Corp オレフィン系熱可塑性エラストマー組成物
JP2005281373A (ja) * 2004-03-29 2005-10-13 Kuraray Co Ltd 熱可塑性エラストマー組成物
JP2005281530A (ja) * 2004-03-30 2005-10-13 Kuraray Co Ltd 熱可塑性エラストマー組成物
JP2014080488A (ja) * 2012-10-16 2014-05-08 Kuraray Co Ltd 熱可塑性エラストマー組成物および該組成物からなる成形体
WO2016136760A1 (fr) * 2015-02-24 2016-09-01 株式会社クラレ Copolymère séquencé hydrogéné, composition de résine, adhésif sensible à la pression, adhésif, objet moulé, récipient d'emballage de liquide, outil médical, sonde médicale, élément d'angle pour joint d'étanchéité, et joint d'étanchéité

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0872556A (ja) * 1994-09-05 1996-03-19 Toyoda Gosei Co Ltd ソリッドゴム製ウェザストリップ

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63112649A (ja) * 1986-10-30 1988-05-17 Asahi Chem Ind Co Ltd 動加硫された水添ブロツク共重合体組成物
JPH03292342A (ja) * 1990-04-09 1991-12-24 Sumitomo Chem Co Ltd 熱可塑性エラストマー組成物
JPH0726105A (ja) * 1993-07-08 1995-01-27 Mitsui Petrochem Ind Ltd オレフィン系熱可塑性エラストマー
JPH07286078A (ja) * 1994-04-18 1995-10-31 Japan Synthetic Rubber Co Ltd 熱可塑性エラストマー組成物
JPH09316286A (ja) * 1996-05-24 1997-12-09 Sumitomo Chem Co Ltd 熱可塑性エラストマー組成物および複合成形体
JP2001131360A (ja) * 1999-11-02 2001-05-15 Mitsubishi Chemicals Corp オレフィン系熱可塑性エラストマー組成物
JP2005281373A (ja) * 2004-03-29 2005-10-13 Kuraray Co Ltd 熱可塑性エラストマー組成物
JP2005281530A (ja) * 2004-03-30 2005-10-13 Kuraray Co Ltd 熱可塑性エラストマー組成物
JP2014080488A (ja) * 2012-10-16 2014-05-08 Kuraray Co Ltd 熱可塑性エラストマー組成物および該組成物からなる成形体
WO2016136760A1 (fr) * 2015-02-24 2016-09-01 株式会社クラレ Copolymère séquencé hydrogéné, composition de résine, adhésif sensible à la pression, adhésif, objet moulé, récipient d'emballage de liquide, outil médical, sonde médicale, élément d'angle pour joint d'étanchéité, et joint d'étanchéité

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109206550A (zh) * 2017-06-30 2019-01-15 翁秋梅 一种杂化超分子作用动态聚合物
WO2019230872A1 (fr) * 2018-05-31 2019-12-05 株式会社クラレ Copolymère séquencé hydrogéné, composition de résine et différentes applications associées
CN112204059A (zh) * 2018-05-31 2021-01-08 株式会社可乐丽 嵌段共聚物的氢化物、树脂组合物和它们的各种用途
JPWO2019230872A1 (ja) * 2018-05-31 2021-07-15 株式会社クラレ ブロック共重合体の水素添加物、樹脂組成物、及びこれらの各種用途
US11492438B2 (en) 2018-05-31 2022-11-08 Kuraray Co., Ltd. Block copolymer hydrogenate, resin composition, and various applications thereof
CN112204059B (zh) * 2018-05-31 2023-02-21 株式会社可乐丽 嵌段共聚物的氢化物、树脂组合物和它们的各种用途
JP2022187476A (ja) * 2021-06-07 2022-12-19 李長榮化學工業股▲ふん▼有限公司 架橋性及び発泡性組成物、それによって得られる発泡体、発泡のための組成物並びにその使用

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