WO2012165286A1 - Matière plastique renforcée par des fibres - Google Patents

Matière plastique renforcée par des fibres Download PDF

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Publication number
WO2012165286A1
WO2012165286A1 PCT/JP2012/063298 JP2012063298W WO2012165286A1 WO 2012165286 A1 WO2012165286 A1 WO 2012165286A1 JP 2012063298 W JP2012063298 W JP 2012063298W WO 2012165286 A1 WO2012165286 A1 WO 2012165286A1
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WO
WIPO (PCT)
Prior art keywords
fiber
plant
reinforced plastic
fibers
thermoplastic resin
Prior art date
Application number
PCT/JP2012/063298
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English (en)
Japanese (ja)
Inventor
三浦　寿久
修久 奥田
Original Assignee
トヨタ車体株式会社
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Filing date
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Publication of WO2012165286A1 publication Critical patent/WO2012165286A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • 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
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/045—Reinforcing macromolecular compounds with loose or coherent fibrous material with vegetable or animal fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
    • 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
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/16—Biodegradable polymers
    • 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
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/22—Thermoplastic resins
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils

Definitions

  • the present invention relates to a fiber reinforced plastic in which a vegetable fiber is blended as a reinforcing fiber in a thermoplastic resin.
  • fiber reinforced plastics in which inorganic fibers such as glass fibers and carbon fibers are blended have been developed as reinforcing fibers for improving mechanical strength in thermoplastic resins.
  • fiber-reinforced plastics containing inorganic fibers have a problem that residues derived from inorganic fibers remain even if they are incinerated. Therefore, fiber reinforced plastics in which plant fibers are blended as reinforcing fibers instead of inorganic fibers have been developed.
  • Such a fiber reinforced plastic is disclosed in, for example, Japanese Patent Application Laid-Open No. 2006-347079.
  • lignocellulose fibers obtained from plants are treated with a long-chain dihydric alcohol having a plurality of ether bonds, or treated with paraffin wax in order to reduce the unique fermentation odor generated in the process of taking out plant fibers. Or treated with isocyanate.
  • the reason why the strength of fiber reinforced plastic using plant fiber is relatively low is that the strength of the plant fiber itself is low as described above, and the interface strength between the plant fiber and the thermoplastic resin is low. Also mentioned. This is because if the interfacial strength between the plant fiber and the thermoplastic resin is low, the adhesive force between the plant fiber and the thermoplastic resin is lowered, and therefore, the interface peels off against the external force, and the breakage occurs therefrom. Therefore, in order to improve the mechanical strength of the fiber reinforced plastic, it is important to improve the interfacial strength between the plant fiber and the thermoplastic resin.
  • a fiber reinforced plastic containing a thermoplastic resin and plant fibers, wherein the plant fiber content (% by weight) / average fiber diameter ( ⁇ m) is 1.2 or more.
  • the interface area between the plant fiber and the thermoplastic resin is 480 cm 2 / cm 3 or more.
  • the interface area between the plant fiber and the thermoplastic resin can be increased to 480 cm 2 / cm 3 or more.
  • the interfacial strength between the vegetable fiber and the thermoplastic resin is improved, and thus the mechanical strength of the fiber reinforced plastic can be improved to a practical level.
  • the balance between the plant fiber content and the average fiber diameter is appropriately designed to increase the interfacial area between the plant fiber and the thermoplastic resin.
  • the interface strength increases.
  • a fiber reinforced plastic having good mechanical strength can be obtained while using environment-friendly plant fibers.
  • FRP fiber reinforced plastic
  • thermoplastic resin examples include polyolefin resins such as polypropylene and polyethylene, polycarbonate resins, polyethylene terephthalate, polybutylene terephthalate, polyester resins such as poly (ethylene-2,6-naphthalate), propylene-ethylene copolymers, polystyrene resins, Copolymers of aromatic vinyl monomers and (meth) acrylic acid alkyl esters having lower alkyl groups, terephthalic acid-ethylene glycol-cyclohexanedimethanol copolymers, (meth) acrylic resins such as polymethyl methacrylate, etc.
  • polyolefin resins such as polypropylene and polyethylene
  • polycarbonate resins such as polyethylene terephthalate, polybutylene terephthalate
  • polyester resins such as poly (ethylene-2,6-naphthalate), propylene-ethylene copolymers, polystyrene resins, Copolymers of aromatic vinyl monomers and (meth) acrylic acid alkyl
  • biodegradable resins such as polylactic acid, polybutylene succinate, polycaprolactone, and polyhydroxybutyrate, and plant-derived resins can be used.
  • thermoplastic resins may be used alone or in combination of two or more.
  • polypropylene, polyethylene, polycarbonate, and polyethylene terephthalate are preferable in terms of moldability and material cost.
  • a biodegradable resin or a plant-derived resin is advantageous for reducing the environmental burden.
  • Plant fibers are not particularly limited, and fibers obtained from herbs and woods can be used.
  • Herbs include pineapples such as Kurrawa and pineapple, as well as kenaf, ramie (flax), linen (flax), abaca (manila hemp), heneken (sisal hemp), jute (cannabis), hemp (cannabis) , Bast plants such as palm, palm, mulberry, straw and bagasse.
  • coniferous trees such as cedar and cypress, broad-leaved trees such as shii, oak and cherry, and tropical trees can be used. If it is a bast plant, it is easy to obtain good quality fibers.
  • Plant fibers include mechanical pulps, chemical pulps, semi-chemical pulps, and various types of artificial cellulose fibers synthesized from these pulps as raw materials. Treatment for obtaining such pulp fibers and cellulose fibers. Is not preferable because it is complicated. These plant fibers may be used alone or in combination of two or more.
  • the content of the plant fiber in the fiber reinforced plastic is not particularly limited, and may be the same as that of the conventional fiber reinforced plastic. Specifically, it may be about 3 to 50% by weight, preferably about 5 to 45% by weight, more preferably about 10 to 40% by weight. This is because if the content of the plant fiber is too small, it is difficult to obtain a reinforcing effect, and if it is too much, the strength tends to decrease and the strength tends to decrease. In addition, it is also preferable to surface-treat plant fiber with a silane coupling agent etc. as needed. This is because the bonding strength between the thermoplastic resin and the plant fiber can be improved.
  • the plant fiber content itself is not so important, but the balance with the fiber diameter is important.
  • the plant fiber content (% by weight) / average fiber diameter ( ⁇ m) is at least 1.2 or more.
  • the total interfacial area between the vegetable fiber and the thermoplastic resin becomes at least 480 cm 2 / cm 3 or more, and the total interfacial area between the plant fiber and the thermoplastic resin can be made larger than that of the conventional fiber reinforced plastic.
  • the overall interface strength between the plant fiber and the thermoplastic resin is improved, and the mechanical strength of the fiber-reinforced plastic can be improved.
  • the average fiber diameter of the plant fiber is as small as possible.
  • the average fiber diameter of the plant fiber is 35 ⁇ m or less, preferably 30 ⁇ m or less, more preferably 25 ⁇ m or less, and still more preferably 20 ⁇ m or less.
  • the fiber diameter of the plant fiber may be the fiber diameter as it is obtained from the plant, or may be appropriately adjusted by defibrating. However, since it takes time and labor to unravel the fiber, it is preferable to use the fiber obtained from the plant as it is. Some plants can be obtained in the form of single fibers and others can be obtained in the form of fiber bundles. Therefore, when referring to the fiber diameter of the plant fiber, the fiber diameter in the state of a single fiber and the fiber diameter in the state of a fiber bundle are included. There is a limit to the fineness of plant fibers. Therefore, the lower limit of the average fiber diameter of the plant fiber is not limited to good. For example, Kurawa fiber and pineapple fiber, which are the smallest fiber diameters, have a fiber diameter of about 7 ⁇ m.
  • the fiber length of the plant fiber is not particularly limited, but the longer the fiber length, the better the mechanical strength. However, if the fiber length of the plant fiber is too long, the moldability of the molded body made of fiber-reinforced plastic may be lowered, for example, the fluidity is lowered when kneaded with the thermoplastic resin. Considering this, the fiber length of the plant fiber is preferably about 0.1 to 30 mm, more preferably about 0.5 to 10 mm. In addition, in order to adjust the fiber length of each fiber, it can also be set as a chopped fiber as needed. Chopped fiber is obtained by bundling continuous fibers and cutting them into predetermined dimensions.
  • additives can be added to the fiber reinforced plastic as long as the effects of the present invention are not impaired. Specifically, pigments, dyes, dispersants, stabilizers, plasticizers, modifiers, UV absorbers, light stabilizers, antioxidants, antistatic agents, lubricants, mold release agents, etc. may be added. it can.
  • the fiber reinforced plastic is formed as a resin molded body having a predetermined shape by kneading the thermoplastic resin and the vegetable fiber and then extruding or injection molding.
  • the obtained resin molded product can be suitably used as an interior material for automobile door trims, inner panels, pillar garnishes, rear packages, interior light lenses, and the like. In addition, it can also be used as building materials, civil engineering materials, packaging materials, daily necessities.
  • Table 1 shows the thermoplastic resins and plant fibers used in each Example and Comparative Example, and their compositions.
  • the content ratio / average fiber diameter is 1.2 or more
  • the total interfacial area between the thermoplastic resin and the plant fiber is 480 cm 2 / cm 3 or more, and a good strength that can be handled even at a practical level is obtained.
  • the Kurrawa fiber and the pineapple fiber have a particularly small fiber diameter among plant fibers, so that the content ratio / average fiber diameter is 4.0 or more and the total interface area between the thermoplastic resin and the plant fibers is 1700 cm 2 / cm 3 or more. It was confirmed that high strength was obtained.

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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)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Reinforced Plastic Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une matière plastique renforcée par des fibres, qui contient une résine thermoplastique et des fibres végétales, et dans laquelle le rapport de la teneur en fibres végétales (% en poids) au diamètre moyen de fibre (µm) est de 1,2 ou plus et la surface des interfaces entre les fibres végétales et la résine thermoplastique est de 480 cm2/cm3 ou plus.
PCT/JP2012/063298 2011-05-31 2012-05-24 Matière plastique renforcée par des fibres WO2012165286A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011-121743 2011-05-31
JP2011121743A JP2012246459A (ja) 2011-05-31 2011-05-31 繊維強化プラスチック

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Publication Number Publication Date
WO2012165286A1 true WO2012165286A1 (fr) 2012-12-06

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WO (1) WO2012165286A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7163046B2 (ja) * 2018-03-29 2022-10-31 大阪瓦斯株式会社 バイオマス樹脂組成物

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007034905A1 (fr) * 2005-09-22 2007-03-29 Fujitsu Limited Composition contenant une résine à base de plantes et corps moulé contenant une résine à base de plantes utilisant celle-ci
JP2008195814A (ja) * 2007-02-13 2008-08-28 Toyobo Co Ltd 繊維強化ポリヒドロキシブチレート樹脂組成物
JP2009132074A (ja) * 2007-11-30 2009-06-18 Kobe Steel Ltd 天然繊維強化熱可塑性樹脂射出成形体
JP2010241986A (ja) * 2009-04-07 2010-10-28 Toyota Boshoku Corp 熱可塑性樹脂組成物の製造方法
JP2011006598A (ja) * 2009-06-26 2011-01-13 Konica Minolta Holdings Inc セルロース繊維分散液の製造方法及びこれを用いた樹脂成形体
JP2011068709A (ja) * 2009-09-24 2011-04-07 Konica Minolta Opto Inc 光学フィルム、それを用いた透明ガスバリアフィルム、および光学フィルムの製造方法
JP2011208015A (ja) * 2010-03-30 2011-10-20 Konica Minolta Holdings Inc 繊維複合材料
JP2011213754A (ja) * 2010-03-31 2011-10-27 Kyoto Univ ミクロフィブリル化植物繊維及びその製造方法、並びにそれを用いた成形材料、及び樹脂成形材料の製造方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007034905A1 (fr) * 2005-09-22 2007-03-29 Fujitsu Limited Composition contenant une résine à base de plantes et corps moulé contenant une résine à base de plantes utilisant celle-ci
JP2008195814A (ja) * 2007-02-13 2008-08-28 Toyobo Co Ltd 繊維強化ポリヒドロキシブチレート樹脂組成物
JP2009132074A (ja) * 2007-11-30 2009-06-18 Kobe Steel Ltd 天然繊維強化熱可塑性樹脂射出成形体
JP2010241986A (ja) * 2009-04-07 2010-10-28 Toyota Boshoku Corp 熱可塑性樹脂組成物の製造方法
JP2011006598A (ja) * 2009-06-26 2011-01-13 Konica Minolta Holdings Inc セルロース繊維分散液の製造方法及びこれを用いた樹脂成形体
JP2011068709A (ja) * 2009-09-24 2011-04-07 Konica Minolta Opto Inc 光学フィルム、それを用いた透明ガスバリアフィルム、および光学フィルムの製造方法
JP2011208015A (ja) * 2010-03-30 2011-10-20 Konica Minolta Holdings Inc 繊維複合材料
JP2011213754A (ja) * 2010-03-31 2011-10-27 Kyoto Univ ミクロフィブリル化植物繊維及びその製造方法、並びにそれを用いた成形材料、及び樹脂成形材料の製造方法

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