WO2013018171A1 - Feuille de matériau de surface - Google Patents

Feuille de matériau de surface Download PDF

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Publication number
WO2013018171A1
WO2013018171A1 PCT/JP2011/067510 JP2011067510W WO2013018171A1 WO 2013018171 A1 WO2013018171 A1 WO 2013018171A1 JP 2011067510 W JP2011067510 W JP 2011067510W WO 2013018171 A1 WO2013018171 A1 WO 2013018171A1
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WIPO (PCT)
Prior art keywords
copolymer
sheet
mass
cross
vinyl compound
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PCT/JP2011/067510
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English (en)
Japanese (ja)
Inventor
荒井　亨
歩 塚本
勝 長谷川
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電気化学工業株式会社
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Application filed by 電気化学工業株式会社 filed Critical 電気化学工業株式会社
Priority to JP2013526636A priority Critical patent/JP5891229B2/ja
Priority to PCT/JP2011/067510 priority patent/WO2013018171A1/fr
Publication of WO2013018171A1 publication Critical patent/WO2013018171A1/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
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms

Definitions

  • the present invention relates to a skin material sheet formed from a thermoplastic resin composition comprising a specific cross copolymer and an ethylene copolymer.
  • automotive interior skin materials include heat resistance, weather resistance, cold resistance, texture retention including heat history during molding, scratch resistance against human contact, and oil resistance to chemical substances accompanying humans.
  • Chemical resistance is required.
  • Soft PVC is a material with excellent softness, oil resistance and scratch resistance, and is advantageous in terms of price, but it is a problem of management at the time of incineration, VOC due to plasticizers contained in large quantities in recent years, and some plasticizers
  • TPO olefin-based thermoplastic elastomer
  • TPS styrene-based thermoplastic elastomer
  • TPO cross-linked ethylene-propylene rubber
  • TPS cross-linked or non-cross-linked styrene hydrogenated block copolymer
  • Patent Documents 1, 2, and 3 a new soft resin, styrene-ethylene cross-copolymer
  • This resin is characterized by its ability to be adjusted in a wide range of hardness from soft to semi-rigid without a plasticizer, as well as excellent abrasion resistance and oil resistance.
  • the present resin itself lacks heat resistance for the above-mentioned applications, and further improvement is desired in terms of the retention of wrinkles during use as a skin material or during molding. From such a background, heat resistance has been improved by blending heat-resistant resins. When PP is added, the scratch resistance and wear resistance is reduced, as in TPO and TPS. Therefore, heat resistance is improved by the addition of PPE (polyphenylene ether) resin (Patent Document 4) and the addition of TPEE (Polyester soft resin) (Patent Document 5).
  • PPE polyphenylene ether
  • TPEE Polyyester soft resin
  • Patent Documents 6 to 8 describe electron beam cross-linked bodies of ethylene-styrene copolymers.
  • Patent Document 9 describes that the electron beam crosslinkability is improved by copolymerizing an alkyl-substituted styrene with the same cross-copolymer as in the present application.
  • the following documents are each incorporated herein by reference. No. 00/037517 WO2007139116 JP 2009-102515 A WO2009-128444 Japanese Patent Application No. 2009-094556 Japanese Patent Publication No. 3-60123 JP-A-8-73668 WO99-10395 Japanese Unexamined Patent Publication No. 2011-74187
  • the electron beam cross-linked body of the cross copolymer particularly the tape base material, the wire coating material, and the foaming agent are described in Patent Documents 1, 2, and 3.
  • the skin material sheet must be decorated with a texture, etc., followed by a step of attaching to the base material and, if necessary, a foamed sheet. In this case, the skin is heated and the texture disappears or fades. Alternatively, improvement has been desired in terms of glossiness.
  • the texture retention the conditions for appropriate electron beam irradiation have not been known.
  • An object of the present invention is to provide a skin sheet having excellent energy ray cross-linking properties and excellent softness, mechanical properties, heat resistance, and texture retention. That is, according to the present invention, there is provided a sheet obtained by crosslinking a thermoplastic resin composition by energy ray irradiation.
  • seat is used suitably as a sheet
  • the thermoplastic resin composition comprises, as a resin component, 20 to 90 parts by mass of the cross copolymer A and 80 to 10 parts by mass of the ethylene copolymer B, for a total of 100 parts by mass.
  • the cross-copolymer A is obtained by a production method including a polymerization step comprising a coordination polymerization step and a subsequent cross-linking step.
  • the ethylene copolymer B is an ethylene-olefin copolymer and / or an ethylene-unsaturated carboxylic acid or ester copolymer thereof.
  • the coordination polymerization step is a process of copolymerizing an olefin monomer, an aromatic vinyl compound monomer, and an aromatic polyene by using a single site coordination polymerization catalyst.
  • a process for synthesizing an aromatic polyene copolymer, and the cross-linking process is an anionic polymerization initiator or radical in which an olefin-aromatic vinyl compound-aromatic polyene copolymer and an aromatic vinyl compound monomer coexist This is a step of polymerizing using a polymerization initiator.
  • the composition of the olefin-aromatic vinyl compound-aromatic polyene copolymer obtained in the coordination polymerization step is preferably an aromatic vinyl compound content of 5 mol% to 30 mol%, and an aromatic polyene content of 0.01 mol. % To 0.3 mol%, the balance being the olefin content.
  • the mass ratio of the olefin-aromatic vinyl compound-aromatic polyene copolymer obtained in the coordination polymerization step to the cross copolymer obtained in the cross-linking step is preferably 50 to 99% by mass.
  • thermoplastic resin composition is excellent in energy beam cross-linking properties.
  • a sheet obtained by crosslinking the thermoplastic resin composition by irradiation with energy rays is excellent in softness, mechanical properties, heat resistance, and grain retention.
  • the “single site coordination polymerization catalyst” in the present specification is a polymerization catalyst composed of a transition metal compound and a promoter. This includes, for example, a metallocene catalyst, a half metallocene catalyst, a soluble Ziegler-Natta catalyst, or an FI (pheniximine) catalyst.
  • substitution in the present specification means a substituent that is generally used for each compound within a range not impairing the effects of the present invention, and is not limited thereto. Substitution with a hydrocarbon group having 1 to 3 carbon atoms is included.
  • the “storage elastic modulus (E ′)” in the present specification is a storage elastic modulus that can be measured by a dynamic viscoelasticity measuring device at 1 Hz and a temperature increase rate of 4 ° C./min.
  • the target component mentioned is 70% by mass or more, preferably 80% by mass or more, more preferably 90% by mass of the total mass. % Or more, more preferably 95% by mass or more, still more preferably 98% by mass or more, or 99% by mass or more or 100%.
  • each numerical range in this specification includes the upper limit value and the lower limit value indicated by “to” and “from”, respectively.
  • the descriptions “A to B” and “A to B” mean that they are A or more and B or less.
  • thermoplastic resin composition comprising 100 parts by mass in total of 20 to 90 parts by mass of the cross-copolymer A and 80 to 10 parts by mass of the ethylene copolymer B is irradiated with energy rays.
  • a sheet for a skin material formed by crosslinking with (1) The cross copolymer A is (I) An arrangement for synthesizing an olefin-aromatic vinyl compound-aromatic polyene copolymer by copolymerizing an olefin monomer, an aromatic vinyl compound monomer and an aromatic polyene using a single site coordination polymerization catalyst.
  • the mass ratio of the olefin-aromatic vinyl compound-aromatic polyene copolymer obtained in the coordination polymerization step to the cross copolymer obtained in the cross-linking step is 50 to 99% by mass;
  • the ethylene-based copolymer B is a sheet for a skin material, characterized by being an ethylene-olefin copolymer and / or a copolymer of ethylene-unsaturated carboxylic acid or ester thereof.
  • the sheet is excellent in energy beam cross-linking properties, softness, mechanical properties, heat resistance, and texture retention. In addition, it has excellent scratch resistance and abrasion resistance.
  • the main chain olefin-aromatic vinyl compound-aromatic polyene copolymer has a polymer chain composed of a cross-chain aromatic vinyl compound monomer as a main chain. It is thought that the structure (cross-copolymerization structure or Segregated star copolymer structure) couple
  • the MFR value of the cross copolymer A of the present invention measured at 200 ° C. and a load of 98 N is not particularly limited, but is generally 0.01 g / 10 min or more and 300 g / 10 min or less.
  • the olefin used in the coordination polymerization step is not limited to this, and examples thereof include ethylene and ⁇ -olefins having 3 to 20 carbon atoms, and these are used alone or in combination of two or more. be able to.
  • Examples of the ⁇ -olefin having 3 to 20 carbon atoms include chain olefins such as propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and vinylcyclohexane, and cyclopentene and norbornene. Of cyclic olefins.
  • ethylene or a mixture of ethylene and ⁇ -olefin is preferably used, and ethylene is more preferably used.
  • the aromatic vinyl compound monomer used in the coordination polymerization step is not limited to this, but examples thereof include styrene and substituted styrene, and these can be used alone or in combination of two or more.
  • substituted styrene include p-methylstyrene, m-methylstyrene, o-methylstyrene, ot-butylstyrene, mt-butylstyrene, pt-butylstyrene, p-chlorostyrene, o- Chlorostyrene and the like are included.
  • styrene is preferably used alone industrially.
  • the aromatic polyene used in the coordination polymerization step is not limited to this.
  • the aromatic polyene has 10 to 30 carbon atoms, and has a plurality of double bonds (vinyl group) and one or more carbon atoms.
  • any one or a mixture of two or more of orthodivinylbenzene, paradivinylbenzene and metadivinylbenzene can be suitably used.
  • the composition of the olefin-aromatic vinyl compound-aromatic polyene copolymer obtained in the above coordination polymerization step has an aromatic vinyl compound content of 5 mol% to 30 mol% and an aromatic polyene content of 0.01 mol% to 0 mol%.
  • a cross copolymer having high softness for example, A hardness of 95 or less, etc.
  • the aromatic vinyl compound content is lower than 5 mol%, the softness may be lost due to ethylene crystallinity, and if it is higher than 30 mol%, the present olefin-aromatic vinyl compound-aromatic polyene copolymer may be lost. Glass transition temperature becomes higher than 0 degreeC, and the softness
  • the composition of the above olefin-aromatic vinyl compound-aromatic polyene copolymer can be achieved by a known general control method, but can be most easily achieved by changing the monomer charge composition ratio.
  • the composition of the olefin-aromatic vinyl compound-aromatic polyene copolymer is an aromatic vinyl compound content of 5 mol% or more, a crystal structure derived from an olefin chain structure, for example, a crystal structure based on an ethylene chain or a propylene chain It can be reduced, the softness of the resin composition of the present invention finally obtained can be enhanced, shrinkage due to crystallization during molding can be prevented, and the dimensional stability of the molded body can be more reliably maintained. If the content of the aromatic vinyl compound is 10 mol% or more, the effect can be obtained more reliably, and therefore, it is more preferable.
  • the cross copolymer A according to the present invention has a total crystal melting heat including the olefin crystallinity and other crystallinity of preferably 100 J / g or less, and more preferably 50 J / g or less.
  • the total heat of melting of the crystal can be determined from the total peak area derived from the melting point observed in the range of 50 ° C. to approximately 200 ° C. by DSC.
  • composition of the olefin-aromatic vinyl compound-aromatic polyene copolymer has an aromatic vinyl compound content of 30 mol% or less, excellent energy beam crosslinking characteristics are exhibited.
  • the aromatic vinyl compound content is preferably 25 mol% or less, and the effect can be more reliably exhibited.
  • the aromatic polyene content of the olefin-aromatic vinyl compound-aromatic polyene copolymer obtained in the above coordination polymerization step is 0.01 mol% or more and 0.3 mol% or less, preferably 0.01 mol% or more. It is 0.1 mol% or less. If the aromatic polyene content is not less than the above lower limit, the properties as the cross-copolymer A of the present invention can be more reliably exhibited. If the aromatic polyene content is not more than the above upper limit, the moldability is improved. Can keep.
  • the weight ratio of the olefin-aromatic vinyl compound-aromatic polyene copolymer obtained in the coordination polymerization step is 50% by mass to 99% by mass of the weight of the cross-copolymer A.
  • the following is preferable. If the mass ratio (mass%) of the olefin-aromatic vinyl compound-aromatic polyene copolymer obtained in the above coordination polymerization process to the cross copolymer A is 50 mass% or more, the softness is increased and the electrons are increased. The wire crosslinkability is improved and the texture is excellent.
  • This ratio is preferably 90% by mass or less, and in this case, heat resistance after electron beam crosslinking can be exhibited, and for example, the creep start temperature can be 150 ° C. or higher.
  • the above ratio is more preferably 60% by mass or more and 90% by mass or less.
  • a cross copolymer having particularly excellent softness is obtained, and the resin composition is excellent in softness (for example, A hardness 95 or less). You can get things.
  • the above ratio is calculated by measuring the amount of main chain polymer obtained by sampling and analyzing a part of the polymerization solution at the end of coordination polymerization, and the cross-copolymerization obtained by sampling and analyzing a part of the polymerization solution after anionic polymerization. It can be determined from the combined mass.
  • the ratio can be obtained by comparing the composition of the main chain olefin-aromatic vinyl compound-aromatic polyene copolymer with the composition of the obtained cross-copolymer A.
  • the weight average molecular weight of the olefin-aromatic vinyl compound-aromatic polyene copolymer obtained in the coordination polymerization step is preferably 1,000,000 or less and 30,000 or more. However, the moldability of the resin composition of the present invention is improved. In consideration, it is more preferably 30,000 or more and 300,000 or less.
  • the molecular weight distribution (Mw / Mn) of the olefin-aromatic vinyl compound-aromatic polyene copolymer obtained in the coordination polymerization step is preferably 1.5 or more and 8 or less, more preferably 1.5 or more and 6 or less, Most preferably, it is 1.5 or more and 4 or less.
  • the aromatic vinyl compound monomer used in the cross-linking step is not limited to this, but examples thereof include p-methylstyrene, p-tert-butylstyrene, p-chlorostyrene, ⁇ -methylstyrene, vinyl. Naphthalene, vinyl anthracene and the like can be mentioned, and these can be used alone or in combination of two or more.
  • the aromatic vinyl compound monomer used in the crossing step is preferably styrene.
  • the aromatic vinyl compound monomer used in the coordination polymerization step is preferably the same as the aromatic vinyl compound monomer used in the crossing step, and is one of the aromatic vinyl compound monomers used in the crossing step.
  • part or all of the monomer is an unreacted aromatic vinyl compound monomer in the coordination polymerization step.
  • the aromatic vinyl compound monomer used in the coordination polymerization step is styrene
  • the aromatic vinyl compound monomer used in the cross-linking step is styrene, part or all of which is the coordination polymerization step. In the unreacted styrene.
  • a monomer capable of anionic polymerization or radical polymerization may be added in addition to the aromatic vinyl compound monomer.
  • the amount added is preferably up to an equimolar amount with respect to the amount of the aromatic vinyl compound monomer used.
  • aromatic polyene that is not polymerized in the coordination polymerization step and remains in a small amount in the polymerization solution may also be polymerized.
  • the length (molecular weight) of the cross chain portion of the cross-copolymer A can be estimated from the molecular weight of the homopolymer that has not been cross-linked, and the length is preferably 5000 or more and 15 as the weight average molecular weight. It is 10,000 or less, more preferably 5000 or more and 100,000 or less, particularly preferably 5000 or more and 70,000 or less.
  • the molecular weight distribution (Mw / Mn) is preferably 5 or less, more preferably 3 or less, and particularly preferably 2 or less.
  • ethylene-olefin copolymer that is, a copolymer of ethylene and one or more olefins is preferably used.
  • olefins include, but are not limited to, aliphatic or alicyclic ⁇ -olefins having 3 to 20 carbon atoms, or cyclic olefins.
  • Aliphatic ⁇ -olefins include, for example, propylene, 1-butene, 1-hexene, 1-octene, alicyclic ⁇ -olefins include, for example, vinylcyclohexane, and cyclic olefins include, for example, norbornene. It is.
  • the specific gravity of the ethylene copolymer is preferably 0.91 or less and 0.84 or more.
  • the ethylene content in the ethylene and olefin copolymer satisfying such a range is generally in the range of 60 to 90% by mass.
  • the MFR of the ethylene copolymer measured at 200 ° C. and 98 N is not particularly limited, but is preferably in the range of 0.2 to 30 g / 10 min. When the MFR is 0.2 g / 10 min or more, better moldability can be maintained. When the MFR is 30 g / 10 min or less, the energy beam cross-linking property is high, and the wrinkle flow and wrinkle disappearance during the molding process. The possibility can be further reduced.
  • a copolymer of ethylene-unsaturated carboxylic acid or ester thereof that is, a copolymer of ethylene and one or more unsaturated carboxylic acids or esters thereof can also be used.
  • unsaturated carboxylic acids or esters thereof include acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, isopropyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, A glycidyl methacrylate etc. can be illustrated.
  • the preferable ethylene content in the copolymer of ethylene and unsaturated carboxylic acid or ester thereof is generally in the range of 60 to 90% by mass. If the ethylene content is 90% by mass or less, the softness and scratch resistance of the finally obtained resin composition sheet can be kept better. Moreover, if the ethylene content is 60% by mass or more, the mechanical properties of the finally obtained resin composition can be kept better.
  • the ethylene copolymer B is one or more copolymers of ethylene and olefins, or one or more copolymers of ethylene and unsaturated carboxylic acids or esters thereof. These ethylene and olefins are used. A copolymer of ethylene and an unsaturated carboxylic acid or ester thereof may be used in combination.
  • any single-site coordination catalyst can be used as long as the effects of the present invention are not impaired.
  • the following general formula (1) or (2) The transition metal compound represented by these is used.
  • a and B may be the same or different, and are derived from an unsubstituted or substituted benzoindenyl group, an unsubstituted or substituted cyclopentadienyl group, an unsubstituted or substituted indenyl group, or an unsubstituted or substituted fluorenyl group.
  • a and B are selected from an unsubstituted or substituted benzoindenyl group and an unsubstituted or substituted indenyl group.
  • Y has a bond with A and B, and additionally has hydrogen or a hydrocarbon group having 1 to 15 carbon atoms (may contain 1 to 3 nitrogen, oxygen, sulfur, phosphorus, or silicon atoms) as a substituent. It has a methylene group. The substituents may be different or the same.
  • Y may have a cyclic structure.
  • X represents hydrogen, a hydroxyl group, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon substituent having 1 to 4 carbon atoms, or a group having 1 to 20 carbon atoms. It is an amide group having a hydrocarbon substituent. When X is plural, Xs may have a bond.
  • M is zirconium, hafnium, or titanium.
  • n is an integer of 1 or 2.
  • transition metal compound examples include substituted methylene bridge structures specifically exemplified in EP-0874922A2, JP-A-11-130808, and JP-A-9-309925, each of which is incorporated herein by reference. And transition metal compounds having a boron crosslinking structure specifically exemplified in WO 01/068719, which is incorporated herein by reference.
  • Cp is an unsubstituted or substituted cyclopentaphenanthryl group, an unsubstituted or substituted benzoindenyl group, an unsubstituted or substituted cyclopentadienyl group, an unsubstituted or substituted indenyl group, or an unsubstituted or substituted fluorenyl group. Chosen from.
  • Y ′ has a bond with Cp and Z, and as a substituent, hydrogen or a hydrocarbon group having 1 to 15 carbon atoms (may contain 1 to 3 nitrogen, oxygen, sulfur, phosphorus, or silicon atoms) And a methylene group, a silylene group, an ethylene group, a germylene group, or a boron residue.
  • the substituents may be different or the same.
  • Y ′ may have a cyclic structure.
  • Z is a ligand containing nitrogen, oxygen or sulfur, coordinated to M ′ with nitrogen, oxygen or sulfur, having a bond with Y ′, and having hydrogen or a carbon number of 1 to 15 as a substituent.
  • X ′ is hydrogen, halogen, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 8 to 12 carbon atoms, or a silyl group having a hydrocarbon substituent having 1 to 4 carbon atoms.
  • M ′ is zirconium, hafnium, or titanium. n is an integer of 1 or 2.
  • a polymerization catalyst comprising a single site coordination polymerization catalyst and a co-catalyst, particularly preferably a single site coordination polymerization catalyst represented by the above general formula (1)
  • a polymerization catalyst composed of a cocatalyst is used.
  • co-catalyst used in the present coordination polymerization step a known co-catalyst conventionally used in combination with a transition metal compound can be used as long as the object of the present invention is not impaired.
  • aluminoxane include, but are not limited to, alumoxane or boron compounds such as methylaluminoxane (or methylalumoxane or MAO) and the like are preferably used.
  • alumoxane or boron compounds such as methylaluminoxane (or methylalumoxane or MAO) and the like are preferably used.
  • cocatalyst used EP-087492A2 publication, JP-A-11-130808, JP-A-9-309925, WO00 / 20426, EP0985689A2 each incorporated herein by reference.
  • Examples thereof include promoters and alkylaluminum compounds described in JP-A-6-184179.
  • the transition metal compound and the cocatalyst may be mixed and prepared outside the polymerization equipment, or may be mixed inside the equipment at the time of polymerization.
  • alumoxane or the like When alumoxane or the like is used as a cocatalyst, it is used at a ratio of aluminum atom / transition metal atom ratio of 0.1 to 100,000, preferably 10 to 10,000, relative to the metal of the transition metal compound. If this ratio is larger than 0.1, the transition metal compound can be activated more effectively, and if it is 100,000 or less, it is economically advantageous.
  • a boron compound is used as the cocatalyst, it is used in a boron atom / transition metal atom ratio of 0.01 to 100, preferably 0.1 to 10, particularly preferably 1. If this ratio is larger than 0.01, the transition metal compound can be activated more effectively, and if it is 100 or less, it is economically advantageous.
  • the above-mentioned various monomers and catalyst are brought into contact with each other.
  • a copolymerization method a method of polymerizing in a liquid monomer without using a solvent, or pentane, hexane, heptane, cyclohexane, benzene, toluene, ethylbenzene, xylene, chloro-substituted benzene, chloro-substituted toluene, methylene chloride, chloroform, etc.
  • a method using a saturated aliphatic or aromatic hydrocarbon or halogenated hydrocarbon alone or in a mixed solvent can be used.
  • a mixed alkane solvent, cyclohexane, toluene, or ethylbenzene is used as the solvent.
  • the polymerization form may be either solution polymerization or slurry polymerization.
  • well-known methods, such as batch polymerization, continuous polymerization, prepolymerization, and multistage polymerization can be used as needed. It is also possible to use a single tank or a plurality of connected tank polymerization cans, or a single linear or loop, or a plurality of connected pipe polymerization equipment.
  • Pipe-shaped polymerization cans are a variety of well-known cooling devices such as dynamic or static mixers and various known mixers such as static mixers that also remove heat, and coolers equipped with thin tubes for heat removal. You may have a vessel. Moreover, you may have a batch type prepolymerization can. Furthermore, methods such as gas phase polymerization can also be used.
  • the polymerization temperature is preferably -78 ° C to 200 ° C. If the polymerization temperature is ⁇ 78 ° C. or higher, it is industrially advantageous, and if it is 200 ° C. or lower, decomposition of the transition metal compound can be suppressed.
  • the polymerization temperature is more preferably industrially preferably 0 ° C. to 160 ° C., particularly preferably 30 ° C. to 160 ° C.
  • the pressure at the time of polymerization is preferably 0.1 to 100 atm, more preferably 1 to 30 atm, and particularly industrially particularly preferably 1 to 10 atm.
  • the transition metal compound of the single site coordination polymerization catalyst used in this production method has a structure represented by the general formula (1), and A and B are unsubstituted or substituted benzoindenyl groups, unsubstituted or substituted indenyl groups.
  • Y has a bond with A and B, and as a substituent hydrogen or a hydrocarbon group having 1 to 15 carbon atoms (1 to 3 nitrogen, oxygen, sulfur, phosphorus, silicon atoms)
  • the transition metal compound is a racemate
  • the olefin-aromatic vinyl compound-aromatic polyene copolymer obtained by this production method is an olefin-
  • the alternating structure of the aromatic vinyl compound, preferably the alternating structure of the ethylene-aromatic vinyl compound has isotactic stereoregularity, and therefore the cross-copolymer of the present invention has the present alternating structure. It can have a microcrystalline derived from.
  • the present olefin-aromatic vinyl compound-aromatic polyene copolymer has better mechanical properties and oil resistance based on the microcrystallinity of the alternating structure as compared with the case where there is no stereoregularity.
  • Features can ultimately be inherited by the cross-copolymers of the present invention.
  • the crystalline melting point due to the microcrystalline nature of the alternating structure of olefin-aromatic vinyl compound-aromatic polyene copolymer is generally in the range of 50 ° C. to 120 ° C., and the heat of crystal melting by DSC is generally 1-30 J / g or less. Therefore, the cross copolymer A of the present invention as a whole can preferably have a heat of crystal fusion of 50 J / g or less, more preferably 30 J / g or less.
  • the crystallinity of the heat of crystal melting within this range does not adversely affect the softness and molding processability of the present cross copolymer A, but rather is advantageous in terms of excellent mechanical properties.
  • ⁇ Cross process> In the cross-linking step of the production method of the present invention, the olefin-aromatic vinyl compound-aromatic polyene copolymer obtained in the coordination polymerization step and the aromatic vinyl compound monomer are allowed to coexist and an anionic polymerization initiator or radical polymerization is performed. Anionic polymerization or radical polymerization is performed using an initiator.
  • anionic polymerization initiator When anionic polymerization is employed in the crossing step, a known anionic polymerization initiator can be used.
  • alkyl lithium compounds, lithium salts such as biphenyl, naphthalene, and pyrene or sodium salts, particularly preferably sec-butyl lithium and n (normal) -butyl lithium are used.
  • the solvent is not limited to this, but a mixed alkane solvent that does not cause inconvenience such as chain transfer or a solvent such as cyclohexane or benzene is particularly preferable. If the polymerization temperature is 150 ° C. or lower, toluene, ethylbenzene, etc. Other solvents can also be suitably used.
  • radical polymerization When radical polymerization is employed in the crossing step, a known radical polymerization initiator that can be used for polymerization or copolymerization of an aromatic vinyl compound can be used.
  • a peroxide (peroxide), an azo polymerization initiator and the like can be freely selected by those skilled in the art as needed.
  • Such examples are described in the Japanese fat catalog organic peroxides 10th edition (http://www.nof.co.jp/business/chemical/pdf/product01/Catalog_all.), Each of which is incorporated herein by reference. It can be downloaded from pdf), Wako Pure Chemicals catalog, etc., and can be obtained from these companies.
  • the amount of the polymerization initiator used is not particularly limited, but 0.001 to 5 parts by mass is preferably used with respect to 100 parts by mass of the monomer.
  • an initiator such as a peroxide (peroxide) or an azo polymerization initiator or a curing agent
  • the curing treatment is performed at an appropriate temperature and time in consideration of its half-life.
  • the conditions in this case are arbitrary according to the initiator and the curing agent, but generally a temperature range of about 50 ° C. to 150 ° C. is preferable.
  • a known chain transfer agent can be used mainly for the purpose of controlling the molecular weight of the cross chain.
  • chain transfer agents include, but are not limited to, mercaptan derivatives such as t-dodecyl mercaptan, ⁇ -styrene dimer, and the like.
  • the solvent is particularly preferably an alkane solvent or a solvent such as cyclohexane or benzene, but other solvents such as toluene or ethylbenzene can also be used.
  • the crossing step of the present invention is performed after the coordination polymerization step.
  • the copolymer obtained in the coordination polymerization step is subjected to any polymer recovery method such as a crumb forming method, a steam stripping method, a devolatilization tank, a direct desolvation method using a devolatilization extruder, etc. Then, it may be separated and purified from the polymerization solution and used in the crossing step.
  • the polymer solution containing the polymer can be used in the cloth forming step without separating the polymer from the polymerization solution.
  • the polymerization temperature is preferably -78 ° C to 200 ° C. If the polymerization temperature is ⁇ 78 ° C. or higher, it is industrially advantageous, and if it is 200 ° C. or lower, chain transfer and the like can be suppressed.
  • the polymerization temperature is particularly preferably 30 ° C. to 150 ° C.
  • the pressure at the time of polymerization is preferably 0.1 to 100 atm, more preferably 1 to 30 atm, and particularly industrially particularly preferably 1 to 10 atm.
  • thermoplastic resin composition of the present invention in addition to the above-mentioned cross copolymer A and ethylene-based copolymer B, additions that are used for ordinary resins as necessary within the range not impairing the object of the present invention Agents, for example, plasticizers, inorganic fillers (fillers), flame retardants, weathering agents, heat stabilizers, antioxidants, antistatic agents, light-resistant agents, UV absorbers, anti-aging agents, fillers, colorants Further, a lubricant, an antifogging agent, a foaming agent, a flame retardant aid and the like may be added. Some of these are exemplified below.
  • the resulting energy beam cross-linked product of the thermoplastic resin composition is It is relatively soft and has the characteristics of excellent abrasion resistance and heat resistance.
  • the amount of each additive is within the range when described below, and within the range of 0 to 5 parts by mass with respect to 100 parts by mass of the thermoplastic resin composition unless otherwise specified. It is preferable to be used.
  • thermoplastic resin composition of the present invention can be blended with any known plasticizer conventionally used for vinyl chloride and other resins.
  • Suitable plasticizers are, for example, hydrocarbon plasticizers or oxygen-containing or nitrogen-containing plasticizers.
  • hydrocarbon plasticizers include aliphatic hydrocarbon plasticizers, aromatic hydrocarbon plasticizers and naphthenic plasticizers.
  • oxygen-containing or nitrogen-containing plasticizers include ester-based plasticizers. Examples thereof include an agent, an epoxy plasticizer, an ether plasticizer, and an amide plasticizer.
  • These plasticizers can be used to adjust the hardness or fluidity (molding processability) of the thermoplastic resin composition of the present invention. Moreover, these plasticizers have the effect of lowering the glass transition temperature and lowering the embrittlement temperature.
  • ester plasticizers that can be suitably used in the present invention include, but are not limited to, phthalic acid esters, trimellitic acid esters, adipic acid esters, sebacic acid esters, and azelate esters. , Citric acid esters, acetyl citrate esters, glutamic acid esters, succinic acid esters, acetic acid esters and other mono fatty acid esters, phosphoric acid esters and polyesters thereof.
  • the epoxy plasticizer that can be suitably used in the present invention include, but are not limited to, epoxidized soybean oil and epoxidized linseed oil.
  • ether plasticizers that can be suitably used in the present invention include, but are not limited to, polyethylene glycol, polypropylene glycol, copolymers thereof, and mixtures thereof.
  • amide plasticizer that can be suitably used in the present invention include, but are not limited to, sulfonic acid amides. These plasticizers may be used alone or in combination.
  • ester plasticizer is particularly preferably used in the present invention.
  • Ester plasticizers have the advantages of excellent compatibility with the cross-copolymer, excellent plasticizing effect (high degree of glass transition temperature reduction), and low bleeding.
  • the compounding amount of the plasticizer is 1 to 25 parts by mass, preferably 1 to 15 parts by mass with respect to 100 parts by mass of the thermoplastic resin composition of the present invention. If it is added in an amount of 1 part by mass or more, the effect as a plasticizer can be expected more reliably. If it is 25 parts by mass or less, it suppresses bleeding, excessive softening, and excessive stickiness. can do.
  • the inorganic filler is also used for imparting flame retardancy to the thermoplastic resin composition of the present invention.
  • the volume average particle diameter of the inorganic filler is preferably 50 ⁇ m or less, preferably 10 ⁇ m or less, and preferably 0.5 ⁇ m or more. If the volume average particle diameter is 0.5 ⁇ m or more and 50 ⁇ m or less, it is possible to suppress a decrease in mechanical properties (tensile strength, elongation at break, etc.), a decrease in flexibility and the occurrence of pinholes when formed into a film. it can.
  • the volume average particle diameter is a volume average particle diameter measured by a laser diffraction method.
  • inorganic fillers include, but are not limited to, aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, calcium hydroxide, potassium hydroxide, barium hydroxide, triphenyl phosphate, ammonium polyphosphate.
  • Polyphosphate amide zirconium oxide, magnesium oxide, zinc oxide, titanium oxide, molybdenum oxide, guanidine phosphate, hydrotalcite, snakerite, zinc borate, anhydrous zinc borate, zinc metaborate, barium metaborate, antimony oxide, three Antimony oxide, antimony pentoxide, red phosphorus, talc, alumina, silica, boehmite, bentonite, sodium silicate, calcium silicate, calcium sulfate, calcium carbonate, magnesium carbonate, and one or more compounds selected from these The It is possible to use.
  • the use of at least one selected from the group consisting of aluminum hydroxide, magnesium hydroxide, hydrotalcite, and magnesium carbonate is excellent in flame retardancy and is economically advantageous.
  • the blending amount of the inorganic filler is preferably 1 to 1000 parts by mass, more preferably 5 to 200 parts by mass with respect to 100 parts by mass of the thermoplastic resin composition of the present invention. If the inorganic filler is 1 part by mass or more, the effect is exhibited in terms of imparting flame retardancy. On the other hand, if the inorganic filler is 1000 parts by mass or less, mechanical properties such as moldability and strength of the thermoplastic resin composition can be maintained. When an inorganic filler is blended as a non-halogen flame retardant, char (carbonized layer) can be formed and the flame retardancy of a film or the like can be improved.
  • the flame retardant that can be used in the present invention will be described.
  • the organic flame retardant include, but are not limited to, bromine compounds such as pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tetrabromobisphenol A, hexabromocyclododecane, and aromatics such as triphenyl phosphate.
  • Illustrative examples include phosphorus compounds such as phosphoric acid group, red phosphorus and halogen-containing phosphate esters, nitrogen-containing compounds such as 1,3,5-triazine derivatives, and halogen-containing compounds such as chlorinated paraffin and brominated paraffin.
  • the inorganic flame retardant include metal hydroxides such as antimony compounds, aluminum hydroxide, and magnesium hydroxide, which are also the above inorganic fillers. These flame retardants can be used in an appropriate amount depending on the application. These may be used together with a known appropriate flame retardant aid. Examples of flame retardants are also described in, for example, JP-A No. 11-199724 and JP-T-2002-533478, each of which is incorporated herein by reference.
  • the light-proofing agent used in the present invention is a known light-proofing agent.
  • the light-resistant agent is composed of an ultraviolet absorber that converts light energy into harmless heat energy and a hindered amine light stabilizer that traps radicals generated by photooxidation.
  • the mass ratio of the ultraviolet absorber to the hindered amine light stabilizer is preferably in the range of 0: 100 to 100: 1.
  • the total mass of the ultraviolet absorber and the hindered amine light stabilizer is defined as the light-proofing agent mass. Generally, it is preferably in the range of 0.05 to 5 parts by mass with respect to 100 parts by mass of the thermoplastic resin composition of the present invention.
  • the thermoplastic resin composition of the present invention contains 0 to 30 parts by mass of a PPE (polyphenylene ether) resin as necessary with respect to 100 parts by mass of the thermoplastic resin composition comprising the above-described components. It can be added in a range. By adding in this range, it can be passed on while suppressing the softness of the thermoplastic resin composition from being impaired. By adding a PPE-based resin, it is possible to adjust the hardness and further improve the abrasion resistance with scratches.
  • the PPE resin used is described in WO2009-128444, which is incorporated herein by reference.
  • the method for mixing the cross copolymer, ethylene copolymer, and additive of the present invention is not particularly limited, and a known appropriate blend method can be used.
  • melt mixing can be performed with a single-screw or twin-screw extruder, a Banbury mixer, a plast mill, a kneader, a heating roll, or the like.
  • the raw materials Prior to melt mixing, the raw materials may be mixed uniformly with a Henschel mixer, ribbon blender, super mixer, tumbler, or the like.
  • the melt mixing temperature is not particularly limited, but is preferably 150 to 300 ° C, more preferably 200 to 250 ° C.
  • thermoplastic resin composition of the present invention can be crosslinked using various energy rays.
  • the energy vinyl crosslinkability is improved when the aromatic vinyl compound content is 30 mol% or less, particularly 25 mol% or less, even at a low dose.
  • a sufficient degree of crosslinking gel content, heat resistance
  • This feature is extremely useful because it means that the productivity of the crosslinked sheet is high from an industrial viewpoint.
  • Cross-linking using energy rays is advantageous in that it can be cross-linked after molding.
  • the energy rays used here include particle rays, electromagnetic waves, and combinations thereof.
  • the particle beam include electron beams (EB) and ⁇ rays
  • the electromagnetic waves include ultraviolet rays (UV), visible rays, infrared rays, ⁇ rays, and X rays.
  • UV ultraviolet rays
  • EB electron beam
  • the acceleration voltage is generally 0.1 to 10 MeV, and the irradiation dose is preferably 10 to 500 kGy.
  • This acceleration voltage is appropriately controlled according to the thickness of the sheet.
  • the acceleration voltage is generally increased.
  • An acceleration voltage of about 500 kV or more is preferably used at 250 kV or more, a sheet thickness of 0.5 mm, and a sheet thickness of 1.0 mm is preferably about 1000 kV or more. Electron beams may be irradiated from both sides of the sheet. For example, at a sheet thickness of 0.5 mm, irradiation from both sides with an acceleration voltage of 250 kV or more enables more reliable crosslinking to the sheet center. In particular, it is preferable to perform crosslinking without using a photopolymerization initiator and a crosslinking aid shown below in view of cost and consideration of these remaining drugs.
  • cross-copolymer of the present invention it is possible to perform crosslinking at a low irradiation dose, and productivity is improved.
  • the entire surface including the back surface of the sheet is to be cross-linked by one irradiation from the front surface, preferably 40 kGy or more, 200 kGy or less, more preferably 50 kGy or more, under the conditions satisfying the above acceleration voltage
  • Crosslinking can be performed at a low irradiation dose of 150 kGy or less, particularly preferably 50 kGy or more and 100 kGy or less.
  • UV ultraviolet rays
  • a lamp having a radiation wavelength of 200 nm to 450 nm can be suitably used as the radiation source.
  • a photopolymerization initiator can be further blended in the cross-copolymer of the present invention and its thermoplastic resin composition as required, particularly when ultraviolet rays (UV) are used as energy rays.
  • Usable photopolymerization initiators include, for example, benzophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, ⁇ -methylol benzoin, ⁇ -methylol benzoin methyl ether, ⁇ -methoxybenzoin methyl ether, benzoin phenyl ether, ⁇ Examples thereof include, but are not limited to, tert-butylbenzoin. These photopolymerization initiators may be used alone or in combination of two or more. When the photopolymerization initiator is blended, the content is preferably in the range of 0.01 to 5% by mass with respect to the total mass of the copolymer or resin component.
  • crosslinking aids that can be used include, but are not limited to, triallyl isocyanurate, triallyl cyanurate, N, N′-phenylenebismaleimide, ethylene glycol di (meth) acrylate, propanediol di (meta) ) Acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, nonanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and the like. These crosslinking aids may be used alone or in combination of two or more. When the crosslinking aid is blended, the content is not particularly limited, but it is usually preferably in the range of 0.01 to 5% by mass with respect to the total mass.
  • crosslinking at a lower irradiation dose under the above acceleration voltage by blending the photopolymerization initiator or the crosslinking aid.
  • sufficient crosslinking can be performed with an irradiation dose of 10 kGy or more and 100 kGy or less, which is industrially preferable.
  • the energy beam cross-linked product of the resin composition of the present invention can have improved heat resistance while maintaining the softness inherent in the thermoplastic resin composition.
  • the energy beam cross-linked product has a higher gel content than before cross-linking, preferably 25% by mass or more, particularly preferably 30% by mass or more and 70% by mass or less.
  • the gel content is at least the lower limit, the heat resistance can be more effectively exhibited.
  • the gel content is at the upper limit or less, the decrease in the elongation of the crosslinked product can be suppressed and the workability can be maintained.
  • the gel content below the upper limit also maintains suitable recyclability, and for example, after adding a certain amount to the recycled material, the possibility of rough skin can be suppressed.
  • the temperature at which the storage elastic modulus (E ′) is reduced to 3 ⁇ 10 5 Pa in the viscoelastic spectrum measurement measured at 1 Hz and the heating rate of 4 ° C./min is 140 ° C. it can.
  • the creep start temperature specified in the present specification can be 150 ° C. or higher.
  • the crosslinked energy beam of the resin composition of the present invention has softness as a skin material and good mechanical properties.
  • the initial elastic modulus in a tensile test at 23 ° C. is 1 to 50 MPa, and the elongation at break is 200 to 200. 1500% and the strength at break can be in the range of 10-50 MPa.
  • the energy ray cross-linked product (sheet) of the resin composition of the present invention can also exhibit an excellent value for grain retention according to the following measurement method.
  • the gloss of the energy beam crosslinked product (sheet) is measured and evaluated according to JIS K7105 at an angle of 60 ° and a light receiving angle of 60 °
  • the energy beam crosslinked product (sheet) of the present invention is: Even after the heat treatment at 120 ° C. for 120 hours, the gloss is maintained at, for example, an initial value + 5% or less, preferably an initial value + 3% or less.
  • the thermoplastic resin composition of the present invention is basically formed into a sheet by a known method and then subjected to a crosslinking treatment with an energy beam (electron beam) to obtain a sheet for a skin material.
  • the thickness of the skin material sheet is not particularly limited, but is preferably 3 ⁇ m to 3 mm, more preferably 10 ⁇ m to 1 mm.
  • a molding method such as inflation molding, T-die molding, calender molding, roll molding or the like can be employed.
  • the sheet for skin material of the present invention is suitable for other sheet materials such as isotactic or syndiotactic polypropylene, high density polyethylene, low density polyethylene (LDPE or LLDPE).
  • sheet materials such as isotactic or syndiotactic polypropylene, high density polyethylene, low density polyethylene (LDPE or LLDPE).
  • LDPE or LLDPE low density polyethylene
  • Polystyrene, polyethylene terephthalate, ethylene-vinyl acetate copolymer (EVA) and other skin material sheets can be multilayered, and multilayered materials are also included in the sheet and skin material sheet of the present invention.
  • EVA ethylene-vinyl acetate copolymer
  • various protective layers may be formed on the synthetic leather or the textured surface.
  • a surface coating material layer of urethane-based resin, acrylic-based resin, or epoxy-based resin by coating or lamination for further improving appearance such as scratch resistance and imparting durability.
  • a thermosetting resin such as a two-component curable urethane coating agent or an ionizing radiation curable resin such as an electron beam curable resin is used.
  • the ionizing radiation curable resin has a faster curing rate and better productivity than the thermosetting resin.
  • the electron beam curable coating layer is preferable in that it can simultaneously irradiate and crosslink the sheet base material of the present invention below the coating layer.
  • the sheet of the present invention and the sheet for skin material can be subjected to surface treatment such as corona, ozone and plasma, application of an antifogging agent, application of a lubricant, printing and the like, if necessary.
  • seat for skin materials of this invention can be produced as a sheet
  • the sheet of the present invention and the sheet for the skin material are bonded to each other or a material such as another thermoplastic resin by a method such as fusion by a method such as heat, ultrasonic wave, high frequency, adhesion by a solvent or the like, if necessary. can do.
  • seat of this invention is not specifically limited, From the outstanding soft property, dynamic physical property, and heat resistance, it is useful as various skin materials.
  • synthetic leather especially synthetic leather for automobile interiors, building materials, and decorative skin materials for home appliances.
  • the hardness of the final skin material sheet finally obtained is not particularly limited, but the A hardness is preferably in the range of about 60 to 95.
  • automobile interior materials include instrument panels, door trims, sheet skins, ceiling materials, floor skins, handles, brakes, levers, and grips.
  • it can be used suitably also as a floor mat material. In the case of these uses, it may be used as a multilayer with a polyolefin-based or polyurethane-based foamed sheet, or may be used by foaming itself.
  • the analysis of the copolymer obtained in the examples was carried out by the following means.
  • the 13C-NMR spectrum was measured using ⁇ -500 manufactured by JEOL Ltd., using deuterated chloroform solvent or deuterated 1,1,2,2-tetrachloroethane solvent and TMS as a reference.
  • the measurement based on TMS here is the following measurement.
  • the shift value of the center peak of the triplet 13C-NMR peak of deuterated 1,1,2,2-tetrachloroethane was determined based on TMS.
  • the copolymer was dissolved in deuterated 1,1,2,2-tetrachloroethane and 13C-NMR was measured, and each peak shift value was determined as the triplet center peak of deuterated 1,1,2,2-tetrachloroethane.
  • the shift value of the triplet center peak of deuterated 1,1,2,2-tetrachloroethane was 73.89 ppm.
  • the measurement was performed by dissolving 3% by mass / volume of the polymer in these solvents.
  • the 13C-NMR spectrum measurement for quantifying the peak area was performed by a proton gate decoupling method in which NOE was eliminated, with a pulse width of 45 ° and a repetition time of 5 seconds as a standard.
  • Determination of the styrene content in the copolymer was performed by 1H-NMR, and equipment used was ⁇ -500 manufactured by JEOL Ltd. and AC-250 manufactured by BRUCKER. It was dissolved in deuterated 1,1,2,2-tetrachloroethane and the measurement was carried out at 80-100 ° C. The area intensity of the peak derived from the phenyl group proton (6.5 to 7.5 ppm) and the proton peak derived from the alkyl group (0.8 to 3 ppm) was compared based on TMS.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of standard polystyrene were determined using GPC (gel permeation chromatography). The measurement was performed under the following conditions. Column: TSK-GEL Multipore HXL-M ⁇ 7.8 ⁇ 300 mm (manufactured by Tosoh Corporation) was connected in series. Column temperature: 40 ° C Solvent: THF Liquid feed flow rate: 1.0 ml / min.
  • DSC measurement was performed under a nitrogen stream using DSC200 manufactured by Seiko Denshi. That is, using 10 mg of the resin composition, DSC measurement was performed from ⁇ 50 ° C. to 240 ° C. at a temperature rising rate of 10 ° C./min, and the melting point, heat of crystal melting, and glass transition point were determined. After the first measurement, the second measurement performed after quenching with liquid nitrogen was not performed.
  • ⁇ Create sample sheet> As a sample for electron beam irradiation, a sheet having a thickness of 0.25 mm formed by a hot press method (temperature 250 ° C., time 5 minutes, pressure 50 kg / cm 2 ) was used. Samples for various tests such as a tensile test and viscoelastic spectrum measurement were obtained by cutting out from a sheet having a thickness of 0.25 mm obtained under the same conditions.
  • ⁇ Viscoelastic spectrum> A sample for measurement (3 mm ⁇ 40 mm) was cut out from a sheet for skin material having a thickness of about 0.25 mm obtained by the above-mentioned hot pressing method, and a dynamic viscoelasticity measuring device (Rheometrics RSA-III) was used, with a frequency of 1 Hz, The temperature range was ⁇ 50 ° C. to + 250 ° C. Other measurement parameters related to the measurement of the residual elongation ( ⁇ L) of the sample are as follows.
  • ⁇ Creep start temperature> A JIS No. 2 small 1/2 dumbbell is suspended in a specified oven and heated at a specified temperature for 1 hour every 5 ° C in the range from 100 ° C to 170 ° C. Then, the length was measured, and the elongation / shrinkage deformation rate was determined by the following formula. The maximum temperature at which the elongation / shrinkage deformation rate was within ⁇ 2% in the machine direction was defined as the heat resistant deformation temperature (creep start temperature).
  • An embossed sheet having a thickness of about 0.25 mm was prepared by the above-described hot press method using an embossed mold. However, 1 part by mass of a black masterbatch (polyethylene base) was added to each resin used in this test and colored black. The glossiness was measured according to JIS 7105 at an incident angle of 60 ° and a light receiving angle of 60 ° with or without electron beam irradiation under predetermined conditions. After the sheet sample was placed in an oven at 120 ° C.
  • the internal temperature was raised to 80 ° C., ethylene was introduced, and after stabilizing at a pressure of 0.4 MPa (3 kg / cm 2 G), from the catalyst tank installed on the autoclave, rac- About 50 ml of a toluene solution in which 100 ⁇ mol of dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride and 1 mmol of triisobutylaluminum were dissolved was added to the autoclave. Furthermore, ethylene was supplied through a flow control valve, and polymerization was carried out while maintaining the internal temperature at 85 ° C. and the pressure at 0.4 MPa. The polymerization progress was monitored from the ethylene flow rate and integrated flow rate.
  • the ethylene supply was stopped, the pressure was released, and the internal temperature was cooled to 70 ° C. (coordination polymerization step). Thereafter, the polymerization liquid was transferred to a heavy can for anionic polymerization having a capacity of 50 L, a stirrer and a heating / cooling jacket. At the same time, several tens ml of the analytical polymerization solution was collected. 260 mmol of n-butyllithium was introduced from the catalyst tank into the polymerization can for anionic polymerization along with nitrogen gas (crossing step). Anion polymerization started immediately, and the internal temperature rose from 70 ° C to 80 ° C temporarily. The temperature was maintained at 70 ° C.
  • Table 1 shows the polymerization conditions
  • Tables 2 to 3 show the compositional analysis values of the cross copolymers and ethylene-styrene copolymers obtained.
  • Analytical values of the polymer obtained in the coordination polymerization process are measured with a small amount (several tens of ml) of the polymerization solution sampled at the end of the coordination polymerization process. The polymer was precipitated and collected by mixing and analyzed and analyzed.
  • the divinylbenzene unit content of the polymer obtained in the coordination polymerization step was determined from the difference between the amount of unreacted divinylbenzene in the polymerization solution determined by gas chromatography analysis and the amount of divinylbenzene used in the polymerization.
  • the ratio (mass%) of the copolymer obtained in the coordination polymerization step in the table to the cross copolymer is the composition of the ethylene-styrene-divinylbenzene copolymer obtained in the coordination polymerization step ( (Styrene content and ethylene content) and the composition of the cross-copolymer obtained through the anionic polymerization process (styrene content and ethylene content) were determined as the amount of change in each composition was due to the mass of cross-chain polystyrene by anionic polymerization.
  • a cross-copolymer is obtained by sampling and analyzing a part of the main chain polymer production mass obtained by sampling and analyzing a part of the polymerization liquid at the end of coordination polymerization and analyzing the polymerization liquid after anionic polymerization.
  • this ratio was calculated
  • thermoplastic resin composition was obtained as follows. Using a Brabender-Plasticorder (PL2000 model manufactured by Brabender), the cross-copolymers (P1 to P4) obtained in Synthesis Examples 1 to 4 and Engage 8100 (Dow Chemical Co., ethylene-1-octene) Polymer, specific gravity 0.87, MFR 200 ° C., 98 N, 10 g / 10 min), antioxidant Irganox 1076 (manufactured by Ciba Specialty Chemicals): 0.1 part by mass, light resistance LA36 (ultraviolet absorber) 0.2 Part by mass, 0.2 part by mass of LA77Y (hindered amine light stabilizer) (both manufactured by ADEKA Corporation) were added, and kneading was performed at 100 rpm at 180 ° C.
  • PL2000 model manufactured by Brabender the cross-copolymers (P1 to P4) obtained in Synthesis Examples 1 to 4 and Engage 8100 (Dow Chemical Co., ethylene-1-octen
  • Example 5 instead of Engage 8100, EVAFLEX EEA (ethylene-ethyl acrylate copolymer A703) was used.
  • TMPTA trimethylolpropane triacrylate
  • Example 11 polyphenylene ether (PX-100L manufactured by Mitsubishi Engineering Plastics) was added.
  • Comparative Examples 1 to 12 Comparative Examples 1 and 5 are examples in which the electron beam irradiation was not performed on P1 and P2 obtained in this synthesis example, respectively.
  • Comparative Examples 2 and 6 are examples in which 50 kGy electron beam irradiation was performed on P1 and P2 obtained in this synthesis example, respectively.
  • Comparative Examples 3 and 7 are examples in which electron beam irradiation was not performed on the same resin compositions as Examples 1 and 2 and Examples 6 and 7, respectively.
  • Comparative Example 8 is an example in which an ethylene-styrene copolymer was blended with an ethylene-styrene copolymer and engage 8100 was blended, and both were irradiated with an electron beam.
  • the sheet after the electron beam cross-linking of the sheet made of the thermoplastic resin composition of the present invention shown in the examples shows a predetermined gel content, and the temperature at which the storage elastic modulus (E ′) decreases to 3 ⁇ 10 5 Pa is shown. It is 140 ° C. or higher, and the creep start temperature is 150 ° C. or higher, indicating that the heat resistance is greatly improved. Glossiness change is also 3% or less, and has high texture retention. Mechanical properties also satisfy the conditions of the present invention.
  • Table 5 shows the results of the abrasion resistance test.
  • Each sheet of the example did not penetrate through the sheet in the abrasion resistance test, had a relatively small abrasion mass, and the visual / tactile sensation was also “good”.
  • seat which irradiated the electron beam to the Engage 8100 independent goods the sheet

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Abstract

L'invention fournit une composition de résine thermoplastique qui est excellente en termes de caractéristiques de réticulation par rayonnement énergétique (rayonnement électronique), et qui est destinée à une feuille pour matériau excellente en termes de flexibilité, de propriétés mécaniques, de résistance à la chaleur, et de maintien de grainage. Plus précisément, l'invention fournit une composition de résine thermoplastique constituée de manière spécifique. Cette composition se révèle tout à fait excellente en termes de caractéristiques de réticulation par rayonnement énergétique (rayonnement électronique), et permet d'obtenir à échelle industrielle un degré de réticulation suffisant avec une faible quantité de rayonnement utile. En outre, cette feuille réticulée sous des conditions spécifiques, est excellente en termes de flexibilité, de propriétés mécaniques, de résistance à la chaleur, et de maintien de grainage, et est donc adéquate pour servir de feuille de surface large, pièce interne de véhicule incluse.
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WO2020045082A1 (fr) * 2018-08-30 2020-03-05 デンカ株式会社 Composition d'élastomère thermoplastique et son procédé de production
CN113462053A (zh) * 2021-06-22 2021-10-01 上海海优威新材料股份有限公司 挠性聚合物耐磨片材
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JPWO2016136534A1 (ja) * 2015-02-25 2017-11-30 デンカ株式会社 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
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
JPWO2018062514A1 (ja) * 2016-09-30 2019-07-11 積水化学工業株式会社 ポリオレフィン系発泡シート、その製造方法及び粘着テープ
WO2018062514A1 (fr) * 2016-09-30 2018-04-05 積水化学工業株式会社 Feuille de mousse de polyoléfine, son procédé de production et ruban adhésif
JPWO2018117212A1 (ja) * 2016-12-21 2019-10-31 デンカ株式会社 樹脂組成物
EP3560993A4 (fr) * 2016-12-21 2019-10-30 Denka Company Limited Composition de résine
WO2018117212A1 (fr) * 2016-12-21 2018-06-28 デンカ株式会社 Composition de résine
JP7008033B2 (ja) 2016-12-21 2022-01-25 デンカ株式会社 樹脂組成物
WO2020045082A1 (fr) * 2018-08-30 2020-03-05 デンカ株式会社 Composition d'élastomère thermoplastique et son procédé de production
JPWO2020045082A1 (ja) * 2018-08-30 2021-08-26 デンカ株式会社 熱可塑性エラストマー組成物およびその製造方法
JP7348191B2 (ja) 2018-08-30 2023-09-20 デンカ株式会社 熱可塑性エラストマー組成物およびその製造方法
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
CN113462053A (zh) * 2021-06-22 2021-10-01 上海海优威新材料股份有限公司 挠性聚合物耐磨片材
CN113462053B (zh) * 2021-06-22 2024-05-07 上海海优威新材料股份有限公司 挠性聚合物耐磨片材

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