WO2022163796A1 - Composition d'élastomère thermoplastique et son procédé de production, et article moulé - Google Patents

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

Info

Publication number
WO2022163796A1
WO2022163796A1 PCT/JP2022/003230 JP2022003230W WO2022163796A1 WO 2022163796 A1 WO2022163796 A1 WO 2022163796A1 JP 2022003230 W JP2022003230 W JP 2022003230W WO 2022163796 A1 WO2022163796 A1 WO 2022163796A1
Authority
WO
WIPO (PCT)
Prior art keywords
thermoplastic elastomer
elastomer composition
resin
styrene
polyurethane
Prior art date
Application number
PCT/JP2022/003230
Other languages
English (en)
Japanese (ja)
Inventor
圭介 知野
Original Assignee
Ｅｎｅｏｓ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ｅｎｅｏｓ株式会社 filed Critical Ｅｎｅｏｓ株式会社
Publication of WO2022163796A1 publication Critical patent/WO2022163796A1/fr

Links

Classifications

    • 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
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof

Definitions

  • the present invention relates to a thermoplastic elastomer composition and a method for producing the same.
  • the present invention also relates to a molded article using the thermoplastic elastomer composition.
  • thermoplastic elastomer composition is an industrially extremely useful material because it melts at a processing temperature during molding and can be molded by a well-known resin molding method.
  • thermoplastic elastomers have been widely used in various applications such as automobile parts, household appliance parts, medical parts, and daily necessities.
  • thermoplastic elastomer compositions with excellent flexibility and moldability have been proposed so that they can be applied to various uses.
  • a thermoplastic polyurethane elastomer (b) a polymer block (A) mainly composed of a vinyl aromatic compound and a conjugated diene polymer or a vinyl aromatic compound and a conjugated diene A (A)-(B) or (A)-(B)-(A) block copolymer consisting of a random copolymer block (B) with or a vinyl aromatic consisting of a vinyl aromatic compound and a conjugated diene
  • a thermoplastic elastomer composition containing (A)-(B)-(C) block copolymer consisting of tapered blocks (C) in which group compounds gradually increase, and (C) 0 to 98% by weight of a polyolefin polymer.
  • Patent Document 2 (A) polyurethane elastomer: 100 parts by weight; A thermoplastic elastomer composition is proposed containing 10-40 weight percent ⁇ -olefin comonomer having 1 carbon atom and 10-900 weight parts of a metallocene polyolefin copolymerized with ethylene.
  • Patent Document 3 proposes a styrene-based thermoplastic elastomer composition characterized by containing a styrene-based block copolymer (A), polypropylene (B), and a polyurethane-based thermoplastic elastomer (C).
  • thermoplastic elastomer composition there is a trade-off relationship between resistance to compression set and fluidity during melt molding.
  • Patent Documents 1 to 3 a thermoplastic elastomer composition is obtained by kneading polyurethane with another resin such as polyolefin.
  • polyurethane polyurethane
  • an object of the present invention is to provide a thermoplastic elastomer composition that has excellent resistance to compression set and excellent fluidity during melt molding.
  • the inventors of the present invention have made intensive studies to solve the above problems, and found that the content of a specific polyurethane-based resin in a thermoplastic elastomer composition containing a specific polyurethane-based resin and a polyolefin-based thermoplastic resin is adjusted. As a result, the inventors have found that the above problems can be solved, and have completed the present invention.
  • thermoplastic elastomer composition comprising a polyurethane resin and a polyolefin thermoplastic resin
  • the polyurethane resin is a reaction product of a polymer containing two or more hydroxyl groups and/or amino groups and a polyisocyanate containing two or more isocyanate groups, and the number of hydroxyl groups and/or amino groups of the polymer and the polyisocyanate At least one of the number of isocyanate groups of is 3 or more
  • a thermoplastic elastomer composition is provided in which the content of the polyurethane resin is 0.1% by mass or more and 60% by mass or less with respect to the total amount of the thermoplastic elastomer composition.
  • the polyurethane-based resin has a three-dimensional network structure, and the polyolefin-based thermoplastic resin is infiltrated into the three-dimensional network structure of the polyurethane-based resin.
  • thermoplastic elastomer composition further contains a styrenic block copolymer.
  • the styrenic block copolymer is a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a styrene-isoprene-butadiene-styrene block copolymer, a styrene- At least one selected from the group consisting of ethylene-butylene-styrene block copolymers, styrene-ethylene-propylene-styrene block copolymers, and styrene-ethylene-ethylene-propylene-styrene block copolymers. preferable.
  • thermoplastic elastomer composition preferably further contains process oil.
  • the process oil is preferably paraffin oil.
  • the polymer is preferably a hydrocarbon-based polymer.
  • the hydrocarbon-based polymer is preferably polybutadiene and/or hydrogenated products thereof.
  • the polyolefin thermoplastic resin is preferably polyethylene and/or polypropylene.
  • thermoplastic elastomer composition (i) mixing a polymer containing at least two or more hydroxyl groups and/or amino groups with a polyolefin thermoplastic resin to obtain a mixture; (ii) further adding a polyisocyanate containing two or more isocyanate groups to the resulting mixture and allowing it to react to form a polyurethane-based resin; including Provided is a method for producing a thermoplastic elastomer composition, wherein at least one of the number of hydroxyl groups and/or amino groups in the polymer and the number of isocyanate groups in the polyisocyanate is 3 or more.
  • thermoplastic elastomer composition there is provided a molded article using the above thermoplastic elastomer composition.
  • thermoplastic elastomer composition that is excellent in resistance to compression set and fluidity during melt molding. Further, according to the present invention, it is possible to provide a method for producing such a thermoplastic elastomer composition. Furthermore, according to the present invention, it is possible to provide a molded article using such a thermoplastic elastomer composition.
  • thermoplastic elastomer composition contains a specific resin component and may further contain additives.
  • the thermoplastic elastomer composition is excellent in resistance to compression set and fluidity during melt molding, and is therefore suitable for rubber parts for automobiles, machinery, electricity and houses, especially for automobile interiors and house interiors.
  • Each component contained in the thermoplastic elastomer composition will be described in detail below.
  • thermoplastic elastomer composition contains at least a polyurethane resin and a polyolefin thermoplastic resin as resin components, and may further contain a styrene block copolymer. Each resin component will be described in detail below.
  • polyurethane resin Polyurethane-based resins in the present invention are polyurethane, polyurea, and polyurethaneurea.
  • a polyurethane resin is a reaction product of a polymer containing two or more hydroxyl groups and/or amino groups (primary and secondary) and a polyisocyanate containing two or more isocyanate groups, and the hydroxyl groups and/or At least one of the number of amino groups (primary and secondary) and the number of isocyanate groups of the polyisocyanate is 3 or more.
  • Such a polyurethane resin preferably has a three-dimensional network structure.
  • the resulting polyurethane-based resin is three-dimensionally bonded, and other resin components, plasticizers, and the like can be introduced into the three-dimensional network structure of the polyurethane-based resin.
  • the glass transition point of the polyurethane-based resin is preferably 25° C. or lower so that the composition containing the polyurethane-based resin becomes a thermoplastic elastomer.
  • a hydrocarbon polymer containing two or more hydroxyl groups and/or amino groups is preferably used as the polymer containing two or more hydroxyl groups and/or amino groups for synthesis of the polyurethane resin.
  • Hydrocarbon polymers containing two or more hydroxyl groups include polyester polyols, polyether polyols, polycarbonate polyols, polybutadiene polyols and hydrogenated products thereof, acrylic polyols, polymer polyols, and the like. Among these, polybutadiene polyol and hydrogenated products thereof are preferred because of their low polarity.
  • Hydrocarbon polymers containing two or more amino groups include low molecular weight amines such as diethylenetriamine (DETA) and triethylenetetramine (TETA), or aliphatic urea and diethyltoluene diamine (DETDA ), dimethylthiotoluenediamine (DMTDA), or N,N'-di(sec.butyl)-aminobiphenylmethane (DBMDA), polyetheramine, polyoxypropylenediamine, triethyleneglycoldiamine, trimethylolpropane poly(oxypropylene)triamine, glycerylpoly(oxypropylene)triamine, polyethyleneimine and the like.
  • DETA diethylenetriamine
  • TETA triethylenetetramine
  • DETDA diethyltoluene diamine
  • DMTDA dimethylthiotoluenediamine
  • DBMDA N,N'-di(sec.butyl)-aminobiphenylmethane
  • the number average molecular weight (Mn) of the polymer containing two or more hydroxyl groups and/or amino groups (primary and secondary) is preferably 500 or more and 100000 or less, more preferably 800 or more and 50000 or less, It is more preferably 1000 or more and 10000 or less.
  • the number average molecular weight (Mn) of the polymer can be determined by a so-called gel permeation chromatography (GPC) method. If the number average molecular weight (Mn) of the polymer is within the above numerical range, a thermoplastic elastomer composition having excellent fluidity during melt molding can be obtained.
  • a commercial product may be used as the polymer containing two or more hydroxyl groups.
  • Commercially available products include, for example, CrayValley brand names "Krasol HLBHP3000”, “Krasol LBHP3000”, “Krasol LBH3000”, “Krasol HLBHP2000”, “Krasol LBHP2000”, “Krasol LBH2000”, “Polybd Lbd, HPtolbd R45" R45V", “Polybd R20LM”; trade names "G-1000", “G-2000”, “G-3000”, “GI-1000", “GI-2000”, “GI-3000” manufactured by Nippon Soda Co., Ltd. ; Trade name “PPG3000” manufactured by Wako Pure Chemical Industries, Ltd., etc. can be used.
  • a commercial product may be used as the polymer containing two or more amino groups.
  • Commercially available products include, for example, Jeffamine D series, Jeffamine ED series, Jeffamine EDR series, Jeffamine T series, Elastamine RT series manufactured by HUNTSMAN, USA; 1000 or the like can be used.
  • Polyisocyanate Polyisocyanates containing two isocyanate groups used for synthesis of polyurethane resins include, for example, 4,4′-diphenylmethane diisocyanate (monomeric/polymeric MDI), tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), Aromatic diisocyanates such as naphthalene diisocyanate (NDI); Alicyclic diisocyanates; aliphatic diisocyanates such as hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHMDI), 1,5-pentamethylene diisocyanate (PDI), and the like.
  • MDI 4,4′-diphenylmethane diisocyanate
  • TDI tolylene diisocyanate
  • XDI xylylene diisocyanate
  • Aromatic diisocyanates such as naphthalene diisocyanate (
  • polyisocyanates containing three or more isocyanate groups include aliphatic polyhydric alcohol adducts, burettes, and isocyanurates of these diisocyanates.
  • the aliphatic polyhydric alcohol used in the adduct preferably has 2 to 5 carbon atoms, such as trimethylolpropane and glycerin. These polyisocyanates may be used singly or in combination of two or more.
  • a commercially available product may be used as the polyisocyanate.
  • Commercially available products include, for example, Mitsui Chemicals' product names "Takenate D-110N, D-120N", “Takenate 500, 600", “Fortimo H6XDI”, “Stabio PDI”, “Stabio 370N, 376N”, and “Takenate D-170N”. , D-131N”, etc., trade names manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd. “Cosmonate MDI, PH, LK, LL”, “Cosmonate MDI, M-50, 100, 200”, “Actocol TL, DL, ML , EDL, EPL, DN” and the like can be used.
  • the blending amount of the polymer and the polyisocyanate is preferably 0.2 or more and 5.0 or less, and preferably 0.5 or more, of the isocyanate groups of the polyisocyanate per one hydroxyl group and/or amino group of the polymer. It is preferably 3.0 or less, and preferably 0.7 or more and 2.0 or less. When the blending amount of the polymer and the polyisocyanate is within the above range, the reactivity becomes good.
  • the content of the polyurethane resin is 0.1% by mass or more and 60% by mass or less, preferably 0.5% by mass or more and 55% by mass or less, more preferably 1 It is more than mass % and below 50 mass %.
  • a thermoplastic elastomer composition having excellent resistance to compression set and excellent fluidity during melt molding can be obtained.
  • polyolefin thermoplastic resin Polyolefin-based thermoplastic resins are not particularly limited, and conventionally known polyolefins can be used. Examples of polyolefins include ethylene, propylene, butene-1, pentene-1, 2-methylbutene-1, 3-methylbutene-1, hexene-1, 3-methylpentene-1, 4-methylpentene-1, 3, 3-dimethylbutene-1, heptene-1, methylhexene-1, dimethylpentene-1, trimethylbutene-1, ethylpentene-1, octene-1, methylpentene-1, dimethylhexene-1, trimethylpentene-1, Ethylhexene-1, methylethylpentene-1, diethylbutene-1, ptopyrpentene-1, decene-1, methylnonene-1, dimethyloctene-1, trimethylheptene-1, ethylocten
  • polyethylene and polypropylene are preferred.
  • These polyolefins may be used singly or in combination of two or more.
  • Such a polyolefin-based thermoplastic resin preferably penetrates into the three-dimensional network structure of the polyurethane-based resin to provide a thermoplastic elastomer composition having excellent resistance to compression set and excellent fluidity during melt molding. be able to.
  • the content of the polyolefin thermoplastic resin is preferably 5 parts by mass or more and 3000 parts by mass or less, more preferably 10 parts by mass or more and 2000 parts by mass or less, and still more preferably It is 20 parts by mass or more and 1500 parts by mass or less.
  • a thermoplastic elastomer composition having excellent resistance to compression set and excellent fluidity during melt molding can be obtained.
  • the thermoplastic elastomer composition preferably contains a styrenic block copolymer.
  • the styrene-based block copolymer is preferably infiltrated into the three-dimensional network structure of the polyurethane-based resin.
  • a plasticizer such as the process oil described below
  • the "styrenic block copolymer” may be a copolymer having a styrene block structure at any site.
  • Styrenic block copolymers include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-isoprene-butadiene-styrene block copolymer (SIBS), Styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), etc. .
  • SBS, SEBS, SIS and SEEPS are more preferred, and SBS, SEBS and SEEPS are more preferred.
  • the styrene content of the styrenic block copolymer is preferably 10 to 70% by mass, more preferably 15 to 65% by mass. If the styrene content is within the above range, the balance between thermoplasticity and rubber elasticity will be good.
  • the styrene content in the styrenic block copolymer can be measured by a method based on the IR method described in JIS K6239 (published in 2007).
  • the weight average molecular weight (Mw) of the styrenic block copolymer is preferably 30,000 or more and 1,000,000 or less, more preferably 100,000 or more and 800,000 or less, from the viewpoint of mechanical strength and the like. More preferably, it is 200,000 or more and 700,000 or less.
  • the number average molecular weight (Mn) is preferably 10,000 or more and 600,000 or less, more preferably 50,000 or more and 550,000 or less, and further preferably 100,000 or more and 500,000 or less.
  • the dispersity (Mw/Mn) of the molecular weight distribution is preferably 5 or less, more preferably 1-3.
  • the weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution dispersity (Mw/Mn) can be determined by a so-called gel permeation chromatography (GPC) method.
  • a commercially available product may be used as the styrene-based block copolymer.
  • Commercially available products include, for example, trade names “G1633”, “D1101”, “DX410", “G1651” and “D1111” manufactured by Kraton; trade names “4055”, “4077” and “4099” manufactured by Kuraray. Asahi Kasei Co., Ltd. product names "H1053” and “H1051”; Li Chang Ying (LCY) product names "GP3501", “GP3502”, “GP3527”, “GP3411”, “GP9901”, “GP7533”, “GP7551” etc. can be used.
  • the content of the styrene block copolymer is preferably 1 part by mass or more and 3000 parts by mass or less, more preferably 30 parts by mass or more and 2000 parts by mass or less, relative to 100 parts by mass of the polyolefin thermoplastic resin. More preferably, it is 50 parts by mass or more and 1000 parts by mass or less. If the content of the styrenic block copolymer is within the above range, the fluidity during melt molding can be improved.
  • thermoplastic elastomer composition contains a plasticizer as an optional additive.
  • a plasticizer it is preferable to use a process oil from the viewpoint that the fluidity during melt molding can be further improved.
  • a process oil is preferable to use a styrene-based block copolymer together as a resin component in order to suppress bleeding of the process oil.
  • the process oil is preferably impregnated into the three-dimensional network structure of the polyurethane-based resin in order to suppress bleeding.
  • Such "process oil” is not particularly limited, and known process oils can be used as appropriate. oil) and the like. As such process oil, a commercially available one may be used as appropriate.
  • paraffin oil is preferred because it has a higher compatibility with elastomers and is capable of suppressing yellowing due to thermal deterioration at a higher level.
  • the paraffin oil suitable as such process oil is not particularly limited, and known paraffin oils (for example, those described in paragraphs [0153] to [0157] of JP-A-2017-57323). Can be used as appropriate.
  • paraffin oil the oil is subjected to a correlation ring analysis (ndM ring analysis) in accordance with ASTM D3238-85, and the number of paraffin carbon atoms is the percentage of the total number of carbon atoms (paraffin part: CP), the percentage of the number of naphthene carbons to the total number of carbons (naphthene part: CN), and the percentage of the number of aromatic carbons to the total number of carbons (aromatic part: CA), respectively.
  • CP total number of carbon atoms
  • the paraffin oil preferably has a kinematic viscosity at 40° C.
  • the paraffin oil preferably has an aniline point of 0° C. to 150° C., more preferably 10 to 145° C., measured by the U-tube method in accordance with JIS K2256 (published in 2013). It is more preferably 15 to 145°C.
  • the content of the process oil is preferably 100 parts by mass or more and 1000 parts by mass or less, more preferably 150 parts by mass or more and 900 parts by mass or less, and still more preferably It is 200 mass parts or more and 800 mass parts or less. If the content of the process oil is within the above range, it is possible to obtain a thermoplastic elastomer composition that is excellent in fluidity during melt molding while suppressing bleeding.
  • thermoplastic elastomer composition may contain any other additive besides the additives mentioned above.
  • additives include reinforcing agents (types of fillers: silica, carbon black, etc.), fillers into which amino groups are introduced, amino group-containing compounds other than the amino group-introduced fillers, and metal elements.
  • antioxidants antioxidants, antioxidants, pigments (dyes), plasticizers other than the above process oils, thixotropic agents, UV absorbers, flame retardants, solvents, surfactants (including leveling agents), deodorants (baking soda, etc.), dispersant, dehydrating agent, antirust agent, adhesion imparting agent, antistatic agent, filler other than clay, lubricant, slip agent, light stabilizer, conductivity imparting agent, antibacterial agent, neutralizing agent, Various additives such as softeners, fillers, colorants, thermally conductive fillers, etc. can be included.
  • thermoplastic elastomer composition comprises the steps of (i) mixing a polymer containing two or more hydroxyl groups and/or amino groups with a polyolefin thermoplastic resin to obtain a mixture; further adding a polyisocyanate containing two or more isocyanate groups to the resulting mixture and allowing it to react to form a polyurethane resin. Each step will be described in detail below.
  • Step (i) a polymer containing at least two hydroxyl groups and/or amino groups, a polyolefin thermoplastic resin, and, if necessary, a styrenic block copolymer, a plasticizer, other additives, etc. Mix to obtain a mixture.
  • the mixing conditions are not particularly limited, and can be appropriately set according to the type of resin component used. Polymers containing two or more hydroxyl groups and/or amino groups, polyolefin thermoplastic resins, styrenic block copolymers, plasticizers, and other additives are described in [Thermoplastic elastomer composition] above. It is as detailed in the column.
  • step (ii) a polyisocyanate containing two or more isocyanate groups is added to the mixture obtained in step (i) and reacted to form a polyurethane resin. It is preferable to form a polyurethane resin having a three-dimensional network structure by such a reaction.
  • the reaction conditions are not particularly limited, and can be appropriately set according to the type of resin component used.
  • the two or more polyisocyanates are as described in detail in the section [Thermoplastic elastomer composition] above.
  • thermoplastic elastomer composition at least one of the number of hydroxyl groups and/or amino groups of the polymer added in step (i) and the number of isocyanate groups of the polyisocyanate added in step (ii) is 3 or more. It is possible to three-dimensionally bond a polyurethane resin, which is a reaction product of a polymer and a polyisocyanate, and allow other resin components, a plasticizer, and the like to enter the three-dimensional network structure of the polyurethane resin. Furthermore, by adjusting the content of the polyurethane-based resin in the thermoplastic elastomer composition to a specific ratio, bleeding can be suppressed even when paraffin oil is used as the plasticizer.
  • the molded article of the present invention is obtained using the above thermoplastic elastomer composition. Since the thermoplastic elastomer composition of the present invention is excellent in resistance to compression set and fluidity during melt molding, the molded articles obtained are useful for automotive, mechanical, electrical, and residential rubber parts, especially automotive interiors. Suitable for housing interiors.
  • polyolefin thermoplastic resin 1 high-den
  • thermoplastic elastomer composition was prepared in the same manner as in Example 1, except that 30.0 g of polyolefin thermoplastic resin 2 (block polypropylene, manufactured by SunAllomer, trade name: PM970A) was added instead of polyolefin thermoplastic resin 1. prepared the product.
  • polyolefin thermoplastic resin 2 block polypropylene, manufactured by SunAllomer, trade name: PM970A
  • Example 3 20.0 g of hydrocarbon polymer 1, 8.0 g of styrene-ethylene-butadiene-styrene block copolymer (SEBS, manufactured by LCY, trade name: GP7533) and paraffin oil (manufactured by ENEOS, trade name: 300HV-S (J)) 24.0 g was premixed and put into the pressure kneader, and the addition amount of polyolefin thermoplastic resin 1 was changed to 4.0 g, and the addition amount of anti-aging agent was changed to 0.0 g.
  • SEBS styrene-ethylene-butadiene-styrene block copolymer
  • paraffin oil manufactured by ENEOS, trade name: 300HV-S (J)
  • Example 4 10.0 g of hydrocarbon polymer 1, 12.0 g of styrene-ethylene-butadiene-styrene block copolymer (SEBS, manufactured by LCY, trade name: GP7533) and paraffin oil (manufactured by ENEOS, trade name: 300HV-S (J)) 36.0 g was premixed and put into the pressure kneader, and the addition amount of polyolefin thermoplastic resin 1 was changed to 6.0 g, and the addition amount of anti-aging agent was changed to 0.0 g.
  • SEBS styrene-ethylene-butadiene-styrene block copolymer
  • paraffin oil manufactured by ENEOS, trade name: 300HV-S (J)
  • Example 5 5.0 g of hydrocarbon polymer 1, 12.0 g of styrene-ethylene-butadiene-styrene block copolymer (SEBS, manufactured by LCY, trade name: GP7533) and paraffin oil (manufactured by ENEOS, trade name: 300HV-S (J)) 36.0 g was premixed and put into the pressure kneader, and the addition amount of polyolefin thermoplastic resin 1 was changed to 6.0 g, and the addition amount of anti-aging agent was changed to 0.0 g.
  • a thermoplastic elastomer composition was prepared in the same manner as in Example 3, except that the amount was changed to 0602 g and the amount of polyisocyanate 1 (glycerin HXDI) was changed to 1.181 g.
  • Example 6 1.1 g of hydrocarbon polymer 1, 13.2 g of styrene-ethylene-butadiene-styrene block copolymer (SEBS, manufactured by LCY, trade name: GP7533) and paraffin oil (manufactured by ENEOS, trade name: 300HV-S (J)) 39.6 g was premixed and put into the pressure kneader, and the amount of polyolefin thermoplastic resin 1 added was changed to 6.6 g, and the amount of anti-aging agent added was changed to 0.6 g.
  • SEBS styrene-ethylene-butadiene-styrene block copolymer
  • paraffin oil manufactured by ENEOS, trade name: 300HV-S (J)
  • Example 7 0.6 g of hydrocarbon polymer 1, 14.4 g of styrene-ethylene-butadiene-styrene block copolymer (SEBS, manufactured by LCY, trade name: GP7533) and paraffin oil (manufactured by ENEOS, trade name: 300HV-S (J)) 43.2 g was premixed and put into the pressure kneader, and the added amount of polyolefin thermoplastic resin 1 was changed to 7.2 g, and the added amount of anti-aging agent was changed to 0.2 g. 0656 g, and polyisocyanate 1 (glycerin HXDI) was changed to 0.142 g, in the same manner as in Example 3 to prepare a thermoplastic elastomer composition.
  • SEBS styrene-ethylene-butadiene-styrene block copolymer
  • paraffin oil manufactured by ENEOS, trade name: 300HV-S (J)
  • SEBS styrene-ethylene-butadiene-styrene block copolymer
  • paraffin oil manufactured by ENEOS, trade name: 300HV-S (J)
  • a thermoplastic elastomer composition was prepared in the same manner as in Example 4, except that the added amount of was changed to 0.976 g and the added amount of the antioxidant was changed to 0.0650 g.
  • thermoplastic elastomer composition was prepared in the same manner as in Example 4, except that Polyisocyanate 1 was not added and the amount of antioxidant added was changed to 0.641 g.
  • thermoplastic elastomer composition was prepared in the same manner as in Example 1, except that the amount of added was changed to 0.0644 g.
  • thermoplastic elastomer composition was prepared in the same manner as in Comparative Example 2, except that 21.0 g of polyolefin thermoplastic resin 2 was added instead of polyolefin thermoplastic resin 1.
  • thermoplastic elastomer composition was prepared in the same manner as in Example 4, except that the amount of added was changed to 0.0647 g.
  • thermoplastic elastomer composition was prepared in the same manner as in Example 4, except that the amount of added was changed to 0.0646 g.
  • Tables 1 and 2 show the formulations of the thermoplastic elastomer compositions prepared in Examples 1-14 and Comparative Examples 1-5. The amount of each component in the table is based on 100 parts by mass of the hydrocarbon polymer. Also, the physical properties of the thermoplastic elastomer composition were evaluated with respect to the following items. Evaluation results are shown in Tables 1 and 2.
  • thermoplastic elastomer composition obtained in each example and comparative example was measured by the ATR method using an FTIR spectrophotometer (manufactured by Thermo Scientific, trade name: NICOLET is10), and the isocyanate group of the polyisocyanate was measured. confirmed the disappearance of In Tables 1 and 2, " ⁇ " indicates that the disappearance of the isocyanate group was confirmed, and "-" indicates that it was not measured.
  • thermoplastic elastomer composition obtained in each example and comparative example was used to form a sheet for use in evaluating the properties of the composition as follows. First, using a pressure press with a water cooling function, 43 g of a thermoplastic elastomer composition was put into a mold measuring 15 cm long, 15 cm wide and 2 mm thick, and heated at 200° C. for 3 minutes before pressing ( preheated), then pressurized (hot press) under the conditions of temperature: 200 ° C., working pressure: 20 MPa, pressurizing time: 5 minutes, and then water cooling under the conditions of working pressure: 20 MPa, pressurizing time: 2 minutes.
  • thermoplastic elastomer composition was taken out from the mold to obtain a sheet for measurement with a thickness of 2 mm.
  • the appearance of the obtained sheet was visually evaluated according to the following criteria, and Tables 1 and 2 show the evaluation results of the sheet formability.
  • Evaluation criteria ⁇ : There was no problem with the appearance of the sheet.
  • x A large number of cracks occurred in the appearance of the sheet.
  • ⁇ indicates good thermoplasticity, and " ⁇ " indicates poor thermoplasticity.
  • thermoplastic elastomer composition obtained in each example and comparative example bleeding of the resin component and plasticizer was confirmed as follows. Specifically, a disk with a diameter of 15 mm was punched out from the above sheet, left on paper for 24 hours, and the size of the mark left on the paper (the amount of oil absorbed) was compared. Bleeding was evaluated according to the following criteria, and the evaluation results are shown in Tables 1 and 2. [Evaluation criteria] 5: No trace remained. 4: A thin trace smaller than a circle with a diameter of 15 mm remained. 3: A trace having a size approximately equal to a circle with a diameter of 15 mm remained. 2: A trace of a circle with a diameter of 20 mm remained. 1: A trace of a circle with a diameter of 20 mm or more remained. In addition, if it is 3 points or more, there is no practical problem, and it can be said that it is a pass.
  • JIS-E hardness Using the sheets for each measurement obtained as described above, the JIS-E hardness of the thermoplastic elastomer composition was measured as follows. Specifically, the JIS-E hardness is measured using a type E durometer (durometer E hardness tester: trade name "Type E durometer GSD-721K” manufactured by Teclock) under a temperature condition of 20 ⁇ 5°C. Measurement of hardness based on JIS K6253-3 (published in 2012) for 5 measurement points (5 measurement points) on the surface of each sheet for measurement (6 sheets stacked, thickness 10 mm or more). gone. The E hardness was determined by determining the average value of hardness at each measurement point (average value of 5 points).
  • the compression set (compression set) was determined as follows. First, the sheet for measurement was heated at 125° C. for 30 minutes to remove residual molding strain. After that, the sheet for measurement was punched out into a disc shape of 29 mm in diameter, and seven discs were superimposed to prepare a sample having a height (thickness) of 12.5 ⁇ 0.5 mm. Using the sample obtained in this way, compress it by 25% with a special jig, leave it at 70 ° C. for 22 hours, release the compression, leave it at room temperature for 30 minutes, and then set it to compression set (unit: % ) was measured according to JIS K6262 (published in 2013). As a compression device, a trade name "vulcanized rubber compression set tester SCM-1008L" manufactured by Dumbbell Co., Ltd. was used. In addition, in Tables 1 and 2, "X" indicates that the measurement is not possible.
  • melt flow rate (MFR, unit: g / 10 minutes) was measured in accordance with B method described in JIS K6922-2 (published in 2010). ) was measured. That is, using each of the thermoplastic elastomer compositions described above, a melt flow rate measuring device manufactured by Toyo Seiki Seisakusho under the trade name "Melt Indexer G-01" was used, and 3 g of the thermoplastic elastomer composition was placed in the furnace body of the device. After the addition, the temperature was raised to 230° C.
  • Example 1 when high-density polyethylene was used as the polyolefin thermoplastic resin and the content of polyurethane was adjusted to 51% by mass, a good thermoplastic elastomer was obtained.
  • Example 2 when block polypropylene was used as the thermoplastic polyolefin resin and the polyurethane content was adjusted to 51% by mass, a good thermoplastic elastomer was obtained.
  • Example 3 to 7 by adding a styrenic block copolymer and paraffin oil, thermoplastic elastomers with reduced hardness and improved fluidity were obtained.
  • Example 8 when polybutadiene with hydroxyl groups on both ends was used to synthesize polyurethane, a good thermoplastic elastomer was obtained.
  • Example 10 when polypropylene glycol was used to synthesize polyurethane, a good thermoplastic elastomer was obtained, but the bleeding was somewhat large.
  • Example 11 when polybutadiene with hydroxyl groups on both ends having Mn: 1430, 1,2-V: 90.1%, t-1,4: 9.9% was used to synthesize polyurethane, a good thermoplastic elastomer was obtained. was gotten.
  • Example 12 when polybutadiene with hydroxyl groups on both ends having Mn: 2980, 1,2-V: 90.6%, t-1,4: 9.4% was used to synthesize polyurethane, a good thermoplastic elastomer was obtained. was gotten. In Example 13, a good thermoplastic elastomer was obtained by synthesizing polyurethane using hydrogenated polybutadiene with hydroxyl groups on both ends. In Example 14, polyurea was synthesized using polyoxypropylene diamine and a good thermoplastic elastomer was obtained. In Comparative Example 1, when the polybutadiene with both hydrogenated hydroxyl groups was added without adding the polyisocyanate, the thermoplastic elastomer had high fluidity, but bleeding occurred.
  • Comparative Example 2 high-density polyethylene was used and the polyurethane content was adjusted to 67% by weight, and the elastomer did not exhibit thermoplasticity.
  • Comparative Example 3 block polypropylene was used and the polyurethane content was adjusted to 67% by weight, and the elastomer did not exhibit thermoplastic properties.
  • Comparative Example 4 when HXDI, a bifunctional isocyanate, was used to synthesize polyurethane, the thermoplastic elastomer bleed significantly.
  • Comparative Example 5 when a polyurethane was synthesized using a bifunctional isocyanate, XDI, the thermoplastic elastomer bleed significantly.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Le problème décrit par la présente invention est de fournir une composition d'élastomère thermoplastique qui présente une remarquable fluidité pendant le moulage par fusion et une excellente résistance à une déformation permanente par compression. La solution consiste en la composition d'élastomère thermoplastique selon la présente invention qui est caractérisée en ce qu'elle contient une résine à base de polyuréthane et une résine thermoplastique à base de polyoléfine, et qui est caractérisée en ce que la résine à base de polyuréthane est le produit d'une réaction entre un polymère comportant au moins deux groupes hydroxy et/ou deux groupes aminés et un polyisocyanate comportant au moins deux groupes isocyanate, la quantité de groupes hydroxy et/ou de groupes aminés dans le polymère et/ou la quantité de groupes isocyanate dans le polyisocyanate étant au moins égales à trois, et la quantité de résine à base de polyuréthane présente dans la composition variant de 0,1 à 60 % en masse par rapport à la quantité totale de la composition d'élastomère thermoplastique.
PCT/JP2022/003230 2021-01-29 2022-01-28 Composition d'élastomère thermoplastique et son procédé de production, et article moulé WO2022163796A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021013725A JP2022117168A (ja) 2021-01-29 2021-01-29 熱可塑性エラストマー組成物およびその製造方法ならびに成形体
JP2021-013725 2021-01-29

Publications (1)

Publication Number Publication Date
WO2022163796A1 true WO2022163796A1 (fr) 2022-08-04

Family

ID=82653471

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/003230 WO2022163796A1 (fr) 2021-01-29 2022-01-28 Composition d'élastomère thermoplastique et son procédé de production, et article moulé

Country Status (3)

Country Link
JP (1) JP2022117168A (fr)
TW (1) TW202239863A (fr)
WO (1) WO2022163796A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06184367A (ja) * 1992-12-17 1994-07-05 Regurusu:Kk ポリマーアロイ
JPH1034843A (ja) * 1996-07-26 1998-02-10 Tosoh Corp 積層体およびそれよりなる用途
JP2001253980A (ja) * 2000-03-09 2001-09-18 Asahi Kasei Corp ウレタン系エラストマー
JP2003335917A (ja) * 2002-05-20 2003-11-28 Kuraray Co Ltd 熱可塑性エラストマー組成物
JP2017206588A (ja) * 2016-05-16 2017-11-24 Ｊｘｔｇエネルギー株式会社 熱可塑性エラストマー組成物及びその製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06184367A (ja) * 1992-12-17 1994-07-05 Regurusu:Kk ポリマーアロイ
JPH1034843A (ja) * 1996-07-26 1998-02-10 Tosoh Corp 積層体およびそれよりなる用途
JP2001253980A (ja) * 2000-03-09 2001-09-18 Asahi Kasei Corp ウレタン系エラストマー
JP2003335917A (ja) * 2002-05-20 2003-11-28 Kuraray Co Ltd 熱可塑性エラストマー組成物
JP2017206588A (ja) * 2016-05-16 2017-11-24 Ｊｘｔｇエネルギー株式会社 熱可塑性エラストマー組成物及びその製造方法

Also Published As

Publication number Publication date
TW202239863A (zh) 2022-10-16
JP2022117168A (ja) 2022-08-10

Similar Documents

Publication Publication Date Title
CA1258144A (fr) Melanges a base de caoutchouc copolymerique d'ester acrylique rendus compatibles
EP2588534B1 (fr) Compositions de polymères
EP0209874B2 (fr) Compositions de copolymères séquencés hydrogénés
CN102159626B (zh) 新型弹性体材料及其获得方法
WO2002090433A1 (fr) Composition elastomere thermoplastique
KR100875406B1 (ko) 열가소성 엘라스토머 조성물의 제조 방법
CN110603273B (zh) 改性嵌段共聚物、改性嵌段共聚物的制造方法以及树脂组合物
JP2013122055A (ja) 溶融粘度が改良された熱可塑性ポリオレフィン組成物および該組成物の作製方法
EP0212831B1 (fr) Compositions copolymères élastomères moulables
TW201728733A (zh) 熱塑性彈性體組成物、構件、耐候密封件、耐候密封件用角構件
KR100843124B1 (ko) 슬러시 성형용 수지분말 조성물 및 성형품
WO2022163796A1 (fr) Composition d'élastomère thermoplastique et son procédé de production, et article moulé
US20070276094A1 (en) Thermoplastic polyolefin compositions having improved adhesion to polymer foams and/or coatings and methods of making and using the same
JP5241558B2 (ja) 電子線架橋性エラストマー組成物および成形体の製造方法
JP3503339B2 (ja) 熱可塑性エラストマー組成物
JP4067935B2 (ja) 熱可塑性発泡体用組成物および発泡体
JP4522728B2 (ja) 熱可塑性重合体組成物
JP2004059636A (ja) 熱可塑性重合体組成物
JP4522729B2 (ja) 熱可塑性エラストマー組成物
JPS60123524A (ja) ポリマ−用組成物
EP4269489A1 (fr) Composition élastomère thermoplastique et corps moulé
KR20230168831A (ko) 고내구성을 가지는 경량 신발 중창용 발포체 조성물
KR20220161904A (ko) 내구성이 우수한 경량 신발 중창용 발포체 조성물
JP2002363417A (ja) 粉体成形用熱可塑性エラストマー組成物粉体及びこれを用いて粉体成形した表皮体
JPH05320442A (ja) プロピレン系重合体組成物

Legal Events

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

Ref document number: 22746015

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22746015

Country of ref document: EP

Kind code of ref document: A1