WO2016104306A1 - Composition de résine thermoplastique - Google Patents

Composition de résine thermoplastique Download PDF

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Publication number
WO2016104306A1
WO2016104306A1 PCT/JP2015/085304 JP2015085304W WO2016104306A1 WO 2016104306 A1 WO2016104306 A1 WO 2016104306A1 JP 2015085304 W JP2015085304 W JP 2015085304W WO 2016104306 A1 WO2016104306 A1 WO 2016104306A1
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WO
WIPO (PCT)
Prior art keywords
resin composition
thermoplastic resin
less
polymer block
thermoplastic
Prior art date
Application number
PCT/JP2015/085304
Other languages
English (en)
Japanese (ja)
Inventor
温諮 牧野
岳洋 宮本
Original Assignee
クラレプラスチックス株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by クラレプラスチックス株式会社 filed Critical クラレプラスチックス株式会社
Publication of WO2016104306A1 publication Critical patent/WO2016104306A1/fr

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Classifications

    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/28—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

Definitions

  • the present invention relates to a thermoplastic resin composition that is lightweight and excellent in flexibility.
  • thermoplastic resin composition containing a conventional glass balloon has a problem in that the glass balloon is destroyed by kneading or molding methods, and the material cannot be sufficiently reduced in weight. Therefore, in Patent Document 1, it is said that the weight can be reduced by blending a specific glass balloon, but the content of the crystalline propylene polymer is large, the hardness of the resulting molded body is high, and there is no flexibility, Sufficient anti-slip properties were not obtained when used for stationery, tools, and sports equipment.
  • Patent Document 4 a glass-containing molding pellet in which a specific amount of glass balloon is blended is proposed, but the blending amount of the glass balloon is large, the surface becomes hard, and the slip resistance deteriorates.
  • Japanese Patent No. 3193433 Japanese Patent Laid-Open No. 7-3073 Japanese Patent No. 5013739 Japanese Patent No. 4320372
  • thermoplastic composition that is lightweight, excellent in flexibility, and excellent in slip resistance.
  • a glass balloon having a specific range of true density, compressive strength, median diameter, and glass bulb thickness with respect to a thermoplastic elastomer having a specific range of weight average molecular weight By using a resin composition containing a specific amount of a softener and a polyolefin resin, a molded product produced by molding the resin composition is lightweight, flexible, and has sufficient slip resistance.
  • the headline and the present invention were completed.
  • the present invention hydrogenates a block copolymer having a polymer block (A) composed of an aromatic vinyl compound in the molecule and a polymer block (B) composed of a conjugated diene compound in the molecule.
  • the thermoplastic elastomer (a) which is a hydrogenated block copolymer obtained by the above process, has a true density of 0.6 g / cm 3 or less, a pressure strength of 100 MPa or more, a median diameter of less than 30 ⁇ m, and a glass sphere thickness of 0.4-0.
  • thermoplastic resin composition characterized in that, in addition to the above (a), (b), (c), further olefin resin d) the above thermoplastic resin composition, wherein the thermoplastic elastomer (a) comprises at least two polymer blocks (A) mainly comprising an aromatic vinyl compound, and a mixture of isoprene and butadiene.
  • thermoplastic resin which is a hydrogenated triblock copolymer composed of a polymer block (B) mainly composed of one conjugated diene compound, and has a weight average molecular weight of 150,000 or more in terms of polystyrene It is a composition.
  • thermoplastic composition that is lightweight, excellent in flexibility, and has sufficient slip resistance.
  • the thermoplastic resin composition of the present invention has a block copolymer having a polymer block (A) composed of an aromatic vinyl compound in the molecule and a polymer block (B) composed of a conjugated diene compound in the molecule.
  • Thermoplastic elastomer (a) which is a hydrogenated block copolymer obtained by hydrogenating the coalescence, has a true density of 0.6 g / cm 3 or less, a pressure strength of 100 MPa or more, a median diameter of less than 30 ⁇ m, and a glass bulb thickness of 0. It contains a glass balloon (b) of 4 to 0.8 ⁇ m and a hydrocarbon rubber softener (c), more preferably an olefin resin (d).
  • the thermoplastic elastomer (a) of the present invention comprises a polymer block comprising an aromatic vinyl compound in the molecule, preferably a polymer block (A) mainly comprising at least two aromatic vinyl compounds, and conjugated in the molecule. It is obtained by hydrogenating a block copolymer comprising a polymer block (B) containing a diene compound.
  • the vinyl aromatic compound include styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene, vinylanthracene and the like. Of these, styrene and ⁇ -methylstyrene are preferred.
  • An aromatic vinyl compound may be used individually by 1 type, and may use 2 or more types together.
  • the content of the vinyl aromatic compound in the thermoplastic elastomer (a) is preferably 5 to 75% by mass, and more preferably 5 to 50% by mass. When the content of the vinyl aromatic compound is within this range, the rubber elasticity of the thermoplastic elastomer composition of the present invention is further improved.
  • conjugated diene compound examples include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like.
  • a conjugated diene compound may be used individually by 1 type, and may use 2 or more types together.
  • the conjugated diene compound is preferably at least one selected from isoprene and butadiene, and a mixture of isoprene and butadiene is more preferable.
  • 50% or more of carbon-carbon double bonds derived from the conjugated diene compound of the polymer block (B) are preferably hydrogenated, and 75% or more are hydrogenated. More preferably, 95% or more is hydrogenated.
  • the thermoplastic elastomer (a) may contain at least one polymer block (A) and polymer block (B). From the viewpoint of heat resistance, mechanical properties, etc., the polymer block ( It is preferable that two or more A) and one or more polymer blocks (B) are contained.
  • the bonding mode of the polymer block (A) and the polymer block (B) may be linear, branched, or any combination thereof.
  • the polymer block (A) is A, and the polymer block ( when representing the B) in B, and triblock structure represented by a-B-a, (a -B) n, (a-B) n -A, n represents an integer of 2 or more (here) Among them, a triblock structure represented by ABA is particularly preferable in view of heat resistance, mechanical properties, handling properties, and the like.
  • the weight average molecular weight of the thermoplastic elastomer (a) is preferably in the range of 150,000, and if it is less than 150,000, the thermoplastic elastomer (a) has an adhesive property, and a tactile sensation with a balance between anti-slip property and adhesive property cannot be obtained.
  • the weight average molecular weight as used in this specification means the weight average molecular weight of standard polystyrene conversion calculated
  • Measurement condition GPC; LC Solution (manufactured by SHIMADZU) Detector: differential refractometer RID-10A (manufactured by SHIMADZU) Column: TSKgel G4000Hxl in series (made by TOSOH) Guard column: TSK guard column Hxl-L (manufactured by TOSOH) Solvent: Tetrahydrofuran Temperature: 40 ° C Flow rate: 1 ml / min Concentration: 2 mg / ml
  • the glass balloon of the present invention is a glass balloon having a true density of 0.6 g / cm 3 or less, a pressure strength of 100 MPa or more, a median diameter of less than 30 ⁇ m, and a glass bulb thickness of 0.4 to 0.8 ⁇ m. . If the glass thickness is less than 0.4 ⁇ m, cracking occurs in the kneading or forming process, and thus a light weight effect cannot be obtained. When the glass thickness is larger than 0.8 ⁇ m, the specific gravity becomes heavy, so that the light weight effect cannot be obtained. When the true density is greater than 0.6 g / cm 3 , the specific gravity increases, so that the light weight effect cannot be obtained.
  • the pressure strength is less than 100 MPa, cracking occurs in the kneading and molding processes, and thus the light weight effect cannot be obtained. Further, when the median diameter is 30 ⁇ m or more, it feels slippery and the slip resistance is poor. True density, from the viewpoint of weight reduction, preferably of less than 0.6 g / cm 3, of less than 0.5 g / cm 3 is more preferable.
  • the pressure strength is preferably 100 MPa or more, more preferably 110 MPa or more, from the viewpoint of weight reduction.
  • the median diameter is preferably 30 ⁇ m or less, more preferably 20 ⁇ m, from the viewpoint of anti-slip properties.
  • the glass sphere thickness is preferably 0.4 to 0.8 ⁇ m and more preferably 0.5 to 0.7 ⁇ m from the viewpoint of weight reduction.
  • thermoplastic resin composition of the present invention further needs to contain a hydrocarbon rubber softener (c).
  • hydrocarbon rubber softener (c) of the present invention include process oils such as paraffinic oil, naphthenic oil, and aroma oil, liquid paraffin, and the like. Among them, paraffinic oil, naphthenic oil, etc. Process oil is preferred. These may be used alone or in combination of two or more.
  • the olefin resin (d) may be contained in the thermoplastic resin composition of the present invention.
  • the olefin resin (d) is preferably a propylene polymer or an ethylene polymer.
  • the propylene polymer for example, homopolypropylene, random polypropylene, block polypropylene, atactic polypropylene, syndiotactic polypropylene and the like can be used. Among them, it is preferable to use random polypropylene, block polypropylene, or homopolypropylene.
  • ethylene polymer examples include ethylene homopolymers such as medium density polyethylene, low density polyethylene (LDPE), and high density polyethylene (HDPE); ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, Ethylene / 1-heptene copolymer, ethylene / 1-octene copolymer, ethylene / 4-methyl-1-pentene copolymer, ethylene / 1-nonene copolymer, ethylene / 1-decene copolymer, etc.
  • An ethylene / ⁇ -olefin copolymer or the like can be used.
  • thermoplastic resin composition of the present invention includes various anti-blocking agents, heat stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, lubricants, crystal nucleating agents, foaming depending on applications. It is also possible to contain a coloring agent, a coloring agent and the like.
  • antioxidants for example, 2,6-ditert-butyl-p-cresol, 2,6-ditert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 4,4′- Dihydroxydiphenyl, tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, tetrakis [methylene-3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate] methane, 3,9 -Bis ⁇ 2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl ⁇ -2,4,8,10-tetraoxaspiro-5, Phenolic antioxidants such as 5-undecane, phosphite antioxidants, thioether antioxidants, and the like can be used.
  • the antioxidant is preferably 0.01 to 3.0 parts by mass with respect to 100 parts by mass in total of the components (A) to (D) contained in the thermoplastic resin composition of the present invention. More preferably, the content is 0.05 to 1.0 part by mass.
  • thermoplastic resin composition in the present invention needs to be adjusted so that the A type durometer hardness according to JIS K6253 is 20 to 70 from the viewpoint of flexibility and anti-slip properties. It is preferable to adjust so that it becomes, and it is more preferable to adjust so that it may become 30-60.
  • thermoplastic resin composition in the present invention needs to be adjusted so that the specific gravity according to JIS K7112 is 0.85 or less from the viewpoint of weight reduction, and is adjusted to 0.80. Is preferable, and it is more preferable to adjust so that it may become 0.75.
  • thermoplastic resin composition As a method for producing the thermoplastic elastomer composition in the present invention, a conventional resin composition or a rubber composition can be used. A single screw extruder, a twin screw extruder, a Banbury mixer. It can be produced by uniformly compounding each component using a melt kneader such as a heating roll or various kneaders. The set temperature of the processing machine can be arbitrarily selected from 150 ° C to 300 ° C.
  • thermoplastic resin composition of the present invention can be obtained by using various molding methods, for example, extrusion molding, injection molding, hollow molding, compression molding, calendar molding, and any other method such as sheet, film, and tube. It can be formed into a shaped molded body.
  • thermoplastic resin composition of the present invention can also be made into a composite molded body formed by compounding with other materials such as plastic and fabric by two-color molding method, insert molding method, co-extrusion and the like.
  • thermoplastic resin composition of the present invention can be used as a raw material for various industrial products and industrial parts.
  • automotive interior parts such as instrument panels, center panels, center console boxes, and handles; remote control switches, various key tops for office automation equipment, televisions, stereos, refrigerators, vacuum cleaners, etc .; sports shoes, fashion sandals It can be used for parts such as stationery, tools, bicycle handles, scissors handles, knife handles, frying pan handles, door handles, tennis rackets, and jumpers.
  • Hardness Hardness was measured by a durometer A hardness measurement method in accordance with JIS K 6253.
  • Specific gravity Specific gravity was measured according to JIS K7112.
  • Adhesiveness Targeting 10 people the adhesiveness when lightly grasping an injection molded sheet was evaluated. 8-10 people rated it as non-sticky: ⁇ Five to seven people rated it as non-sticky: ⁇ Two to four people rated it as non-sticky: ⁇ 0-4 people rated as non-sticky: ⁇ (4) Anti-slip property
  • the coefficient of friction was measured according to JIS K 7125. The higher the coefficient of friction, the better the slip resistance.
  • thermoplastic elastomer (a) which is a hydrogenated block copolymer obtained by hydrogenation, is a true density of 0.6 gcm / cm 3 or less, a pressure strength of 100 MPa or more, a median diameter of less than 30 ⁇ m, and a glass sphere thickness of 0
  • a thermoplastic resin composition characterized by containing a glass balloon (b) having a diameter of 4 to 0.8 ⁇ m and a softening agent for hydrocarbon rubber (c) is lightweight, flexible, and anti-slip. Excellent.
  • a hydrogenated block copolymer of styrene-isoprene-butadiene-styrene type triblock copolymer having a weight average molecular weight of 270,000 is used as the component (a), and the component (c) is not contained. In case the compound was impossible.
  • a hydrogenated block copolymer of styrene-isoprene-butadiene-styrene type triblock copolymer having a weight average molecular weight of 80,000 is used as the component (a), and the component (c) is not contained. In the case, it was lightweight and flexible, but it was strong.
  • thermoplastic resin composition of the present invention is lightweight and excellent in flexibility, it is suitable for various applications that require grip comfort and lightness, such as automobile interior materials, stationery, tools, handles for sports equipment, and handles for cooking utensils. Can be used.

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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)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Le problème décrit par la présente invention est de fournir une composition de résine thermoplastique qui est légère, présente une souplesse exceptionnelle, et présente des propriétés antidérapantes appropriées. La solution selon l'invention porte sur une composition de résine thermoplastique caractérisée en ce qu'elle contient au moins un constituant (a), un constituant (b), et un constituant (c), la dureté mesurée par un duromètre de type A selon la norme JIS K6253 étant de 20 à 70 et le poids spécifique selon la norme JIS K7112 étant inférieur ou égal à 0,85. (a) Un élastomère thermoplastique qui est un copolymère séquencé hydrogéné obtenu par hydrogénation d'un copolymère séquencé comprenant des séquences (A) de polymère comprenant un composé vinylique aromatique dans la molécule et des séquences (B) de polymère comprenant un composé diène conjugué dans la molécule. (b) Des ballons de verre ayant une masse volumique réelle inférieure ou égale à 0,6 g/cm3, une résistance à la compression supérieure ou égale à 100 MPa, un diamètre médian inférieur à 30 μm, et une épaisseur d'ampoule de verre de 0,4 à 0,8 µm. (c) Un agent adoucissant à base d'hydrocarbure pour le caoutchouc.
PCT/JP2015/085304 2014-12-22 2015-12-17 Composition de résine thermoplastique WO2016104306A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014-258529 2014-12-22
JP2014258529 2014-12-22

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WO2016104306A1 true WO2016104306A1 (fr) 2016-06-30

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018030954A (ja) * 2016-08-25 2018-03-01 パナソニックＩｐマネジメント株式会社 ポリオレフィン樹脂組成物、およびこれを用いたポリオレフィン樹脂成形体、並びに、これを用いた掃除機
CN109124469A (zh) * 2017-06-28 2019-01-04 松下知识产权经营株式会社 聚烯烃树脂组合物和使用其的聚烯烃树脂成型体、以及使用其的电动吸尘器
WO2020066705A1 (fr) 2018-09-28 2020-04-02 日本ゼオン株式会社 Composition de résine et corps moulé formé de cette composition

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05306362A (ja) * 1992-01-24 1993-11-19 Takeda Chem Ind Ltd 不飽和ポリエステル樹脂組成物、成形材料及び成形物
JP2003020382A (ja) * 2001-03-08 2003-01-24 Riken Technos Corp 熱可塑性エラストマー組成物及びそれを用いた熱可塑性樹脂組成物
WO2003074574A1 (fr) * 2002-03-01 2003-09-12 Asahi Kasei Chemicals Corporation Copolymere hydrogene modifie
JP2007277485A (ja) * 2006-04-11 2007-10-25 Riken Technos Corp 自動車用樹脂シート
JP2013166817A (ja) * 2012-02-14 2013-08-29 Sumitomo Chemical Co Ltd ガラス微粒子中空球粉体含有ポリプロピレン系樹脂組成物及びその射出成形体
WO2013151151A1 (fr) * 2012-04-05 2013-10-10 ジャパンコンポジット株式会社 Matériau de moulage pour des réflecteurs de lampe et article moulé
JP2014513185A (ja) * 2011-05-02 2014-05-29 スリーエム イノベイティブ プロパティズ カンパニー 中空ガラスマイクロスフェアを含有した熱可塑性樹脂複合材料
JP2014218546A (ja) * 2013-05-01 2014-11-20 スリーエム イノベイティブプロパティズカンパニー 複合材料及びそれを含む成形品

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05306362A (ja) * 1992-01-24 1993-11-19 Takeda Chem Ind Ltd 不飽和ポリエステル樹脂組成物、成形材料及び成形物
JP2003020382A (ja) * 2001-03-08 2003-01-24 Riken Technos Corp 熱可塑性エラストマー組成物及びそれを用いた熱可塑性樹脂組成物
WO2003074574A1 (fr) * 2002-03-01 2003-09-12 Asahi Kasei Chemicals Corporation Copolymere hydrogene modifie
JP2007277485A (ja) * 2006-04-11 2007-10-25 Riken Technos Corp 自動車用樹脂シート
JP2014513185A (ja) * 2011-05-02 2014-05-29 スリーエム イノベイティブ プロパティズ カンパニー 中空ガラスマイクロスフェアを含有した熱可塑性樹脂複合材料
JP2013166817A (ja) * 2012-02-14 2013-08-29 Sumitomo Chemical Co Ltd ガラス微粒子中空球粉体含有ポリプロピレン系樹脂組成物及びその射出成形体
WO2013151151A1 (fr) * 2012-04-05 2013-10-10 ジャパンコンポジット株式会社 Matériau de moulage pour des réflecteurs de lampe et article moulé
JP2014218546A (ja) * 2013-05-01 2014-11-20 スリーエム イノベイティブプロパティズカンパニー 複合材料及びそれを含む成形品

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018030954A (ja) * 2016-08-25 2018-03-01 パナソニックＩｐマネジメント株式会社 ポリオレフィン樹脂組成物、およびこれを用いたポリオレフィン樹脂成形体、並びに、これを用いた掃除機
CN109124469A (zh) * 2017-06-28 2019-01-04 松下知识产权经营株式会社 聚烯烃树脂组合物和使用其的聚烯烃树脂成型体、以及使用其的电动吸尘器
WO2020066705A1 (fr) 2018-09-28 2020-04-02 日本ゼオン株式会社 Composition de résine et corps moulé formé de cette composition

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