WO2017170903A1 - Composition de résine thermoplastique et son objet moulé - Google Patents

Composition de résine thermoplastique et son objet moulé Download PDF

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Publication number
WO2017170903A1
WO2017170903A1 PCT/JP2017/013332 JP2017013332W WO2017170903A1 WO 2017170903 A1 WO2017170903 A1 WO 2017170903A1 JP 2017013332 W JP2017013332 W JP 2017013332W WO 2017170903 A1 WO2017170903 A1 WO 2017170903A1
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thermoplastic resin
mass
resin composition
resin
amorphous
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Japanese (ja)
Inventor
賢一 瀬野
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Priority to JP2018509452A priority Critical patent/JP6835069B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity

Definitions

  • the present invention relates to a thermoplastic resin composition capable of self-healing even if a scratch occurs, and a molded body thereof.
  • Patent Document 1 describes an incompatible composition composed of poly (styrene-butadiene) and sulfonated poly (styrene-butadiene).
  • Patent Document 1 In recent years, transparency is also required for self-healing materials.
  • the composition described in Patent Document 1 is opaque because it is incompatible, and a necessary polymer is designed according to a temperature at which self-repair occurs (hereinafter, referred to as a repair temperature). There is a problem that it is necessary to synthesize and it is difficult to adjust the repair temperature.
  • An object of the present invention is to provide a thermoplastic resin composition that can give a molded article that is transparent and has self-healing performance, and that can easily adjust the repairing temperature by adjusting the content of its constituent components. And a molded article comprising the thermoplastic resin composition.
  • the present invention provides the following thermoplastic resin composition and molded article.
  • Amorphous thermoplastic resin (A) having a weight average molecular weight of 50,000 to 500,000 and a molecular weight distribution of 1.0 to 3.5, and a weight average molecular weight of 500 to 50,
  • An amorphous thermoplastic resin (B) that is less than 000, the total amount of the amorphous thermoplastic resin (A) and the amorphous thermoplastic resin (B) being 100% by mass
  • the content of the crystalline thermoplastic resin (A) is 25% by mass to 85% by mass
  • the content of the amorphous thermoplastic resin (B) is 15% by mass to 75% by mass
  • Thermoplastic resin composition satisfying (1) and requirement (2): Requirement (1)
  • the glass transition temperature of the thermoplastic resin composition is 0 ° C.
  • thermoplastic resin composition further contains a crystalline thermoplastic resin (C), The thermoplastic resin composition according to [1], wherein the total amount of the thermoplastic resin in the thermoplastic resin composition is 100% by mass, and the content of the crystalline thermoplastic resin (C) is 0.01 to 9% by mass. object.
  • a molded article comprising the thermoplastic resin composition according to [1] or [2].
  • thermoplastic resin composition which can give the molded object which is transparent and has self-repair performance, and can perform adjustment of repair temperature easily, and shaping
  • the body can be provided.
  • the amorphous thermoplastic resin is a thermoplastic resin having a crystal melting enthalpy (hereinafter sometimes referred to as ⁇ H) observed by differential scanning calorimetry of 40 J / g or less.
  • ⁇ H of the amorphous thermoplastic resin (A) and the amorphous thermoplastic resin (B) is preferably 10 J / g or less, more preferably 1 J / g or less.
  • the melting enthalpy is obtained by analyzing a portion in the temperature range of ⁇ 50 ° C. or higher and 200 ° C. or lower of a melting curve measured by the following differential scanning calorimetry by a method based on JIS K7122.
  • thermoplastic resin composition of the present invention Next, a specific configuration of the thermoplastic resin composition of the present invention will be described.
  • thermoplastic resin composition of the present invention contains an amorphous thermoplastic resin (A) having a weight average molecular weight of 50,000 to 500,000 and a molecular weight distribution of 1.0 to 3.5. .
  • the weight average molecular weight of the amorphous thermoplastic resin (A) is 50,000 or more and 500,000 or less, and the self-repairing performance and molding processability are improved, and the rigidity of the molded body made of the resin composition is increased. From the viewpoint, it is preferably 75,000 or more and 400,000 or less, more preferably 100,000 or more and 300,000 or less.
  • the molecular weight distribution is the ratio of the weight average molecular weight to the number average molecular weight.
  • the weight average molecular weight is a polystyrene equivalent weight average molecular weight measured by gel permeation chromatography
  • the molecular weight distribution is a polystyrene equivalent number average measured by gel permeation chromatography.
  • a polymer soluble in chloroform is subjected to gel permeation chromatography using chloroform as a solvent.
  • those insoluble in chloroform are dissolved in xylene and then subjected to gel permeation chromatography using chloroform as a solvent.
  • the melt flow rate of the amorphous thermoplastic resin (A) measured at a temperature of 190 ° C. and a load of 21 N in accordance with JIS K7210 is preferably 0.01 g / 10 minutes from the viewpoint of improving moldability. As mentioned above, More preferably, it is 0.05 g / 10min or more, More preferably, it is 0.1 g / 10min or more.
  • the melt flow rate of the amorphous thermoplastic resin (A) is preferably 500 g / 10 min or less, more preferably from the viewpoint of improving the molding processability and increasing the rigidity of the molded body made of the resin composition. Is 50 g / 10 min or less, more preferably 10 g / 10 min or less.
  • the glass transition temperature of the thermoplastic amorphous resin (A) is preferably ⁇ 70 ° C. or higher and 150 ° C. or lower, more preferably ⁇ 50 ° C. or higher and 120 ° C. or lower, and further preferably ⁇ 30 ° C. or higher and 100 ° C. or lower. It is below °C.
  • the glass transition temperature is an intermediate glass transition temperature obtained by analyzing a melting curve measured by the following differential scanning calorimetry method by a method based on JIS K7121. [Differential scanning calorimetry] By means of a differential scanning calorimeter, an aluminum pan encapsulating about 5 mg of sample in a nitrogen atmosphere was (1) held at 200 ° C.
  • amorphous thermoplastic resin (A) examples include olefin resins, styrene elastomers, acrylic resins, polyester resins, polyamide resins, styrene / acrylonitrile resins, engineering plastics, polyvinyl chloride, chlorinated rubber, natural rubber, and chloroprene. Examples thereof include rubber, fluorine rubber, silicon rubber, and urethane rubber. Among these, olefin resin, styrene elastomer, acrylic resin, and engineering plastic are preferable. These may be used alone or in combination of two or more. Moreover, the amorphous thermoplastic resin (A) may be cross-linked.
  • the copolymer exemplified below may be a random copolymer or a block copolymer.
  • the olefin resin is a resin containing monomer units derived from olefins.
  • the olefin resin include amorphous propylene resin, amorphous ethylene resin, amorphous cyclic olefin resin, butyl rubber, polybutadiene, and isoprene resin.
  • the amorphous propylene resin is a polymer containing monomer units derived from propylene and having a ⁇ H of 40 J / g or less.
  • Amorphous propylene resins include propylene homopolymer, propylene-ethylene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-4-methyl-1-pentene copolymer , Propylene-vinylcyclohexane copolymer, propylene-4-vinylcyclohexene copolymer, propylene-norbornene copolymer, propylene-styrene copolymer, maleic anhydride modified propylene homopolymer, maleic anhydride modified propylene-ethylene copolymer Polymer, maleic anhydride modified propylene-butene copolymer, ethylene-propylene-1-butene copolymer, ethylene-propylene-1-hexene copolymer, ethylene-propylene-1-octene copolymer, ethylene-propylene -4-methyl-1-pentene copoly
  • the amorphous propylene resin is, for example, an atactic propylene resin.
  • the amorphous ethylene resin is a polymer containing 100% by mass of the amorphous ethylene resin, containing 50% by mass or more of monomer units derived from ethylene, and ⁇ H of 40 J / g or less.
  • Amorphous ethylene resins include ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene- Vinylcyclohexane copolymer, ethylene-4-vinylcyclohexene copolymer, ethylene-norbornene copolymer, ethylene-tetracyclododecene copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer Ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, and the like.
  • the amorphous cyclic olefin resin is a polymer having a mass of the cyclic olefin resin of 100% by mass, containing 50% by mass or more of monomer units derived from the cyclic olefin, and a ⁇ H of 40 J / g or less.
  • Examples of the amorphous cyclic olefin resin include a norbornene ring-opening polymer, a tetracyclododecene ring-opening polymer, a norbornene-ethylene copolymer, a tetracyclododecene-ethylene copolymer, and the like.
  • the isoprene resin examples include polyisoprene, a copolymer of a C10 alicyclic compound that is a dimerized product of isoprene and a C10 chain compound, and the like.
  • the olefin resin is preferably an amorphous propylene resin, more preferably a propylene homopolymer, a propylene-1-butene copolymer, or an ethylene-propylene-1-butene copolymer.
  • styrene elastomer examples include styrene-butadiene-styrene triblock copolymer (SBS), styrene-isoprene-styrene triblock copolymer (SIS), styrene-butadiene random copolymer (SBR), and styrene- Isobutylene-styrene block copolymers (SIBS), hydrogenated products in which some or all of the carbon-carbon double bonds of these SBS copolymers are hydrogenated, maleic anhydride modified styrene-isoprene-styrene block copolymers Examples thereof include a polymer (MAH-SIS) and a maleic anhydride-modified styrene-butadiene-styrene block copolymer (MAH-SBS).
  • SBS styrene-butadiene-styrene triblock copolymer
  • These hydrogenated products include styrene- (ethylene / propylene) -styrene block copolymer (SEPS; SIS hydrogenated product), styrene- (ethylene / butylene) -styrene block copolymer (SEBS; hydrogenated SBS).
  • SEPS styrene- (ethylene / propylene) -styrene block copolymer
  • SEBS hydrogenated SBS
  • SEEPS Styrene-ethylene- (ethylene / propylene) -styrene block copolymer
  • SEEPS Styrene-ethylene- (ethylene / propylene) -styrene block copolymer
  • SBR hydrogenated polystyrene block copolymer
  • MAH-SEBS maleic anhydride modified styrene- ( And ethylene / butylene) -styrene block copolymer
  • MAH-SEPS maleic anhydride-modified styrene- (ethylene / propylene) -styrene block copolymer
  • a styrene-butadiene-styrene triblock copolymer a styrene-isoprene-styrene triblock copolymer, a styrene-butadiene random copolymer, a styrene- (ethylene / propylene) -styrene block copolymer, A styrene- (ethylene / butylene) -styrene block copolymer, a hydrogenated product in which part or all of these carbon-carbon double bond portions are hydrogenated.
  • acrylic resin examples include polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, methyl acrylate-methyl methacrylate copolymer, and the like. . Of these, polybutyl methacrylate and polybutyl acrylate are preferable.
  • polyester resin examples include amorphous polyethylene terephthalate.
  • polyamide resin examples include amorphous polyamide.
  • styrene / acrylonitrile resin examples include polystyrene, ⁇ -methylstyrene-vinyltoluene copolymer, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer, styrene-acrylonitrile-indene copolymer, polyacrylonitrile and the like. Can be mentioned.
  • Examples of the engineering plastic include polysulfone, polyethersulfone, polyarylate, polyamideimide, polyetherimide, modified polyphenylene ether, and polycarbonate. Of these, polycarbonate is preferable.
  • thermoplastic resin composition of the present invention contains an amorphous thermoplastic resin (B) having a weight average molecular weight of 500 or more and less than 50,000.
  • the weight average molecular weight of the amorphous thermoplastic resin (B) is 500 or more and less than 50,000, and is preferably 700 from the viewpoint of improving self-healing performance, increasing the strength of the molded product, and suppressing tackiness. It is 40,000 or less, and more preferably 900 or more and 30,000 or less.
  • the glass transition temperature of the amorphous thermoplastic resin (B) is preferably 0 ° C. or higher and 200 ° C. or lower, more preferably 30 ° C. or higher and 150 ° C. or lower, and further preferably 40 ° C. or higher and 120 ° C. or lower. is there.
  • the molecular weight distribution of the amorphous thermoplastic resin (B) is preferably 1.0 or more and 4.5 or less, more preferably 1.0 or more, from the viewpoint of increasing the strength of the molded body and suppressing the adhesiveness. 4.0 or less, more preferably 1.0 or more and 3.5 or less.
  • Examples of the amorphous thermoplastic resin (B) in the present invention include the olefin resin, styrene elastomer, acrylic resin, polyester resin, polyamide resin, styrene / acrylonitrile resin, engineering plastic, polyvinyl chloride, and chlorinated rubber. Natural rubber, chloroprene rubber, fluorine rubber, silicon rubber, urethane rubber, rosin resin, terpene resin, petroleum resin, coumarone resin, xylene resin, styrene / maleic anhydride resin, and the like. Among them, rosin resin, terpene resin, styrene-maleic anhydride resin and the like are preferable.
  • the amorphous thermoplastic resin (B) may be cross-linked.
  • the amorphous thermoplastic resin (B) is a copolymer
  • the copolymer may be a random copolymer or a block copolymer.
  • rosin resin examples include natural rosin, polymerized rosin, partially hydrogenated rosin, fully hydrogenated rosin, esterified products of these rosins (for example, glycerin ester, pentaerythritol ester, ethylene glycol ester, methyl ester), rosin derivatives (for example, Disproportionated rosin, fumarized rosin, lime rosin).
  • terpene resin examples include homopolymers of cyclic terpenes such as ⁇ -pinene, ⁇ -pinene, and dipentene, copolymers of cyclic terpenes, and copolymers of cyclic terpenes and phenolic compounds such as phenol and bisphenol (for example, Terpene-phenol resins such as ⁇ -pinene-phenol resins, dipentene-phenol resins and terpene-bisphenol resins), aromatic modified terpene resins which are copolymers of cyclic terpenes and aromatic monomers, and carbons thereof
  • a hydrogenated terpene resin which is a hydrogenated product in which part or all of the intercalated double bond portion is hydrogenated can be mentioned.
  • Examples of the petroleum resin include homopolymers and copolymers of naphtha cracked oil C5 fraction, C6 to C11 fraction and other olefinic fractions, and carbon-carbon double bond portions of these homopolymers and copolymers.
  • Examples thereof include aliphatic petroleum resins, aromatic petroleum resins, alicyclic petroleum resins, and aliphatic-alicyclic copolymer resins, which are hydrogenated products in which a part or all of them are hydrogenated.
  • the synthetic petroleum resin further includes a copolymer of naphtha cracked oil and the above terpene, and a copolymer petroleum resin that is a hydrogenated product of the copolymer.
  • Examples of the coumarone resin include a polymer having one or more monomer units selected from the group consisting of coumarone, indene and styrene.
  • the thermoplastic resin composition of the present invention is the amorphous thermoplastic resin (A), wherein the total amount of the amorphous thermoplastic resin (A) and the amorphous thermoplastic resin (B) is 100% by mass. Is 25 mass% or more and 85 mass% or less, and content of the said amorphous thermoplastic resin (B) is 15 mass% or more and 75 mass% or less. From the viewpoint of the strength of the molded body made of the thermoplastic resin, the content of the amorphous thermoplastic resin (A) is preferably 30% by mass or more, more preferably 35% by mass or more. From the viewpoint of the self-healing performance of the molded body made of the thermoplastic resin, the content of the amorphous thermoplastic resin (A) is preferably 80% by mass or less, more preferably 70% by mass or less.
  • the thermoplastic resin composition of the present invention satisfies the requirements (1) and (2).
  • the glass transition temperature of the thermoplastic resin composition of the present invention is 0 ° C. or higher and 200 ° C. or lower.
  • the glass transition temperature of the thermoplastic resin composition is preferably 0 ° C. or higher and 150 ° C. or lower, more preferably 0 ° C. or higher and 100 ° C. or lower.
  • only one glass transition temperature of the thermoplastic resin composition is observed within a temperature range of ⁇ 50 ° C. to 200 ° C. Is preferred. Only one glass transition temperature of the thermoplastic resin composition is observed within a temperature range of ⁇ 50 ° C. or higher and 200 ° C. or lower, which means that the thermoplastic resin contained in the thermoplastic resin composition is compatible.
  • the haze of a sheet having a thickness of 1 mm made of a thermoplastic resin composition is less than 8.0%.
  • the haze is preferably less than 7%, more preferably less than 5%.
  • the amorphous thermoplastic resin (A) and the amorphous thermoplastic resin (B) are in phase so that the haze of the 1 mm thick sheet made of the thermoplastic resin composition of the present invention is less than 8.0%. Select a combination to dissolve.
  • the thermoplastic resin composition further contains a crystalline thermoplastic resin (C) described later, the crystallinity is set so that the haze of the 1 mm thick sheet made of the thermoplastic resin composition is less than 8.0%.
  • the content of the thermoplastic resin (C) is adjusted.
  • the crystalline thermoplastic resin (C) and the amorphous thermoplastic resin (A) are amorphous so that the haze of the 1 mm thick sheet made of the thermoplastic resin composition of the present invention is less than 8.0%. It is preferable to be compatible with the thermoplastic resin (B).
  • the combination of the amorphous thermoplastic resin (A) and the amorphous thermoplastic resin (B) contained in the thermoplastic resin composition of the present invention includes olefin resin and olefin resin, styrene elastomer and styrene elastomer, acrylic Resin and acrylic resin, polycarbonate and polycarbonate, olefin resin and rosin resin, olefin resin and terpene resin, olefin resin and petroleum resin, styrene elastomer and rosin resin, styrene elastomer and terpene resin, styrene elastomer and petroleum resin, acrylic resin And rosin resin, acrylic resin and terpene-phenol resin, polycarbonate and styrene-maleic anhydride resin.
  • the melt flow rate of the thermoplastic resin composition of the present invention measured at a temperature of 190 ° C. and a load of 21 N in accordance with JIS K7210 is preferably 0.05 to 300 g / 10 minutes, more preferably 0.1 to It is 200 g / 10 minutes, and more preferably 0.2 to 100 g / 10 minutes.
  • the thermoplastic resin composition of the present invention may contain a crystalline thermoplastic resin (C) in order to increase the rigidity of the molded body made of the thermoplastic resin composition.
  • the crystalline thermoplastic resin is a thermoplastic resin having a ⁇ H greater than 40 J / g.
  • the ⁇ H of the crystalline thermoplastic resin (C) is preferably 80 J / g or more.
  • crystalline thermoplastic resin (C) As said crystalline thermoplastic resin (C), crystalline olefin resin, wax, and paraffin are mentioned.
  • a crystalline olefin resin is a polymer containing monomer units derived from olefins and having a ⁇ H greater than 40 J / g.
  • Examples of the crystalline olefin resin include crystalline propylene resin and crystalline ethylene resin.
  • the crystalline propylene resin is a polymer containing monomer units derived from propylene and having a ⁇ H of greater than 40 J / g.
  • the crystalline propylene resin includes a propylene homopolymer, a propylene copolymer containing a monomer unit derived from propylene, and a monomer unit selected from the group consisting of ethylene and an ⁇ -olefin having 4 to 10 carbon atoms.
  • a polymer is mentioned.
  • the propylene-based copolymer include a propylene-ethylene copolymer.
  • the propylene-based copolymer may be a random copolymer or a block copolymer.
  • the crystalline propylene resin may be modified with at least one compound selected from unsaturated carboxylic acids and derivatives thereof.
  • the at least one compound selected from unsaturated carboxylic acids and derivatives thereof includes maleic anhydride.
  • the crystalline ethylene resin is a polymer containing 50% by mass or more of monomer units derived from ethylene with a mass of the crystalline ethylene resin of 100% by mass and a ⁇ H of greater than 40 J / g.
  • Examples of the crystalline ethylene resin include high-density polyethylene, high-pressure low-density polyethylene, and ethylene- ⁇ -olefin copolymer.
  • the crystalline ethylene resin may be modified with at least one compound selected from unsaturated carboxylic acids and derivatives thereof.
  • the at least one compound selected from unsaturated carboxylic acids and derivatives thereof includes maleic anhydride. These resins may be used alone or in combination of two or more.
  • the crystalline thermoplastic resin (C) may be cross-linked.
  • the total amount of the thermoplastic resin in the thermoplastic resin composition is 100% by mass, and the content of the crystalline thermoplastic resin (C) is 0.
  • the content is preferably 0.01 to 9% by mass, more preferably 0.01 to 8% by mass, and still more preferably 0.01 to 6% by mass.
  • the total amount of the thermoplastic resin in the thermoplastic resin composition is 100% by mass, and the content of the crystalline thermoplastic resin (C) is as follows.
  • the content is preferably 0 to less than 0.01% by mass.
  • thermoplastic resin composition of the present invention if necessary, an antioxidant, an ultraviolet absorber, a crosslinking agent, a thermal stabilizer, a photodegradation inhibitor, an impact modifier, a plasticizer, a lubricant, a mold release agent, Nucleating agents, halogen-based flame retardants and non-halogen (polyphosphoric acid-based, red phosphorus-based, etc.) flame retardants, flame retardant aids, colorants such as pigments and dyes, mineral oil-based softeners, foaming agents, processing aids, An antistatic material or the like may be added.
  • an antioxidant an ultraviolet absorber, a crosslinking agent, a thermal stabilizer, a photodegradation inhibitor, an impact modifier, a plasticizer, a lubricant, a mold release agent, Nucleating agents, halogen-based flame retardants and non-halogen (polyphosphoric acid-based, red phosphorus-based, etc.) flame retardants, flame retardant aids, colorants such as pigments and dye
  • the total amount of the thermoplastic resin composition of the present invention is 100% by mass, and the total content of the amorphous thermoplastic resin (A), the amorphous thermoplastic resin (B), and the crystalline thermoplastic resin (C).
  • the amount is preferably 90% by mass or more, more preferably 91% by mass or more, further preferably 95% by mass or more, and further preferably 98% by mass or more.
  • thermoplastic resin composition and molded article are also included.
  • Amorphous thermoplastic resin (A) having a weight average molecular weight of 50,000 to 500,000 and a molecular weight distribution of 1.0 to 3.5, and a weight average molecular weight of 500 to 50, Amorphous thermoplastic resin (B) that is less than 000, no filler, and the total amount of the amorphous thermoplastic resin (A) and the amorphous thermoplastic resin (B).
  • Amorphous thermoplastic resin (A) having a weight average molecular weight of 50,000 to 500,000 and a molecular weight distribution of 1.0 to 3.5, and a weight average molecular weight of 500 to 50
  • Amorphous thermoplastic resin (B) that is less than 000, no filler, and the total amount of the amorphous thermoplastic resin (A) and the amorphous thermoplastic resin (B).
  • the content of the amorphous thermoplastic resin (A) is 25 mass% or more and 85 mass% or less
  • Thermoplastic resin composition satisfying the following requirement (1) and requirement (2): Requirement (1)
  • the glass transition temperature of the thermoplastic resin composition is 0 ° C. or higher and 200 ° C. or lower; and Requirement (2)
  • the haze of a 1 mm thick sheet made of the thermoplastic resin composition is less than 8.0% It is.
  • the thermoplastic resin composition further contains a crystalline thermoplastic resin (C),
  • the thermoplastic resin composition according to [4] wherein the total amount of the thermoplastic resin in the thermoplastic resin composition is 100% by mass, and the content of the crystalline thermoplastic resin (C) is 0.01 to 9% by mass. object.
  • a molded article comprising the thermoplastic resin composition according to [4] or [5].
  • the filler include inorganic fillers and organic fillers.
  • the thermoplastic resin composition is obtained by melt-mixing an amorphous thermoplastic resin (A), an amorphous thermoplastic resin (B), and a crystalline thermoplastic resin (C) as necessary. can get.
  • the method of melt mixing is not particularly limited, and examples thereof include known mixing methods, for example, a mixing method using an extruder, an open roll mill, a Banbury mixer, a kneader, or a melt mixing tank.
  • the temperature at the time of melt mixing is usually from 100 to 250 ° C., preferably from 130 to 200 ° C.
  • the molded body composed of the thermoplastic resin composition can self-repair not only the surface of the molded body but also the internal damage of the molded body.
  • the shape of the molded body includes a sheet, mat, film, pipe, tube, container, net, fiber, connector and the like.
  • Examples of the method for producing the molded body include injection molding, injection compression molding, press molding, and extrusion molding.
  • thermoplastic resin composition may be dissolved in a good solvent and used as a coating liquid.
  • a coating film formed by applying the coating liquid to a substrate and removing the solvent from the obtained coating film is also an example of the molded body.
  • the sheet composed of the thermoplastic resin composition may be used as a single layer, or the sheet composed of the thermoplastic resin composition is used as at least one layer. You may use as a multilayer sheet containing.
  • the multilayer sheet is a multilayer sheet having three or more layers, an adhesive layer may be provided as one layer.
  • the thickness of the sheet made of the thermoplastic resin composition is not particularly limited, but is usually 0.5 to 500 mm. In a multilayer sheet including the sheet made of the thermoplastic resin composition as at least one layer, the thickness of the layer made of the sheet made of the thermoplastic resin composition is usually 0, with the thickness of the multilayer sheet being 100%. 0.01 to 99.99%.
  • the film made of the thermoplastic resin composition may be used as a single layer, or the film made of the thermoplastic resin composition is used as at least one layer. It may be used as a multilayer film.
  • an adhesive layer may be provided as one layer.
  • the thickness of the film made of the thermoplastic resin composition is not particularly limited, but is usually 10 to 500 ⁇ m. In a multilayer film including the film composed of the thermoplastic resin composition as at least one layer, the thickness of the multilayer film is 100%, and the thickness of the layer composed of the film composed of the thermoplastic resin composition is usually 0. 0.01 to 99.99%.
  • the layer composed of the film or sheet made of the thermoplastic resin composition of the present invention is applied by applying a coating liquid containing the thermoplastic resin composition of the present invention to the substrate. It may be a layer formed by removing the solvent from the film.
  • the resin constituting the layer different from the layer composed of the film or sheet made of the thermoplastic resin composition of the present invention includes olefin resin, acrylic resin, styrene / acrylonitrile resin, polysulfone.
  • the olefin resin include ethylene resin, propylene resin, polybutene resin, and poly (4-methyl-1-pentene) resin.
  • the olefin resin may be modified with at least one compound selected from unsaturated carboxylic acids and derivatives thereof.
  • the olefin resin may be an amorphous olefin resin or a crystalline olefin resin.
  • the ethylene resin include high-density polyethylene, high-pressure low-density polyethylene, ethylene- ⁇ -olefin copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene -Methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-glycidyl methacrylate copolymer, ethylene-acrylic acid ester-glycidyl methacrylate copolymer.
  • styrene / acrylonitrile resin examples include polystyrene, styrene-acrylonitrile copolymer, and styrene-acrylonitrile-butadiene copolymer.
  • polyester resin examples include polyethylene terephthalate and polybutylene terephthalate.
  • Rubbers include natural rubber, polybutadiene rubber, polyacrylonitrile rubber, acrylonitrile-butadiene copolymer rubber, partially hydrogenated acrylonitrile-butadiene copolymer rubber, butyl rubber, chloroprene rubber, fluoro rubber, chlorosulfonated polyethylene, silicon rubber, Examples thereof include urethane rubber, isobutylene-isoprene copolymer rubber, halogenated isobutylene-isoprene copolymer rubber, chlorinated rubber, and styrene rubber.
  • Examples of the method for producing the multilayer film or multilayer sheet include a coextrusion inflation molding method, a coextrusion T-die casting molding method, a dry laminating method, a wet laminating method, a sand laminating method, and a hot melt laminating method.
  • the molded body may be subjected to surface treatment such as corona discharge treatment, flame treatment, plasma treatment, ozone treatment on the surface of the molded body. Moreover, in the manufacturing method of said multilayer film or multilayer sheet, you may perform the said surface treatment to at least one layer before lamination
  • the molded body may be coated on the surface of the molded body.
  • Coating treatment includes antistatic treatment, insulating treatment, conductive treatment, antiglare treatment, antireflection treatment, antifogging treatment, rustproofing treatment, waterproof treatment, antifouling treatment, antibacterial treatment, water repellent treatment, hydrophilic treatment, oil repellent treatment Treatment, water / oil repellency treatment, hydrophilic / lipophilic treatment, hard coat treatment, gas barrier treatment, sound absorption / vibration treatment, high refractive index treatment, scratch resistance treatment, weather resistance treatment, mold release treatment, biocompatibility treatment, etc. .
  • molded product of the present invention will be described below. Specific applications include sealing materials, heat insulation materials, soundproofing materials, shoe soles, packaging materials, coating materials, patches, bandages, hose clips, fluid transport pipes, flexible hoses, asphalt additives, hot melt adhesives, and adhesives Additives for agents, articles that generally need to exhibit good fracture resistance and / or fatigue resistance, and the like.
  • Optical applications include optical films, optical sheets, optical filters, high-intensity prism sheets, optical condensing spheres, antireflection optical articles, light controllable laminates, transparent daylighting materials, antiglare films, protective films, and pen input. Examples include surface materials for devices.
  • Electrical equipment relations include electrical cables, sheaths, wire coating materials, electrical insulation members, electronic equipment casings, machine parts, vibration-resistant fatigue members, capacitors, solid electrolytes, and the like.
  • Tire materials include tire tubes and tire puncture sealing.
  • Others include fiber reinforced materials, rust preventives, corrosion inhibitors, spray pigments, paints such as barrier materials (organic matter, gas, humidity), pet building materials, building materials such as floors, walls, doors, waterproof sheets, waterproofing Sheet, Actuator, Cleaning pad, Automobile material, Artificial leather, Synthetic leather, Artificial skin, Endovascular stent, Septum, Dental composite restoration material, Sleeve material, Laminated glass, Transfer foil, Flame retardant film, Writing instrument shaft Tube, cushion material, cushioning agent, agricultural film, decorative film, decorative sheet, greenhouse sheet, insect net, furniture, clothes, bag, shoes, sports equipment, container, cutting board, cutting board, antibacterial film, antibacterial molding Body, barrier film, packing and the like.
  • barrier materials organic matter, gas, humidity
  • pet building materials building materials such as floors, walls, doors, waterproof sheets, waterproofing Sheet, Actuator, Cleaning pad
  • Automobile material Artificial leather, Synthetic leather, Artificial skin, Endovascular stent, Septum, Dental composite restoration material, Sleeve material, Laminated glass, Transfer foil, Flame retardant film
  • the melting curve was analyzed by a method based on JIS K7121, and the melting point and glass transition temperature were determined.
  • the melting enthalpy ⁇ H (J / g) was obtained by analyzing the melting curve by a method based on JIS K7122.
  • Melt flow rate (MFR, unit: g / 10 minutes) According to the method defined in JIS K7210, measurement was performed by the A method under the conditions of a load of 21 N and a temperature of 190 ° C. or 230 ° C.
  • a press sheet (thickness: 1 mm) of the resin composition
  • the obtained composition was sandwiched between a PET film or a release PET film, an aluminum plate, and a steel plate, and a hot press at 190 ° C. for 5 minutes. After preheating, the pressure was applied for 5 minutes. After completion of pressurization, the sheet was cooled with a cooling press at 30 ° C. to obtain a press sheet. At this time, the thickness of the press sheet was adjusted to 1 mm using a steel spacer.
  • Each test piece was subjected to a tensile test using a tensile testing machine (RTF-1325-PL-WS, manufactured by A & D) at a distance between grips of 60 mm and a speed of 100 mm / min. The measurement was performed at a temperature of 23 ° C. ⁇ 2 ° C. and a humidity of 50% ⁇ 5%. In addition, the said tension test was complete
  • a tensile testing machine RTF-1325-PL-WS, manufactured by A & D
  • Repair rate (%) ((Elongation when cutting a sample after repair) ⁇ (Elongation when cutting a damaged sample)) / ((Elongation when cutting without a scratch) ⁇ (Elongation when cutting with a wound)) ⁇ 100
  • the repair rate calculated by measuring elongation at break using a test piece heated at 40 ° C. for 17 hours in a blow dryer is referred to as a repair rate (40 ° C.).
  • the repair rate calculated by measuring the elongation at break using a test piece heated at 80 ° C. for 17 hours in a blow dryer is referred to as the repair rate (80 ° C.).
  • the reaction mixture was continuously withdrawn so that the reaction mixture in the polymerization vessel maintained an amount of 100 L.
  • dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride as a component of the polymerization catalyst at a supply rate of 0.005 g / hour
  • Triphenylmethyltetrakis (pentafluorophenyl) borate was continuously fed at a feed rate of 0.298 g / hr and triisobutylaluminum was fed at a feed rate of 2.315 g / hr.
  • the copolymerization reaction was carried out at 45 ° C. by circulating cooling water through a jacket attached to the outside of the polymerization vessel. A small amount of ethanol was added to the reaction mixture continuously extracted from the upper part of the polymerization vessel to stop the polymerization reaction, and then the monomer was removed and washed with water. Next, the solvent was removed with steam in a large amount of water, and further dried under reduced pressure at 80 ° C. for 24 hours to obtain an amorphous propylene-1-butene copolymer. The production rate of the copolymer was 7.10 kg / hour.
  • n-butyllithium n-hexane solution (Tokyo Chemical Industry Co., Ltd., n-butyllithium concentration 1.6 mol / L) until it is colored, scavenge impurities contained in the system, add 0.05 mL, 30 Polymerization was started by raising the temperature to 0 ° C. After 300 minutes, 1 mL of Echinen F-6 (Nihon Alcohol Sales) was added to stop the polymerization. After the termination of the polymerization, 600 mL of toluene was added to the tetrahydrofuran solution containing the polymer, and the resulting solution was washed with about 500 mL of pure water until the solution became neutral.
  • Echinen F-6 Nehon Alcohol Sales
  • the polymer was precipitated by adding the washing liquid into Echinen F-6, and the polymer separated by filtration was further washed twice with Echinen F-6.
  • the obtained polymer was vacuum dried at 80 ° C. to obtain 35 g of a polymer.
  • the MFR could not be measured because the sample did not flow under the conditions of 190 ° C. and 21N.
  • Example 1 39% by mass of the amorphous propylene-1-butene copolymer produced in Synthesis Example 1 as the amorphous thermoplastic resin (A), and the hydrogenated terpene resin “Clearon P— as the amorphous thermoplastic resin (B).
  • Example 2 48% by mass of the amorphous propylene-1-butene copolymer produced in Synthesis Example 1 as the amorphous thermoplastic resin (A), and the hydrogenated terpene resin “Clearon P— as the amorphous thermoplastic resin (B).
  • 150 (manufactured by Yasuhara Chemical Co., Ltd.) 48% by mass, and 4% by mass of“ Sumitomo Nobrene FLX80E4 ” was used as the crystalline thermoplastic resin (C).
  • MFR of the obtained resin composition was 22 g / 10min (190 degreeC, 21N), and Tg was 9.1 degreeC.
  • the press sheet produced from the obtained resin composition was punchable, and the repair rate (80 ° C.) was 74%, the repair rate (40 ° C.) was 0%, the Young's modulus was 250 MPa, and the haze was 4.0%.
  • Example 3 57% by mass of the amorphous propylene-1-butene copolymer produced in Synthesis Example 1 as the amorphous thermoplastic resin (A), and the hydrogenated terpene resin “Clearon P— as the amorphous thermoplastic resin (B).
  • MFR of the obtained resin composition was 15 g / 10min (190 degreeC, 21N), and Tg was 5.0 degreeC.
  • the press sheet produced from the obtained resin composition was punchable, and the repair rate (80 ° C.) was 100%, the repair rate (40 ° C.) was 40%, the Young's modulus was 35 MPa, and the haze was 3.7%.
  • Example 4 Styrene-isoprene-styrene block copolymer “Hibler 5127” (manufactured by Kuraray Co., Ltd.) 60% by mass as the amorphous thermoplastic resin (A), hydrogenated terpene resin “Clearon P” as the amorphous thermoplastic resin (B) The same procedure as in Example 1 was carried out except that 40% by mass of “ ⁇ 105” was used. MFR of the obtained resin composition was 54 g / 10min (190 degreeC, 21N), and Tg was 19.3 degreeC. The press sheet produced from the obtained resin composition was punchable, and the repair rate (80 ° C.) was 61%, Young's modulus 374 MPa, and haze 7.8%.
  • Example 5 Hydrogenated styrene-isoprene-styrene block copolymer “HIBLER 7311F” (manufactured by Kuraray Co., Ltd.) 40% by mass as the amorphous thermoplastic resin (A), hydrogenated terpene resin “Amorphous thermoplastic resin (B)” The same procedure as in Example 1 was performed except that 60% by mass of Clearon P-150 was used. MFR of the obtained resin composition was 37 g / 10min (190 degreeC, 21N), and Tg was 19.4 degreeC. The press sheet produced from the obtained resin composition was punchable, and the repair rate (80 ° C.) was 97%, Young's modulus 556 MPa, and haze 2.6%.
  • Example 3 84% by mass of the amorphous propylene-1-butene copolymer produced in Synthesis Example 1 as the amorphous thermoplastic resin (A), and the hydrogenated terpene resin “Clearon P— as the amorphous thermoplastic resin (B).
  • Example 10 was carried out in the same manner as in Example 1 except that 9% by mass of 105 ”and 7% by mass of“ Sumitomo Nobrene FLX80E4 ”were used as the crystalline thermoplastic resin (C).
  • the obtained resin composition had an MFR of 6.2 g / 10 min (190 ° C., 21 N), and a Tg of ⁇ 7.5 ° C.
  • the press sheet produced from the obtained resin composition had high adhesiveness, was not stampable, and the repair rate could not be measured.
  • the haze was 9.2%.
  • Example 4 50% by mass of propylene resin “Best Plast 703” (manufactured by Evonik) as amorphous thermoplastic resin (A) and 50% by mass of hydrogenated terpene resin “Clearon P-150” as amorphous thermoplastic resin (B)
  • the same operation as in Example 1 was carried out except that it was used.
  • the obtained resin composition had an MFR of 2000 g / 10 min (190 ° C., 21 N) or more, and a Tg of ⁇ 2.5 ° C.
  • the press sheet produced from the obtained resin composition was cracked at the time of punching, and the repair rate could not be measured.
  • the haze was 15.6%.
  • amorphous thermoplastic resin (A) 50% by mass of propylene resin “Best Plast 708” (Evonik) and 50% by mass of hydrogenated terpene resin “Clearon P-150” as amorphous thermoplastic resin (B).
  • the same operation as in Example 1 was carried out except that it was used.
  • the obtained resin composition had an MFR of 2000 g / 10 min (190 ° C., 21 N) or more, and a Tg of ⁇ 5.3 ° C.
  • the press sheet produced from the obtained resin composition was cracked at the time of punching, and the repair rate could not be measured.
  • the haze was 56.4%.
  • Example 6 50% by mass of propylene resin “Best Plast 792” (manufactured by Evonik) as amorphous thermoplastic resin (A), and 50% by mass of hydrogenated terpene resin “Clearon P-150” as amorphous thermoplastic resin (B)
  • the same operation as in Example 1 was carried out except that it was used.
  • the obtained resin composition had an MFR of 904 g / 10 min (190 ° C., 21 N), and a Tg of ⁇ 3.1 ° C.
  • the press sheet produced from the obtained resin composition was cracked at the time of punching, and the repair rate could not be measured.
  • the haze was 55.0%.
  • the obtained resin composition had an MFR of 124 g / 10 min (190 ° C., 21 N), and a Tg of 5.0 ° C.
  • the press sheet produced from the obtained resin composition was punchable, and the repair rate (80 ° C.) was 0%, Young's modulus 118 MPa, and haze 8.3%.
  • the obtained resin composition had an MFR of 5 g / 10 min (190 ° C., 21 N), and a Tg of ⁇ 13.9 ° C.
  • the press sheet produced from the obtained resin composition was punchable, and the repair rate (80 ° C.) was 0%, Young's modulus 70 MPa, and haze 10.0%.
  • amorphous thermoplastic resin (A) 41% by mass of the amorphous propylene-1-butene copolymer produced in Synthesis Example 1, and as the amorphous thermoplastic resin (B), a hydrogenated petroleum resin “Alcon P— 90 "(Arakawa Chemical Industries, Ltd.) 45% by mass, 4% by mass of Sumitomo Nobrene FLX80E4 as crystalline thermoplastic resin (C), and 10% by mass of petroleum wax” Paraffin Wax 155 "(Nippon Seiwa Co., Ltd.) The same procedure as in Example 1 was performed except that% was used. MFR of the obtained resin composition was 132 g / 10min (190 degreeC, 21N). The haze of the press sheet produced from the obtained resin composition was 77.2%.
  • MFR of the obtained resin composition was 196 g / 10min (190 degreeC, 21N), and Tg was 2.2 degreeC.
  • the press sheet produced from the obtained resin composition was punchable, and the repair rate (80 ° C.) was 0%, Young's modulus 1100 MPa, and haze 36.1%.
  • thermoplastic resin (A) As the amorphous thermoplastic resin (A), 5.6% by mass of the propylene resin “Tough Selenium X1107”, as the amorphous thermoplastic resin (B), 55.5% by mass of the hydrogenated terpene resin “Clearon P-125”, crystalline Example except that 16.7% by mass of crystalline propylene resin “Wintech WFX4” and 22.2% by mass of crystalline propylene resin “Biscol 660P” (manufactured by Sanyo Chemical Industries, Ltd.) were used as the thermoplastic resin (C). 1 was carried out. The MFR of the obtained resin composition was 2000 g / 10 min (190 ° C., 21 N) or more. The press sheet produced from the obtained resin composition was cracked at the time of punching, and the repair rate could not be measured. The haze was 3.7%.
  • the same procedure as in Example 1 was performed except that 12% by mass of petroleum-based wax “paraffin wax 155” (manufactured by Nippon Seiwa Co., Ltd.) was used as (C).
  • the obtained resin composition had an MFR of 1183 g / 10 min (190 ° C., 21 N), and a Tg of ⁇ 16.9 ° C.
  • the press sheet produced from the obtained resin composition was punchable, and the repair rate (80 ° C.) was 0%, Young's modulus 39 MPa, and haze 88.8%.
  • Example 14 45% by mass of propylene resin “Best Plast 792” as amorphous thermoplastic resin (A), 45% by mass of hydrogenated petroleum resin “Alcon P-90” as amorphous thermoplastic resin (B), crystalline thermoplastic resin
  • the same procedure as in Example 1 was performed except that 10% by mass of petroleum-based wax “paraffin wax 155” (manufactured by Nippon Seiwa Co., Ltd.) was used as (C).
  • the obtained resin composition had an MFR of 2000 g / 10 min (190 ° C., 21 N) or more and a Tg of ⁇ 12.8 ° C.
  • the press sheet produced from the obtained resin composition had high adhesiveness, was not stampable, and the repair rate could not be measured.
  • the haze was 31.4%.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

La présente invention décrit : une composition de résine thermoplastique qui comprend une résine thermoplastique amorphe (A) ayant un poids moléculaire moyen en poids de 50 000 à 500 000 et une distribution des poids moléculaires de 1,0 à 3,5 et une résine thermoplastique amorphe (B) ayant un poids moléculaire moyen en poids de 500 ou plus mais inférieur à 50 000 et, lorsque la quantité totale de la résine thermoplastique amorphe (A) et de la résine thermoplastique amorphe (B) représente 100 % en masse, alors la teneur de la résine thermoplastique amorphe (A) est de 25 à 85 % en masse et la teneur de la résine thermoplastique amorphe (B) est de 15 à 75 % en masse, la composition satisfaisant les exigences suivantes (1) et (2) ; et un objet moulé comprenant la composition de résine thermoplastique. Exigence (1) : la composition de résine thermoplastique présente une température de transition vitreuse de 0 à 200 °C. Exigence (2) : une feuille d'une épaisseur de 1 mm formée à partir de la composition de résine thermoplastique présente un trouble inférieur à 8,0 %.
PCT/JP2017/013332 2016-03-31 2017-03-30 Composition de résine thermoplastique et son objet moulé Ceased WO2017170903A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021070729A (ja) * 2019-10-29 2021-05-06 パナソニックＩｐマネジメント株式会社 樹脂組成物及び成形体
WO2021230241A1 (fr) * 2020-05-11 2021-11-18 国立大学法人 東京大学 Matériau polymère auto-cicatrisant

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WO2004067627A1 (fr) * 2003-01-27 2004-08-12 Mitsui Chemicals, Inc. Composition polymere de propylene et son utilisation
WO2006123759A1 (fr) * 2005-05-18 2006-11-23 Mitsui Chemicals, Inc. Catalyseur pour la polymerisation d'olefine, procede de production d’une polyolefine, procede de production d’un copolymere de propylene, polypropylene, composition de polypropylene, et leur utilisation
JP2011222562A (ja) * 2010-04-02 2011-11-04 Tokyo Ohka Kogyo Co Ltd 剥離方法、および剥離液
JP2015189802A (ja) * 2014-03-27 2015-11-02 株式会社ダイセル シート状透明封止材及びその製造方法

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WO2004067627A1 (fr) * 2003-01-27 2004-08-12 Mitsui Chemicals, Inc. Composition polymere de propylene et son utilisation
WO2006123759A1 (fr) * 2005-05-18 2006-11-23 Mitsui Chemicals, Inc. Catalyseur pour la polymerisation d'olefine, procede de production d’une polyolefine, procede de production d’un copolymere de propylene, polypropylene, composition de polypropylene, et leur utilisation
JP2011222562A (ja) * 2010-04-02 2011-11-04 Tokyo Ohka Kogyo Co Ltd 剥離方法、および剥離液
JP2015189802A (ja) * 2014-03-27 2015-11-02 株式会社ダイセル シート状透明封止材及びその製造方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021070729A (ja) * 2019-10-29 2021-05-06 パナソニックＩｐマネジメント株式会社 樹脂組成物及び成形体
WO2021230241A1 (fr) * 2020-05-11 2021-11-18 国立大学法人 東京大学 Matériau polymère auto-cicatrisant
JPWO2021230241A1 (fr) * 2020-05-11 2021-11-18
JP7468932B2 (ja) 2020-05-11 2024-04-16 国立大学法人 東京大学 自己修復性ポリマー材料

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