WO2018230614A1 - Composition élastomère thermoplastique - Google Patents

Composition élastomère thermoplastique Download PDF

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Publication number
WO2018230614A1
WO2018230614A1 PCT/JP2018/022616 JP2018022616W WO2018230614A1 WO 2018230614 A1 WO2018230614 A1 WO 2018230614A1 JP 2018022616 W JP2018022616 W JP 2018022616W WO 2018230614 A1 WO2018230614 A1 WO 2018230614A1
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Prior art keywords
copolymer
vinyl compound
aromatic vinyl
ethylene
thermoplastic elastomer
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PCT/JP2018/022616
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English (en)
Japanese (ja)
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亘佑 中村
雄志 熊谷
勝 長谷川
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デンカ株式会社
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Publication of WO2018230614A1 publication Critical patent/WO2018230614A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • 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

Definitions

  • the present invention relates to a thermoplastic elastomer composition excellent in transparency, softness, low temperature characteristics, tensile characteristics, and blocking resistance, and a molded body, a sheet, and a medical tube using the same.
  • thermoplastic elastomers having excellent productivity have been increasingly used for applications such as automobile parts, home appliance parts, medical parts or sundries, where vulcanized rubber has been the mainstream.
  • many new thermoplastic elastomers having required characteristics according to various uses have been proposed.
  • a so-called styrene-ethylene copolymer is obtained by a method in which a small amount of divinylbenzene is copolymerized and a polystyrene chain (cross chain) is introduced via a vinyl group of a divinylbenzene unit.
  • Cross copolymers have been proposed.
  • the cross-copolymer obtained by this method is a block copolymer having a branched structure having a styrene-ethylene copolymer chain as a soft segment and polystyrene as a hard segment, and is extremely excellent in scratch resistance and molding processability. It has become a material.
  • the cross-copolymer is a thermoplastic elastomer that has extremely excellent properties such as scratch resistance, softness, transparency, and moldability, but depending on the application, curing at low temperatures is an issue, and excellent low-temperature softness, etc. It was necessary to use a processing technique such as blending with a resin, elastomer, rubber, additive, etc. having the above characteristics.
  • low temperature characteristics may be required because it may be connected to an infusion pump used at low temperatures.
  • blocking resistance at high temperatures may be required because heating is performed during sterilization. Transparency decreases when pursuing low-temperature properties and blocking resistance with a cross-copolymer alone. There was a problem to do.
  • a support layer occupying 50% or more of the tube thickness is a cross-copolymer having sufficient softness
  • an inner layer is a multi-layer tube having a small blocking property. It is proposed to improve the blockage caused by the close contact between the inner walls when clamped with a.
  • the dissemination of medical parts has been promoted, and in many cases it is incinerated after use to prevent biohazards, and it is important to use non-soft PVC material that does not generate chlorine compounds as gas during incineration. It has become.
  • An object of the present invention is to provide a thermoplastic elastomer composition excellent in transparency, softness, low temperature characteristics, tensile characteristics, and blocking resistance, and a molded article, a sheet, and a medical tube using the same.
  • the gist of the present invention is as follows.
  • Olefin-aromatic vinyl compound system in which aromatic vinyl compound monomer unit is 10 to 23 mol%, aromatic polyene monomer unit is 0.01 to 0.5 mol%, and the balance is an olefin monomer unit.
  • the acetylated monoglyceride plasticizer (B) is used for 100 parts by mass of the cross-copolymer (A) containing the main chain of the copolymer and the cross-chain of the aromatic vinyl compound polymer comprising the aromatic vinyl compound monomer unit.
  • a thermoplastic elastomer composition comprising 3 to 10 parts by mass.
  • the cross copolymer (A) contains 70 to 95% by mass of an olefin-aromatic vinyl compound copolymer and 5 to 30% by mass of an aromatic vinyl compound polymer.
  • Thermoplastic elastomer composition contains 70 to 95% by mass of an olefin-aromatic vinyl compound copolymer and 5 to 30% by mass of an aromatic vinyl compound polymer. Thermoplastic elastomer composition.
  • thermoplastic elastomer composition according to any one of [1] or [2], wherein the aromatic vinyl compound monomer unit is styrene.
  • thermoplastic elastomer composition according to any one of [2] to [3], wherein the olefin monomer unit is ethylene.
  • thermoplastic elastomer composition according to any one of [1] to [4], wherein the aromatic polyene monomer unit is divinylbenzene.
  • thermoplastic elastomer composition according to any one of [1] to [5], wherein the acetylated monoglyceride plasticizer (B) is substantially acetylated monolauryl glyceride.
  • the cross copolymer (A) has a structure in which an ethylene-aromatic vinyl compound-aromatic polyene copolymer chain and an aromatic vinyl compound polymer chain are bonded via an aromatic polyene monomer unit.
  • the content of the aromatic vinyl compound monomer unit in the ethylene-aromatic vinyl compound-aromatic polyene copolymer is 10 to 23 mol%, and the content of the aromatic polyene monomer unit is 0.01 mol% or more. 0.5 mol% or less, and the balance is the content of ethylene monomer units.
  • the ethylene-aromatic vinyl compound-aromatic polyene copolymer has a weight average molecular weight of 50,000 to 300,000 and a molecular weight distribution (Mw / Mn) of 1.8 to 6.
  • the content of the ethylene-aromatic vinyl compound-aromatic polyene copolymer contained in the cross copolymer is in the range of 70 to 95% by mass.
  • thermoplastic elastomer composition comprising 3 to 10 parts by mass of an acetylated monoglyceride plasticizer (B) per 100 parts by mass of a cross copolymer (A), the cross copolymer (A ) Satisfies all the following conditions (4) to (7).
  • B acetylated monoglyceride plasticizer
  • the content is 10 to 23 mol%, and the content of the ethylene-aromatic vinyl copolymer component contained is in the range of 70 to 95% by mass, (5) The ethylene-aromatic vinyl compound copolymer and aromatic vinyl compound polymer contained have a bond, (6) MFR (200 ° C., weight 49 N) is in the range of 0.05 to 50 g / 10 minutes, (7) The gel content is 0.2% by mass or less.
  • thermoplastic elastomer composition according to any one of [1] to [8].
  • thermoplastic elastomer composition that is excellent in transparency, softness, low temperature characteristics, tensile characteristics, and blocking resistance, and a molded article, sheet, and medical tube using the same.
  • thermoplastic elastomer composition The present invention relates to aromatic vinyl compound monomer units of 10 to 23 mol%, aromatic polyene monomer units of 0.01 to 0.5 mol%, preferably 0.01 to 0.2 mol%, and the balance being olefin.
  • a cross copolymer (A) 100 comprising a main chain of an olefin-aromatic vinyl compound copolymer as a monomer unit and a cross chain of an aromatic vinyl compound polymer comprising an aromatic vinyl compound monomer unit.
  • a thermoplastic elastomer composition comprising 3 to 10 parts by mass of an acetylated monoglyceride plasticizer (B) per part by mass.
  • a to B means not less than A and not more than B.
  • the cross copolymer (A) is an olefin-aromatic vinyl compound copolymer comprising an aromatic vinyl compound monomer unit, an olefin monomer unit, and an aromatic polyene monomer unit.
  • the polymer which consists of an aromatic vinyl compound monomer unit has the structure couple
  • aromatic vinyl compound monomer unit examples include styrene and various substituted styrenes such as p-methylstyrene, m-methylstyrene, o-methylstyrene, ot-butylstyrene, mt-butylstyrene, p- Examples thereof include units derived from styrene monomers such as t-butylstyrene, p-chlorostyrene and o-chlorostyrene.
  • a styrene unit, a p-methylstyrene unit, and a p-chlorostyrene unit are preferable, and a styrene unit is particularly preferable.
  • One type of these aromatic vinyl compound monomer units may be used, or two or more types may be used in combination.
  • olefin monomer units include ethylene and ⁇ -olefins having 3 to 20 carbon atoms such as propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, vinylcyclohexane, cyclic olefins, Examples thereof include units derived from each ⁇ -olefin monomer and cyclic olefin monomer such as cyclopentene and norbornene.
  • a mixture of an ethylene unit, a propylene unit, a 1-butene unit, a 1-hexene unit, a 1-octene unit or the like is used, and an ethylene unit is particularly preferably used.
  • the aromatic polyene monomer unit is an aromatic polyene having 10 to 30 carbon atoms and having a plurality of double bonds (vinyl group) and one or more aromatic groups, such as o- Divinylbenzene, p-divinylbenzene, m-divinylbenzene, 1,4-divinylnaphthalene, 3,4-divinylnaphthalene, 2,6-divinylnaphthalene, 1,2-divinyl-3,4-dimethylbenzene, 1,3 -Units derived from an aromatic polyene monomer such as divinyl-4,5,8-tributylnaphthalene, preferably any one or two of orthodivinylbenzene unit, paradivinylbenzene unit and metadivinylbenzene unit A mixture of seeds or more is preferably used.
  • aromatic groups such as o- Divinylbenzene, p-divinylbenzene, m-divinylbenz
  • each structural unit in the olefin-aromatic vinyl compound-based copolymer is 10 to 23 mol% of the aromatic vinyl compound monomer unit from the viewpoint of flexibility and transparency, and the aromatic polyene monomer unit. 0.01 to 0.5 mol%, the balance being olefin monomer units, and from the viewpoints of softness and blocking resistance as a thermoplastic elastomer composition, preferably aromatic vinyl compound monomer units 12 ⁇ 18 mol%, aromatic polyene monomer units 0.01 to 0.2 mol%, and the balance is olefin monomer units.
  • the content ratio of the olefin-aromatic vinyl compound copolymer and the polymer comprising the aromatic vinyl compound monomer unit is preferably an olefin-aromatic vinyl compound copolymer from the viewpoint of transparency and flexibility. Is from 70 to 95% by weight, and the polymer comprising aromatic vinyl compound monomer units is from 5 to 30% by weight. From the viewpoint of physical properties as a thermoplastic elastomer composition, olefin-aromatic vinyl is particularly preferable.
  • the compound-based copolymer is 82 to 92% by mass, and the polymer composed of aromatic vinyl compound monomer units is 8 to 18% by mass.
  • the peak intensity (area) of vinyl group hydrogen (proton) of the divinylbenzene unit of the cross-copolymer is compared with the same peak intensity (area) of the divinylbenzene unit of the ethylene-styrene-divinylbenzene copolymer macromonomer. And less than 50%, preferably less than 20%.
  • the divinylbenzene unit is copolymerized simultaneously with the polymerization of the styrene unit, and the ethylene-styrene-divinylbenzene copolymer chain and the polystyrene chain are bonded via the divinylbenzene unit.
  • the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain and the aromatic vinyl compound polymer chain are bonded via an aromatic polyene monomer unit.
  • the fact that the ethylene-styrene-divinylbenzene copolymer chain and the polystyrene chain are bonded via a divinylbenzene unit can be proved by the following observable phenomenon. That is, even after the Soxhlet extraction is carried out a sufficient number of times using an appropriate solvent, the contained ethylene-styrene-divinylbenzene copolymer chain cannot be separated from the polystyrene chain.
  • the ethylene-styrene-divinylbenzene copolymer and polystyrene of the same composition as the ethylene-styrene-divinylbenzene copolymer chain contained in this cross copolymer are subjected to Soxhlet extraction with boiling acetone, so that the acetone insoluble part As an ethylene-styrene-divinylbenzene copolymer and as an acetone soluble part into polystyrene.
  • the expression defining the cross copolymer of this embodiment is that the cross copolymer (A) has an ethylene-aromatic vinyl compound-aromatic polyene copolymer chain and an aromatic vinyl compound polymer chain. And a copolymer having a structure in which an ethylene-aromatic vinyl compound-aromatic polyene copolymer chain and an aromatic vinyl compound polymer chain are bonded via an aromatic polyene monomer unit.
  • the cross-copolymer may contain a relatively small amount of an aromatic vinyl compound (polystyrene) homopolymer.
  • the cross copolymer (A) comprises an ethylene-aromatic vinyl compound-aromatic polyene copolymer chain and an aromatic vinyl compound polymer chain via an aromatic polyene monomer unit.
  • the copolymer has a bonding structure and further satisfies all the following conditions (1) to (3).
  • the content of the aromatic vinyl compound monomer unit in the ethylene-aromatic vinyl compound-aromatic polyene copolymer is 10 to 23 mol%, preferably 12 to 18 mol%, The content is 0.01 mol% or more and 0.5 mol% or less, preferably 0.01 mol% or more and 0.2 mol% or less, and the balance is the content of ethylene monomer units.
  • the ethylene-aromatic vinyl compound-aromatic polyene copolymer has a weight average molecular weight of 50,000 to 300,000 and a molecular weight distribution (Mw / Mn) of 1.8 to 6.
  • the content of the ethylene-aromatic vinyl compound-aromatic polyene copolymer contained in the cross-copolymer is in the range of 70 to 95% by mass, preferably 82 to 92% by mass.
  • the weight average molecular weight Mw of the aromatic vinyl compound polymer chain is arbitrary, but is generally in the range of 10,000 to 80,000. In the cross copolymer, the molecular weight of the aromatic vinyl compound polymer chain bonded to the main chain ethylene-aromatic vinyl compound-aromatic polyene copolymer cannot be determined.
  • the weight average molecular weight Mw of the aromatic vinyl compound polymer homopolymer contained in a relatively small amount in the copolymer is defined as the weight average molecular weight Mw of the aromatic vinyl compound polymer chain contained in the cross copolymer. Yes.
  • the peak derived from the ethylene-aromatic vinyl compound copolymer (ethylene-styrene copolymer) and the peak derived from the aromatic vinyl compound polymer (polystyrene) The ethylene unit content, the aromatic vinyl compound (styrene) unit content derived from the ethylene-aromatic vinyl compound copolymer (ethylene-styrene copolymer) of the cross copolymer, and the weight of the aromatic vinyl compound
  • the content of coalesced (polystyrene) can be determined.
  • aromatic polyene actually contained in an ethylene-aromatic vinyl compound copolymer (ethylene-styrene-divinylbenzene copolymer) in an amount of 0.01 mol% to 0.5 mol%.
  • Content is included in the aromatic vinyl compound (styrene) unit content in which the peak positions overlap, and each content is obtained.
  • the acetone-insoluble part occupying most of the cross-copolymer contains both an ethylene-aromatic vinyl compound copolymer (ethylene-styrene copolymer) and an aromatic vinyl compound polymer (polystyrene). This cannot be separated by further fractionation operations.
  • the ethylene-aromatic vinyl compound copolymer chain and the aromatic vinyl compound polymer chain have a bond (for example, the ethylene-styrene copolymer chain and the polystyrene chain). Can be proved).
  • This cross-copolymer is substantially free of gels and has thermoplasticity despite the fact that the ethylene-aromatic vinyl compound copolymer chain and the aromatic vinyl compound polymer chain have a bond. Practical moldability as a resin, that is, a specific MFR value can be shown.
  • thermoplastic elastomer composition obtained by blending 3 to 10 parts by mass of an acetylated monoglyceride plasticizer (B) with 100 parts by mass of a cross copolymer (A)
  • the copolymer (A) can be defined as a copolymer that satisfies all of the following conditions (4) to (7).
  • the manufacturing method of the cross copolymer (A) based on this invention is demonstrated.
  • the polymerization mode is not particularly limited and can be produced by a known method such as solution polymerization or bulk polymerization, but is more preferable because solution polymerization has a high degree of freedom in controlling polymerization in obtaining a desired cross-copolymer. is there.
  • the polymerization method is not particularly limited as long as the desired cross-copolymer (A) can be obtained.
  • a coordination polymerization step of polymerizing an olefin-aromatic vinyl compound copolymer using a coordination polymerization catalyst, and a coordination In the coexistence of the olefin-aromatic vinyl compound copolymer obtained in the polymerization step and the aromatic vinyl compound monomer, polymerization is performed using an anionic polymerization initiator to form an aromatic polyene monomer unit of the main chain.
  • the coordination polymerization process will be specifically described.
  • the coordination polymerization catalyst a single site coordination polymerization catalyst composed of a transition metal compound and a promoter can be used.
  • Methylaluminoxane can be suitably used as a cocatalyst that assists the activity of the single site coordination polymerization catalyst.
  • alkyl aluminum can be used suitably.
  • the solvent to be used is preferably a hydrocarbon system such as cyclohexane, methylcyclohexane, toluene, ethylbenzene, or an aromatic hydrocarbon system because it poisons the single-site coordination polymerization catalyst if it has a polar functional group.
  • the amount of the solvent added is preferably 200 to 900 parts by mass with respect to 100 parts by mass of the obtained copolymer. If it is 200 mass parts or more, it is suitable when controlling a polymerization-solution viscosity and reaction rate, and if it is 900 mass parts or less, it is preferable from a viewpoint of productivity.
  • the anionic polymerization process will be specifically described.
  • the main chain is polymerized by using an anionic polymerization initiator in the coexistence of the olefin-aromatic vinyl compound copolymer obtained in the coordination polymerization step and the aromatic vinyl compound monomer.
  • a cross-copolymer (A) having a structure in which a polymer composed of an aromatic vinyl compound monomer unit is cross-linked to a vinyl group remaining in the aromatic polyene monomer unit is synthesized.
  • the olefin-aromatic vinyl compound copolymer obtained in the coordination polymerization step is precipitated by a poor solvent such as methanol, the solvent is evaporated by a heating roll or the like (drum dryer method), and the concentrator. Concentrate the solution after removing the solvent with a vent type extruder, disperse the solution in water, blow off water vapor to remove the solvent by heating (steam stripping method), crumb forming Any method such as a method may be used for the anionic polymerization step after separation and purification from the polymerization solution after the coordination polymerization.
  • a polymerization solution containing an olefin-aromatic vinyl compound copolymer may be used in the anionic polymerization step without separating and purifying the olefin-aromatic vinyl compound copolymer from the polymerization solution.
  • the anionic polymerization initiator known anionic polymerization initiators such as n-butyllithium and sec-butyllithium can be used.
  • the aromatic vinyl compound monomer the aromatic vinyl compound monomer remaining in the polymerization solution after the coordination polymerization can be used as it is.
  • the target cross-copolymer (A) can be obtained by adding a required amount before the start of anionic polymerization, or adding or adding in the middle of anionic polymerization.
  • the method for recovering the cross-copolymer (A) is not particularly limited, a method for precipitation with a poor solvent such as methanol, a method for evaporation by evaporation with a heating roll or the like (drum dryer method), and a solution of water.
  • a known method such as a method of recovering a copolymer by blowing water vapor and removing the solvent by heating (a steam stripping method) or a crumb forming method can be used.
  • a polymerization solution is continuously fed to a twin-screw devolatilizing extruder using a gear pump, and a polymerization solvent is devolatilized.
  • This method is economical because the devolatilizing component containing the polymerization solvent is condensed and recovered using a condenser, etc., and the polymerization solvent can be reused by purifying the condensate in the distillation tower. It is preferable from the viewpoint.
  • acetylated monoglyceride plasticizer (B) examples include, but are not limited to, acetylated monolauryl glyceride, acetylated monocapryl glyceride, acetylated monostearyl glyceride, and acetylated monooleyl. A glyceride is mentioned. These plasticizers may be used alone or in combination.
  • the plasticizer used in the present invention is preferably an acetylated monoglyceride plasticizer from the viewpoints of transparency and blocking resistance. Particularly preferred is substantially acetylated monolauryl glyceride. If the acetylated monoglyceride plasticizer (B) is substantially acetylated monolauryl glyceride, it is particularly preferred because blocking resistance is improved.
  • substantially means that 70% by mass or more of the contained plasticizer is acetylated monolauryl glyceride.
  • the structure of the glycerin fatty acid ester plasticizer (B) used was measured by performing composition analysis using ACQUITY UPLC manufactured by Waters as a liquid chromatography (LC) and Synapt G2 manufactured by Waters as a mass spectrometer (MS). .
  • acetylated monoglyceride plasticizer (B) a commercially available product can be used, and it can also be produced using a known production method.
  • These acetylated monoglyceride lubricants can be purchased from, for example, Riken Vitamin.
  • the blending amount of the acetylated monoglyceride plasticizer (B) is preferably 3 to 10 parts by mass of the acetylated monoglyceride plasticizer (B) with respect to 100 parts by mass of the cross copolymer (A). If the amount of the acetylated monoglyceride plasticizer (B) is 3 parts by mass or more, low temperature curing is suppressed, which is preferable. A blending amount of the acetylated monoglyceride plasticizer (B) of 10 parts by mass or less is preferable because a decrease in tensile strength is suppressed.
  • the blending amount of the acetylated monoglyceride plasticizer (B) is most preferably 4 to 8 parts by mass.
  • thermoplastic elastomer composition of this embodiment is excellent in transparency, softness, low temperature characteristics, tensile characteristics, and blocking resistance. Specifically, the transparency is 20% or less for a 1 mm-thick sheet, the softness is 79 or less in terms of A hardness, the tensile property is a tensile stress of 3.0 MPa or more at 23 ° C. and 100% elongation, and Tensile stress at 5 ° C. and 100% elongation is 7.5 MPa or less, low temperature characteristics (low temperature curing), the difference in tensile stress at 100% elongation at 5 ° C. and 23 ° C.
  • the anti-blocking property is evaluated by the method defined in this example, and the evaluation level is 2 or more. Furthermore, most preferably, the transparency is 15% or less for a 1 mm thick sheet, the softness is 75 or less in terms of A hardness, and the tensile properties are 23 ° C., 100% elongation tensile stress 3.5 MPa or more, And the tensile stress at 100% elongation at 5 ° C is 6.5 MPa or less, and the low temperature property (low temperature curing) is the difference between the tensile stress at 100% elongation at 5 ° C and 23 ° C is 3.0 MPa or less.
  • the anti-blocking property is evaluated by the method defined in this example, and the evaluation level is 3 or more.
  • thermoplastic elastomer composition of the present invention a lubricant, a stabilizer, an antistatic agent, an impact strength improver, a processing aid, an ultraviolet absorber, and an antioxidant are added to the thermoplastic elastomer composition of the present invention, as necessary.
  • thermoplastic resins such as ethylene-based resins, propylene-based resins, or styrene-diene block copolymers such as SBS, SIS, SEBS, and SEPS and hydrogenated products thereof may be used as the cross-copolymer (A) 100. It can add in the ratio of 1 to 30 mass parts with respect to the mass part.
  • the method for producing the thermoplastic elastomer composition of the present invention is not particularly limited, but a single-screw extruder, a mating co-rotating or mating counter-rotating twin-screw extruder, a non- or incomplete mating two It can be manufactured using a known melt-kneading apparatus such as a screw extruder such as a screw extruder, Banbury mixer, a kneader, and a mixing roll. Among them, the melt-mixing method using an extruder is from the viewpoint of productivity and good kneadability. preferable.
  • thermoplastic elastomer composition of the present embodiment is excellent in transparency, softness, low temperature characteristics, tensile characteristics, and blocking resistance, and can be used for various molded articles, particularly suitable for sheets and medical tubes. It is. There is no restriction
  • molding method of a molded object Well-known methods, such as an extrusion molding method, an injection molding method, a blow molding method, a rotation molding method, can be used.
  • thermoplastic elastomer composition of the present invention can be synthesized by, for example, synthesis described in JP2009-102515A, WO09 / 128444, WO13 / 018171, or JP2011-153214A. It is suitably used for leather, grips or exterior members, foams, skin materials, tape substrates, wire coating materials, gaskets, or conductive sheets.
  • the sheet using the thermoplastic elastomer composition of the present invention may be a single layer or a multilayer. In the case of a multilayer, you may use as a multilayer which has the layer which consists of another resin component.
  • the thermoplastic elastomer composition of the present invention is, for example, a medical device described in International Publication No.
  • thermoplastic elastomer composition of the present invention may be a single layer or multiple layers. Moreover, in the case of a multilayer, you may use as a multilayer which has the layer which consists of another resin component.
  • Cross copolymer (A) The following cross copolymers 1 to 7 were used. These cross-copolymers were produced by the production methods of Examples or Comparative Examples described in International Publication No. 2000/37517, International Publication No. 2007/139116, and Japanese Unexamined Patent Publication No. 2009-12092. Was similarly determined by the method described in these publications. In other words, the composition in the cross-copolymer or ethylene-aromatic vinyl compound-aromatic polyene copolymer, ie, the content of ethylene, aromatic vinyl compound or aromatic vinyl compound polymer is determined by 1 H-NMR (proton NMR).
  • the content of aromatic polyene in the ethylene-aromatic vinyl compound-aromatic polyene copolymer was determined from the amount of aromatic polyene charged at the time of polymerization and gas chromatographic analysis of the polymerization solution sampled after completion of coordination polymerization. It calculated by calculating
  • the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polystyrene chain were determined by GPC measurement of the aromatic vinyl compound polymer separated by solvent fractionation.
  • the vinyl group hydrogen (proton) peak intensity (area) of the divinylbenzene unit is the same peak of the divinylbenzene unit of the ethylene-styrene-divinylbenzene copolymer obtained in the coordination polymerization step.
  • the strength (area) was less than 20%.
  • the hydrogen (proton) peak of the vinyl group of the divinylbenzene unit substantially disappeared in the cross-copolymer after anionic polymerization.
  • cross copolymer was subjected to Soxhlet extraction using boiling acetone.
  • the ethylene-styrene-divinylbenzene copolymer chain substantially ethylene-styrene copolymer chain
  • the polystyrene chain contained therein were removed. I could't sort it.
  • Mw weight average molecular weight
  • Mw / Mn molecular weight distribution
  • Mw molecular weight distribution
  • ⁇ GPC measurement conditions Device name: HLC-8220 (manufactured by Tosoh Corporation) Column: Four series of Shodex GPC KF-404HQ Temperature: 40 ° C Detection: Differential refractive index Solvent: Tetrahydrofuran Calibration curve: Prepared using standard polystyrene (PS).
  • Cross copolymer (A-1) An ethylene-styrene-divinylbenzene copolymer having a styrene content of 11 mol%, a divinylbenzene content of 0.06 mol%, a weight average molecular weight of 121,000, a molecular weight distribution of 2.2, -Content of ethylene-styrene-divinylbenzene copolymer: 88% by mass, -Weight average molecular weight of polystyrene chain 13,000, molecular weight distribution 1.2 A hardness 83 -MFR 0.7g / 10min (200 ° C, weight 49N)
  • Cross copolymer (A-2) An ethylene-styrene-divinylbenzene copolymer having a styrene content of 15 mol%, a divinylbenzene content of 0.06 mol%, a weight average molecular weight of 141,000, a molecular weight distribution of
  • Acetylated monoglyceride plasticizer (B) Acetylated monoglyceride plasticizer (B-1): Acetylated monolauryl glyceride Riquemar PL-012 (manufactured by Riken Vitamin Co., Ltd.) was used. The content of acetylated monolauryl glyceride was 80% by mass or more. A mixture of acetylated monoglyceride plasticizer (B-2): acetylated monolauryl glyceride: acetylated monocaprylic glyceride (mass ratio 50:50) Riquemar PL-019 (manufactured by Riken Vitamin Co., Ltd.) was used.
  • the structures of the plasticizers (B-1) to (B-2) used were subjected to composition analysis using ACQUITY UPLC manufactured by Waters as a liquid chromatography (LC) and SynaptG2 manufactured by Waters as a mass spectrometer (MS). Performed and measured.
  • Other plasticizers (C) Other plasticizer (C-1): Liquid paraffin Hicol M-352 (manufactured by Kaneda) was used.
  • the structure of the plasticizer (C-1) used was measured by composition analysis using ACQUITY UPLC manufactured by Waters as a liquid chromatography (LC) and SynaptG2 manufactured by Waters as a mass spectrometer (MS). The results are shown in Table 1.
  • Table 3 shows the ratios of the cross copolymers (A-1) to (A-7) and the acetylated monoglyceride plasticizers (B-1) to (B-2) or other plasticizers (C-1).
  • (Mass part) was melt-kneaded at a cylinder temperature of 200 ° C. with a twin-screw extruder (TEM-35B manufactured by Toshiba Machine Co., Ltd.) and pelletized to obtain a thermoplastic elastomer composition. About the obtained thermoplastic elastomer composition, the test piece according to the following evaluation criteria was created and evaluated. The results are shown in Table 2.
  • Sheet preparation was as follows. As a sample for physical property evaluation, a square mirror surface press sheet having a thickness (1 mm) formed by a heat press method (200 ° C., time 5 minutes, pressure 50 kg / cm 2) using a mirror surface mold (manufactured by STAVAX) was used. .
  • a haze meter (Nippon Denshoku Industries Co., Ltd. NDH-1001DP type) was used to measure the haze of a square mirror surface press sheet having a thickness of 1 mm and a side of 50 mm in accordance with JIS K7136. In addition, the haze of 20% or less was set as an acceptable level, and 15% or less was set as a particularly preferable level.
  • the tensile stress at 100% elongation is the tensile stress when 100% elongation is given to the test piece.
  • a 1 mm thick press sheet was punched into a No. 3 dumbbell mold and used.
  • the tensile speed was 500 mm / min.
  • the tensile property is a tensile stress of 3.0 MPa or more at 23 ° C.
  • the tensile stress is 7.5 MPa or less at 100 ° elongation of 5 ° C.
  • the tensile property is a tensile stress of 3 at 23 ° C. and 100% elongation.
  • a tensile stress of 6.5 MPa or less at 5 ° C. and 100% elongation was set to a particularly preferable level.
  • Softness In accordance with JIS K6253-3, instantaneous hardness was determined using type A durometer hardness. Six 1 mm-thick press sheets were used as test pieces. In addition, A hardness 79 or less was made into the acceptable level, and 75 or less was made into the most preferable level.
  • Examples 1 to 9 all had a haze of 20% or less, 23 ° C., 100% elongation tensile stress of 3.0 MPa or more, 5 ° C., 100% elongation tensile stress of 7.5 MPa or less, low temperature curing of 3.5 MPa or less, A It had a hardness of 79 or less and a blocking resistance evaluation of 2 or more, was excellent in transparency, tensile properties, softness and blocking resistance, and low-temperature curing was suppressed. On the other hand, Comparative Examples 1 to 6 were inferior in any of physical properties among transparency, tensile properties, softness and anti-blocking properties, or weakly suppressed at low temperature.
  • Example 10 Using the thermoplastic elastomer composition obtained in Example 2, a tube having an outer diameter of 3.6 mm, an inner diameter of 2.4 mm, and a tube thickness of 0.6 mm was formed by extrusion molding. The characteristics as a medical tube were evaluated according to the following criteria. The results are shown in Table 3.
  • the subject is touched at 23 ° C. with the prepared tube cut to a length of 20 cm and a comparative soft polyvinyl chloride medical single-layer tube, and the one with the soft touch is selected. If the created tube was softer than a soft polyvinyl chloride medical single-layer tube, ⁇ (excellent), if equal, ⁇ (good), and if the created tube was clearly hard, ⁇ (impossible). As for the softness of the tube, ⁇ (good) or better was regarded as acceptable.
  • the kink start radius is preferably 10 mm or less.
  • the shape of the generated kink (bending) was observed. Observe the situation where crushing occurs relatively uniformly in a wide part of the tube. ⁇ (excellent): Wide kink is generated and crushing occurs in a narrower range ⁇ (good): A relatively wide kink is generated, crushing occurs in a narrower range, and the tube is broken ⁇ (defective) ): Classified as acute-angle kink. The shape of the kink was set to pass (good) or better.
  • Nitroglycerin adsorptivity Nitroglycerin injection solution (active ingredient 50 mg / 100 mL, Millisrol injection, Nippon Kayaku Co., Ltd.) 60 mL was injected into 1 L of Japanese Pharmacopoeia physiological saline and gently stirred. Immediately, the sample was sampled with a syringe with a syringe needle to obtain a blank. The tube of the infusion set was closed with a flow rate adjusting clamp, and the drip tube was pierced through a rubber stopper. The lower half of the drip tube was filled with the solution by pumping the drip tube.
  • the clamp for adjusting the flow rate was gradually loosened, and the tube was filled with the solution, and then set on the infusion pump.
  • the flow rate was set to 36 mL / h, the flow rate adjusting clamp was opened, the switch was turned on, and infusion was started.
  • the solution flowing out from the tip was sampled over time, and the concentration was measured using ACQUITY UPLC manufactured by Waters as liquid chromatography (LC).
  • the infusion was performed for 180 minutes, and the first 60 minutes were sampled every 5 minutes and thereafter every 15 minutes. If the density drop was within 10% compared to the blank density, the test was accepted.
  • the tube was closed with a flow rate adjusting clamp, and the drip tube was pierced through a rubber stopper of Japanese Pharmacopoeia saline.
  • the lower half of the drip tube was filled with the saline by pumping the drip tube.
  • the flow rate adjusting clamp was gradually loosened, and the tube was filled with the saline solution, and then set on the infusion pump.
  • the flow rate was set to 250 mL / h, the flow rate adjusting clamp was opened, the switch was turned on, and infusion was started. Immediately after this, the amount of physiological saline per minute flowing out from the tip was measured and used as the initial flow rate. After 24 hours, the flow rate per minute was again measured in the same manner.
  • Tube state after completion of pump infusion After completion of the above-mentioned pump flow rate stability, the squeezed portion of the tube was incised, and the surface state of the inner and outer surfaces, the change in tube diameter, and the presence or absence of cracks were observed.
  • thermoplastic elastomer composition of the present invention is excellent in transparency, softness, low temperature characteristics, tensile characteristics, and blocking resistance, and can be suitably used for molded articles, sheets, and medical tubes.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Materials For Medical Uses (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

L'invention fournit une composition élastomère thermoplastique excellente en termes de transparence, de souplesse, de caractéristiques à basse température, de caractéristiques de traction et de résistance à l'adhérence, et un corps moulé, une feuille ainsi qu'un tube pour application médicale mettant en œuvre cette composition. La composition élastomère thermoplastique de l'invention est constituée par mélange de 10 à 23% en moles d'une unité monomère de composé vinyle aromatique, de 0,01 à 0,5% en moles d'une unité monomère de polyène aromatique, et de 3 à 10 parties en masse d'un plastifiant à base de monoglycéride acétylé (B) pour 100 parties en masse d'un copolymère réticulé (A) qui contient une chaîne principale d'un copolymère à base d'oléfine et de composé vinyle aromatique dont un résidu consiste en une unité monomère oléfine, et une chaîne réticulée d'un polymère de composé vinyle aromatique constituée d'une unité monomère de composé vinyle aromatique.
PCT/JP2018/022616 2017-06-13 2018-06-13 Composition élastomère thermoplastique WO2018230614A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11124420A (ja) * 1997-10-24 1999-05-11 Idemitsu Petrochem Co Ltd 芳香族ビニルグラフト共重合体及びその製造方法
JP2001316431A (ja) * 2000-05-08 2001-11-13 Denki Kagaku Kogyo Kk 医療用成形体
JP2002020553A (ja) * 2000-07-04 2002-01-23 Shin Etsu Polymer Co Ltd 食品包装用ポリオレフィン系樹脂組成物
JP2013202133A (ja) * 2012-03-27 2013-10-07 Denki Kagaku Kogyo Kk 医療用チューブ

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11124420A (ja) * 1997-10-24 1999-05-11 Idemitsu Petrochem Co Ltd 芳香族ビニルグラフト共重合体及びその製造方法
JP2001316431A (ja) * 2000-05-08 2001-11-13 Denki Kagaku Kogyo Kk 医療用成形体
JP2002020553A (ja) * 2000-07-04 2002-01-23 Shin Etsu Polymer Co Ltd 食品包装用ポリオレフィン系樹脂組成物
JP2013202133A (ja) * 2012-03-27 2013-10-07 Denki Kagaku Kogyo Kk 医療用チューブ

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