WO2020095845A1 - Composition de résine renforcée par des fibres et son procédé de production - Google Patents

Composition de résine renforcée par des fibres et son procédé de production Download PDF

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WO2020095845A1
WO2020095845A1 PCT/JP2019/043079 JP2019043079W WO2020095845A1 WO 2020095845 A1 WO2020095845 A1 WO 2020095845A1 JP 2019043079 W JP2019043079 W JP 2019043079W WO 2020095845 A1 WO2020095845 A1 WO 2020095845A1
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fiber
group
chemically modified
carbon atoms
cellulosic
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PCT/JP2019/043079
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English (en)
Japanese (ja)
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矢野　浩之
文明 中坪
尾村　春夫
健 仙波
和男 北川
伊達　隆
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国立大学法人京都大学
地方独立行政法人京都市産業技術研究所
日本製紙株式会社
王子ホールディングス株式会社
星光Pmc株式会社
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Application filed by 国立大学法人京都大学, 地方独立行政法人京都市産業技術研究所, 日本製紙株式会社, 王子ホールディングス株式会社, 星光Pmc株式会社 filed Critical 国立大学法人京都大学
Publication of WO2020095845A1 publication Critical patent/WO2020095845A1/fr

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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
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • 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

Definitions

  • the present invention relates to a fiber reinforced resin composition, a method for producing the same, and a molded product.
  • the fiber-reinforced resin composition has a smaller energy load during manufacturing than metal and is lightweight, and thus has been used in a wide range of fields such as automobile members, aircraft members, household equipment members, and construction members (for example, Patent Documents 1 to 7).
  • Patent Document 1 discloses a board obtained by heating and compressing a composite material in which a mat of plant bast fibers such as ramie, kenaf, jute and the like is impregnated with a resin and a base material are heated and compressed.
  • Patent Document 2 discloses a method of repeatedly modifying a mechanical property of a plant fiber by repeatedly applying a tensile load to a twisted yarn of a plant bast fiber such as ramie, and a resin of the plant fiber thus modified. It is disclosed that intermediate materials such as wires, pellets, and thin plates can be prepared through processes such as impregnation, mixing, and hot pressing.
  • Patent Documents 3 to 5 disclose composites composed of a mixture of two different kinds of fibers and a resin (resin adhesive). Specifically, Patent Document 3 discloses a board made of a mixture of plant bast fibers and wood-derived fibers and an adhesive. Patent Document 4 discloses a board in which a mixture of a plant fiber having an average fiber diameter of 70 to 400 ⁇ m (main constituent fiber) and a finer plant fiber having an average fiber diameter of 20 to 70 ⁇ m is bonded with a granular adhesive. Document 5 discloses the manufacturing method thereof.
  • Patent Document 6 contains a nonwoven fabric composed of a cellulose fiber having a nano-order fiber width (number average fiber width of 2 nm or more and less than 1000 nm) and a thicker second fiber (number average fiber width of 1000 nm or more and 100000 nm or less) and a resin.
  • a complex is disclosed.
  • Patent Document 7 discloses a fiber-reinforced resin composition having improved strength characteristics (elastic modulus and strength) by combining chemically modified cellulose nanofibers and a thermoplastic resin, and a method for producing the same.
  • the resin composition containing the cellulosic microfibrillated fiber is excellent as a structural material because it has higher strength and elastic modulus than a resin containing no fiber, but when the amount of the contained fiber is increased, the impact resistance becomes higher. Since it tends to decrease, there is room for improvement.
  • Patent Document 1 the test results of impact resistance of a board produced by heating and compressing a plant bast fiber mat impregnated with a resin such as ramie and a base material are described together with other test results. However, it does not describe or suggest the impact resistance of the plant bast fiber kneaded with the thermoplastic resin.
  • Patent Document 2 discloses a resin composition containing ramie
  • Patent Documents 3 to 6 describe a composite composed of a mixture of two kinds of different fibers and a resin (resin adhesive). However, there is no description about impact resistance of these composites.
  • Patent Document 7 discloses a resin composition reinforced with chemically modified cellulose nanofibers derived from wood, but does not contain a plant fiber as used in the present invention.
  • the present inventors prepared a fiber-reinforced resin composition by using a specific cellulosic microfibrillated fiber and a specific plant fiber in combination, and a molded article made of the composition has excellent strength characteristics (high bending Strength and elastic modulus), and further has excellent characteristics that the impact resistance is improved or the impact resistance is less deteriorated (impact resistance can be maintained) as compared with a resin molded product containing no fiber. Based on the findings, they have completed the present invention.
  • the present invention relates to the following fiber-reinforced resin composition, molded article, and method for producing a fiber-reinforced resin composition.
  • the microfibrillated cellulosic fiber has the following formula (1): (Lg) Cell-OR (1) [In the formula (1), (Lg) Cell- represents a residue obtained by removing a hydroxyl group from the polysaccharide and lignin constituting cellulose, holocellulose and / or lignocellulose in the cellulosic polymer. -OR represents a hydroxyl group in the cellulose and holocellulose and / or lignocellulosic polysaccharides and lignin in the cellulosic polymer, or a hydrogen atom of a part of the hydroxyl group is substituted with a substituent R. R represents a hydrogen atom, an acyl group having 2 to 4 carbon atoms, and the following formula (2):
  • R 1 and R 2 are the same or different and each represents a hydrogen atom, a methyl group, an ethyl group, or an optionally branched alkenyl group or alkyl group having 3 to 20 carbon atoms. Provided that when one of R 1 and R 2 has 4 to 20 carbon atoms, the other of R 1 and R 2 is a hydrogen atom.), Or a carboxy group-containing acyl group represented by A salt of a group-containing acyl group is shown. ] It is a microfibrillated fiber of a fiber composed of a non-chemically modified or chemically modified cellulosic polymer represented by.
  • a part of hydrogen atoms of a hydroxyl group of cellulose constituting the plant fiber of (B-1) is an acyl group having 2 to 4 carbon atoms, and the following formula (2):
  • R 1 and R 2 are the same or different and each represents a hydrogen atom, a methyl group, an ethyl group, or an optionally branched alkenyl group or alkyl group having 3 to 20 carbon atoms. Provided that when one of R 1 and R 2 has 4 to 20 carbon atoms, the other of R 1 and R 2 is a hydrogen atom.
  • a carboxy group-containing acyl group represented by One or more chemically modified plant fibers modified with a salt of a group-containing acyl group.
  • R in the formula (1) of the requirement (a) is an acyl group having 2 to 4 carbon atoms, and the following formula (2):
  • R 1 and R 2 are the same or different and each represents a hydrogen atom, a methyl group, an ethyl group, or an optionally branched alkenyl group or alkyl group having 3 to 20 carbon atoms. Provided that when one of R 1 and R 2 has 4 to 20 carbon atoms, the other of R 1 and R 2 is a hydrogen atom.
  • a carboxy group-containing acyl group represented by Item 2 or a carboxy group-containing acyl group represented by Item 2.
  • Item 3 The fiber-reinforced resin composition according to Item 1 or 2, wherein R in the formula (1) of the requirement (a) is an acetyl group.
  • (B) vegetable fiber is (B-1) one or more vegetable fibers selected from the group consisting of ramie, hemp, linen, jute, abaca, sisal, kenaf, and cotton.
  • the fiber reinforced resin composition according to any one of items 1 to 3 above.
  • Item 6. The fiber-reinforced resin composition according to any one of Items 1 to 3, wherein the (B) vegetable fiber of the requirement (b) is a ramie and / or a ramie modified with an acetyl group.
  • thermoplastic resin (C) is polyamide, polyolefin, aliphatic polyester, aromatic polyester, polyacetal, polycarbonate, polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS resin), polycarbonate-ABS alloy (PC-ABS alloy).
  • ABS resin acrylonitrile-butadiene-styrene copolymer
  • PC-ABS alloy polycarbonate-ABS alloy
  • m-PPE modified polyphenylene ether
  • Item 8 A molded article comprising the fiber-reinforced resin composition according to any one of items 1 to 7 above.
  • a method for producing a fiber-reinforced resin composition containing (A-1) a chemically modified microfibrillated cellulosic fiber, (B) a plant fiber, and (C) a thermoplastic resin, (AP) chemically modified cellulosic pulp, (B) vegetable fiber, and (C) thermoplastic resin is melt-kneaded, and the step of microfibrillating the chemically modified cellulosic pulp during the melt-kneading,
  • the (AP) chemically modified cellulosic pulp, the (B) plant fiber, and the (A-1) chemically modified microfibrillated cellulosic fiber have the following requirements (ap), (b), and (a-1), respectively. ), The manufacturing method.
  • Chemically modified cellulosic pulp has the following formula (1-1): (Lg) Cell-OR (1-1) [In the formula (1-1), (Lg) Cell- represents a residue obtained by removing a hydroxyl group from the polysaccharide and lignin that constitute cellulose, holocellulose, and / or lignocellulose in the cellulosic polymer.
  • R 1 and R 2 are the same or different and each represents a hydrogen atom, a methyl group, an ethyl group, or an optionally branched alkenyl group or alkyl group having 3 to 20 carbon atoms. Provided that when one of R 1 and R 2 has 4 to 20 carbon atoms, the other of R 1 and R 2 is a hydrogen atom.), Or a carboxy group-containing acyl group represented by A salt of a group-containing acyl group is shown. ] It is a chemically modified cellulosic pulp composed of a chemically modified cellulosic polymer.
  • a part of hydrogen atoms of a hydroxyl group of cellulose constituting the plant fiber of (B-1) is an acyl group having 2 to 4 carbon atoms, and the following formula (2):
  • R 1 and R 2 are the same or different and each represents a hydrogen atom, a methyl group, an ethyl group, or an optionally branched alkenyl group or alkyl group having 3 to 20 carbon atoms. Provided that when one of R 1 and R 2 has 4 to 20 carbon atoms, the other of R 1 and R 2 is a hydrogen atom.
  • the (A-1) chemically modified microfibrillated cellulosic fiber is a microfibrillated fiber composed of the chemically modified cellulosic polymer represented by the formula (1-1).
  • a method for producing a fiber-reinforced resin composition containing (A-1) a chemically modified microfibrillated cellulosic fiber, (B) a plant fiber, and (C) a thermoplastic resin Process (1): (AP) a chemically modified cellulosic pulp and (C) a thermoplastic resin are kneaded to microfibrillize the chemically modified cellulosic pulp during the melt-kneading, and step (2): Including the step of compounding the kneaded product obtained in the step (1), and (B) plant fiber, or a resin composition containing a plant fiber and a thermoplastic resin,
  • the (AP) chemically modified cellulosic pulp, the (B) plant fiber, and the (A-1) chemically modified microfibrillated cellulosic fiber have the following requirements (ap), (b), and (a-1), respectively.
  • Chemically modified cellulosic pulp has the following formula (1-1): (Lg) Cell-OR (1-1) [In the formula (1-1), (Lg) Cell- represents a residue obtained by removing a hydroxyl group from the polysaccharide and lignin that constitute cellulose, holocellulose, and / or lignocellulose in the cellulosic polymer.
  • R 1 and R 2 are the same or different and each represents a hydrogen atom, a methyl group, an ethyl group, or an optionally branched alkenyl group or alkyl group having 3 to 20 carbon atoms. Provided that when one of R 1 and R 2 has 4 to 20 carbon atoms, the other of R 1 and R 2 is a hydrogen atom.), Or a carboxy group-containing acyl group represented by A salt of a group-containing acyl group is shown. ] It is a chemically modified cellulosic pulp composed of a chemically modified cellulosic polymer.
  • a part of hydrogen atoms of a hydroxyl group of cellulose constituting the plant fiber of (B-1) is an acyl group having 2 to 4 carbon atoms, and the following formula (2):
  • R 1 and R 2 are the same or different and each represents a hydrogen atom, a methyl group, an ethyl group, or an optionally branched alkenyl group or alkyl group having 3 to 20 carbon atoms. Provided that when one of R 1 and R 2 has 4 to 20 carbon atoms, the other of R 1 and R 2 is a hydrogen atom.
  • the (A-1) chemically modified microfibrillated cellulosic fiber is a microfibrillated fiber composed of the chemically modified cellulosic polymer represented by the formula (1-1).
  • the fiber-reinforced resin composition of the present invention contains a specific microfibrillated cellulosic fiber, and a specific plant fiber
  • a molded article comprising this fiber-reinforced resin composition is a molded article of a resin containing no fiber.
  • the strength characteristics are significantly improved, the impact resistance is also improved, or the impact resistance of the resin itself is maintained.
  • the molded article composed of the fiber reinforced resin composition by including both the fibrillated cellulosic fiber and the plant fiber in the resin composition, the molded article composed of the fiber reinforced resin composition, the bending elastic modulus and bending strength is improved, the impact resistance is maintained. Alternatively, the effect of improvement can be obtained.
  • the fiber-reinforced resin composition of the present invention can be molded by an injection molding method, the productivity of molded products is high. Therefore, the molded body can be manufactured at a low manufacturing cost.
  • the fiber-reinforced resin composition of the present invention if a step of melt-kneading a chemically modified cellulosic fiber, a plant fiber, and a resin is adopted, melt kneading and microfibrillation of the chemically modified cellulosic fiber are performed. Since they can be performed simultaneously, the resin composition can be produced with high productivity.
  • the fiber reinforced resin composition of the present invention contains (A) microfibrillated cellulosic fibers, (B) plant fibers, and (C) thermoplastic resin.
  • the (A) microfibrillated cellulosic fiber satisfies the following requirement (a).
  • (A) The microfibrillated cellulosic fiber has the following formula (1): (Lg) Cell-OR (1) [In the formula (1), (Lg) Cell- represents a residue obtained by removing a hydroxyl group from the polysaccharide and lignin constituting cellulose, holocellulose and / or lignocellulose in the cellulosic polymer.
  • R represents a hydrogen atom, an acyl group having 2 to 4 carbon atoms, and the following formula (2):
  • R 1 and R 2 are the same or different and each represents a hydrogen atom, a methyl group, an ethyl group, or an optionally branched alkenyl group or alkyl group having 3 to 20 carbon atoms. Provided that when one of R 1 and R 2 has 4 to 20 carbon atoms, the other of R 1 and R 2 is a hydrogen atom.), Or a carboxy group-containing acyl group represented by A salt of a group-containing acyl group is shown. ] It is a microfibrillated fiber of a fiber composed of a non-chemically modified or chemically modified cellulosic polymer represented by.
  • the (B) vegetable fiber satisfies the following requirement (b).
  • (B) vegetable fiber (B-1) one or more plant fibers selected from the group consisting of ramie, hemp, linen, jute, abaca, sisal, kenaf, and cotton, or
  • a part of hydrogen atoms of a hydroxyl group of cellulose constituting the plant fiber of (B-1) is an acyl group having 2 to 4 carbon atoms, and the following formula (2):
  • R 1 and R 2 are the same or different and each represents a hydrogen atom, a methyl group, an ethyl group, or an optionally branched alkenyl group or alkyl group having 3 to 20 carbon atoms. Provided that when one of R 1 and R 2 has 4 to 20 carbon atoms, the other of R 1 and R 2 is a hydrogen atom.
  • a carboxy group-containing acyl group represented by One or more chemically modified plant fibers modified with a salt of a group-containing acyl group.
  • Microfibrillated cellulosic fibers means microfibrillated cellulosic fibers.
  • MFC microfibrillated cellulosic fiber
  • Cellulosic fiber means a fiber composed of at least one polymer (cellulosic polymer) selected from the group consisting of cellulose, holocellulose, and lignocellulose (polymer group).
  • the cellulosic polymer may be referred to as “(Lg) Cell-OH”. That is, in the present specification, the cellulosic fiber means a fiber composed of a cellulosic polymer “(Lg) Cell-OH”.
  • (Lg) Cell- means a residue obtained by removing a hydroxyl group from a polysaccharide or lignin that constitutes at least one kind of polymer selected from the above-mentioned polymer group.
  • the cellulosic fiber used in the present invention is a fiber composed of a cellulosic polymer [(Lg) Cell-OH], or a polysaccharide constituting cellulose, holocellulose and / or lignocellulose in the cellulosic polymer. And a fiber composed of a polymer in which hydrogen atoms of some hydroxyl groups in lignin are substituted with a substituent R (the details of the substituent R will be described later).
  • the cellulosic fiber used in the present invention has the following formula (1): (Lg) Cell-OR (1)
  • (Lg) Cell- is a cellulose in the cellulosic polymer, A residue obtained by removing a hydroxyl group from a polysaccharide or lignin that constitutes holocellulose and / or lignocellulose is shown.
  • OR represents a hydroxyl group in the cellulose and holocellulose and / or lignocellulosic polysaccharide and lignin in the cellulosic polymer, or a part of the hydrogen atoms of the hydroxyl group is substituted with a substituent R.
  • a fiber composed of a non-chemically modified cellulose-based polymer hereinafter, also referred to as “non-chemically modified cellulose-based fiber” or a fiber composed of a chemically-modified cellulose-based polymer (hereinafter, “chemically modified cellulose”). It is also defined as "system fiber”).
  • the microfibrillated cellulosic fiber (MFC) used in the present invention is (i) a fiber (i.e., a non-chemically modified MFC) in which non-chemically modified cellulosic fiber [a fiber composed of a polymer in which OR is a hydroxyl group in the above formula (1)] is microfibrillated, and (ii) Chemically modified cellulosic fiber (OR in the above formula (1) is a polysaccharide constituting cellulose, holocellulose and / or lignocellulose in the cellulosic polymer and hydrogen atoms of some hydroxyl groups in lignin are substituted by a substituent R. Fibers composed of substituted cellulosic polymers] include microfibrillated fibers (ie chemically modified MFCs).
  • the chemically modified MFC is also a fiber in which the hydrogen atoms of some hydroxyl groups of the polysaccharide and lignin in the cellulose, holocellulose and / or lignocellulose constituting the non-chemically modified MFC are replaced by the substituent R.
  • Chemically modified MFC is a method of chemically modifying cellulosic pulp (hereinafter also referred to as “CP”) to form a chemically modified CP, and fibrillating the obtained chemically modified CP to form microfibrils, or It can be obtained by a method of chemically modifying MFC.
  • CP cellulosic pulp
  • cellulosic pulp means a fiber aggregate composed of a cellulosic polymer.
  • Cellulosic pulp includes lignin-free pulp (cellulose-based pulp, holocellulose-based pulp, etc.) and lignin-containing pulp (ligno pulp).
  • the MFC contained in the fiber reinforced resin composition of the present invention is a non-chemically modified MFC or a chemically modified MFC. From the viewpoint of dispersibility in a resin and defibration, the MFC is preferably a chemically modified MFC.
  • the substituent R in the above formula (1) is an acyl group having 2 to 4 carbon atoms, and the following formula (2):
  • R 1 and R 2 are the same as above.
  • the substituent R in the above formula (1) is more preferably an acyl group having 2 to 3 carbon atoms (acetyl group and propionyl group).
  • an acetyl group is most preferable from the viewpoint of ease of production and production cost.
  • the salt of the carboxyl group-containing acyl group represented by the above formula (2) means that the carboxy group is in the state of an inorganic salt or an organic salt.
  • alkali metal salts such as sodium salt, lithium salt and potassium salt; divalent metal salts such as calcium salt, barium salt, zinc salt and copper salt; trivalent metal salts such as aluminum salt are preferable. ..
  • organic salt a primary to quaternary ammonium salt and a salt with a polyamine are preferable.
  • the above chemically modified MFC having various substituents is preferable because it has good dispersibility in the fiber reinforced resin composition.
  • the non-chemically modified MFC and the chemically modified MFC may be combined (combined) and contained in the fiber-reinforced resin composition of the present invention. Further, two kinds of chemically modified MFCs different from each other may be combined (used together) and contained in the fiber-reinforced resin composition of the present invention.
  • these chemically modified MFCs can be well dispersed in the fiber reinforced resin composition.
  • Raw material for chemically modified MFC and non-chemically modified MFC As a raw material for the chemically modified MFC and the non-chemically modified MFC, pulp is preferably used.
  • Pulp is obtained by separating fibers contained in plant materials such as wood, bamboo, hemp, jute, kenaf, cotton, beet, rice straw, bagasse, beet marc, cellulose, hemicellulose, holocellulose and And / or contains lignocellulose.
  • wood for example, pine (Todo pine, red pine, ezo nut, etc.), Douglas fir, hemlock spruce, sitka spruce, conifer such as cedar, cypress, or eucalyptus, acacia, poplar, beech, oak, oak, alder, etc.
  • Hardwood-derived wood is preferably used.
  • Agricultural waste products, waste paper, knitted fabrics, etc. may be used as the plant raw materials other than the above.
  • the used paper is preferably deinked used paper, corrugated used paper, magazines and used copy paper.
  • the pulp raw material is not limited to these. One type of pulp may be used alone, or two or more types selected from these may be used.
  • pulp which is a raw material of non-chemically modified MFC and chemically modified MFC
  • CP cellulosic pulp
  • pulp containing lignocellulose pulp containing no lignin and pulp containing lignin
  • pulp containing lignocellulose pulp containing lignocellulose
  • Ligno pulp (LP) is preferably used for the pulp that is the raw material of non-chemically modified MFC and chemically modified MFC. That is, it is preferable that (Lg) Cell- in the formula (1) of the requirement (a) is a residue obtained by removing a hydroxyl group from the polysaccharide and lignin constituting lignocellulose.
  • Lignocellulose is a complex hydrocarbon polymer (natural polymer mixture) that constitutes the cell wall of trees. It is known that lignocellulose is mainly composed of polysaccharide cellulose, hemicellulose, and lignin which is an aromatic polymer (see Reference Example 1 and Reference Example 2 below).
  • Reference Example 1 Review Article Conversion of Lignocellulosic Biomass to Nanocellulose: Structure and Chemical Process HV Lee, SBA Hamid, and SK Zain, Scientific World Journal Volume 2014 ,, Article ID 631013, 20 pages, http://dx.doi.org /10.1155/2014/631013
  • Reference Example 2 New lignocellulose pretreatments using cellulose solvents: A review, Noppadon Sathitsuksanoh, Anthe George and YH Percival Zhang, J Chem Technol Biotechnol 2013; 88: 169-180
  • lignocellulose means a lignocellulose having a chemical structure naturally present in plants, artificially modified lignocellulose, or a mixture thereof. This is a lignocellulose having a naturally occurring chemical structure contained in various pulps obtained by mechanically and / or chemically treating plants, for example, wood, chemically or mechanically modified lignocellulose. Cellulose or a mixture thereof.
  • the fiber made of lignocellulose used in the present invention is not limited to the fiber made of lignocellulose having a naturally occurring chemical structure. Moreover, the lignin content in the lignocellulose is not limited. Therefore, "lignocellulose” means a substance in which lignin and cellulose are present in a plant, and / or a mixture of lignin and cellulose, regardless of the lignin content. Therefore, the terms "lignocellulose” and “ligno pulp” are to be construed as lignocellulose and lignopulp, respectively, even if the content of lignin component is very small.
  • Pulp or lignopulp can be obtained by treating the above-mentioned plant-derived raw material by a mechanical pulping method, a chemical pulping method, or a combination of a mechanical pulping method and a chemical pulping method.
  • various kraft pulps softwood unbleached kraft pulp (NUKP), softwood oxygen bleached kraft pulp (NOKP), and softwood bleached kraft pulp (NBKP)
  • NUKP softwood unbleached kraft pulp
  • NOKP softwood oxygen bleached kraft pulp
  • NKP softwood bleached kraft pulp
  • Mechanical pulp (MP) such as groundwood pulp (GP), refiner GP (RGP), thermomechanical pulp (TMP) and chemithermomechanical pulp (CTMP) is also preferable.
  • Some kraft pulp does not contain lignin, but regardless of its content, it can be used as a raw material for non-chemically modified MFC and chemically modified MFC.
  • lignopulp compared to cellulose fiber or pulp that does not contain lignin, that the number of manufacturing steps is small, that the yield from the raw material (for example, wood) is good, there are few chemical agents required for its production. In addition, since it can be manufactured with less energy, it is advantageous in terms of manufacturing cost. Therefore, lignopulp can be advantageously used in the present invention.
  • Ligno pulp obtained from Todo pine, Japanese red pine, or cedar is a fiber having excellent strength characteristics by containing a non-chemically modified MFC and / or a chemically modified MFC produced by using the same. It is preferable because a reinforced resin composition can be obtained.
  • the amount of lignin contained in lignocellulose and lignopulp can be quantified by the Klarson method.
  • the lignin content of the ligno pulp is more preferably about 0.1 to 35% by mass, and particularly preferably about 0.1 to 30% by mass.
  • Non-chemically modified MFC for example, a suspension or slurry of non-chemically modified CP, refiner, high pressure homogenizer, grinder, single-screw or multi-screw kneader (preferably twin-screw kneader), bead mill It can be prepared by defibrating and microfibrillating the non-chemically modified CP using a known means such as mechanical grinding or beating by the above.
  • the chemically modified MFC can be obtained by chemically modifying a cellulosic pulp (CP) to obtain a chemically modified cellulosic pulp (chemically modified CP) and defibrating it.
  • CP cellulosic pulp
  • chemically modified CP chemically modified cellulosic pulp
  • chemically modified MFC can be obtained by defibrating cellulosic pulp (CP) to obtain microfibrillated cellulosic fiber (MFC) and chemically modifying it.
  • CP defibrating cellulosic pulp
  • MFC microfibrillated cellulosic fiber
  • hydroxyl groups such as cellulose, hemicellulose, and lignin hydroxyl groups present on the fiber surface or the amorphous portion of the raw material CP so as not to destroy the cellulose crystal structure originally present in the raw material CP.
  • hydroxyl groups such as cellulose, hemicellulose, and lignin hydroxyl groups present on the fiber surface or the amorphous portion of the raw material CP so as not to destroy the cellulose crystal structure originally present in the raw material CP.
  • the acylation reaction involves suspending the raw material CP in an anhydrous aprotic polar solvent capable of swelling the raw material CP, such as N-methylpyrrolidone, N, N-dimethylformamide, etc., and having a corresponding acyl group. It can be carried out by a conventional method (method described in JP 2016-176052 A) using a carboxylic acid anhydride or an acid chloride in the presence of a base.
  • the method for measuring the degree of substitution by R in formula (1) can be according to the conventional method (method described in JP 2016-176052 A).
  • the degree of substitution can be adjusted by adjusting the amount of the acylating agent in the above-mentioned acylation, the reaction temperature, the reaction time and the like.
  • the carboxy group-containing acylated cellulose pulp represented by (carboxyacylated CP) is a conventional method (method described in Patent No. 5496435 etc.), in which the raw material CP has the following formula (3):
  • R 1 and R 2 are the same or different and each represents a hydrogen atom, a methyl group, an ethyl group, or an optionally branched alkenyl group or alkyl group having 3 to 20 carbon atoms. However, when either one of R 1 and R 2 has 4 to 20 carbon atoms, the other of R 1 and R 2 is a hydrogen atom.
  • succinic anhydride Or its derivative (hereinafter referred to as succinic anhydride). , These are sometimes referred to as “acid anhydrides of the formula (3)”, and some of the hydroxyl groups present in the CP of the raw material are acylated (represented by the formula (2), carboxy It can be produced by half-esterification with a group-containing acyl group.
  • the chemical modification (half-esterification) of the raw material CP with the acid anhydride of the formula (3) is carried out by mixing the raw material CP dispersed in an aprotic polar organic solvent and the acid anhydride of the formula (3) in the presence of a base. It can be carried out by heating and reacting to partially esterify the hydroxyl groups present in the raw material CP.
  • the half ester means that one of the two carbonyl groups present in the acid anhydride of formula (3) forms an ester bond with the hydroxyl group in the raw material CP, and the other carbonyl group is a hydroxycarbonyl group. It means the ester in the finished state.
  • the carboxyl group present in the carboxyacylated CP represented by the above formula (2) may be in the state of an inorganic salt or an organic salt.
  • a salt of carboxyacylated CP is obtained by dispersing the carboxyacylated CP in a liquid such as water or a hydroalcohol, and a hydroxide of an alkali metal such as sodium, lithium or potassium, a hydrogen carbonate, Carbonate; divalent metal salt such as calcium salt, barium salt, zinc salt, copper salt; trivalent metal salt such as aluminum salt; primary to quaternary ammonium salt, and aqueous solution or dispersion of salt with polyamine Can be prepared by adding.
  • alkenylsuccinic anhydride belonging to the acid anhydride of the above formula (3) examples include compounds having a skeleton derived from an olefin having 4 to 20 carbon atoms and a maleic anhydride skeleton.
  • Alkenyl succinic anhydrides such as cenylsuccinic anhydride and octadecenyl succinic anhydride can be preferably used.
  • each compound may be used alone, or two or more kinds may be used in combination.
  • an alkenyl succinic anhydride having an olefin chain having a specific carbon number may be represented by a combination of the abbreviation (ASA) of the alkenyl succinic anhydride and the carbon number of the olefin chain.
  • ASA abbreviation
  • an alkenyl succinic anhydride (hexadecenyl succinic anhydride) having an olefin chain with 16 carbon atoms may be referred to as “ASA-C16”.
  • the ASA used in the present invention may be described by a product name or a product code number.
  • AS1533 manufactured by Seikou PMC Co., Ltd.
  • TNS135 manufactured by Seikou PMC Co., Ltd.
  • RIKACID DDSA tetrapropenyl succinic anhydride, manufactured by Shin Nihon Rikagaku Co., Ltd.
  • alkyl succinic anhydride examples include those obtained by reducing the unsaturated bond of the alkenyl group of the alkenyl succinic anhydride represented by the above formula (3) by hydrogenation (that is, succinic acid in which the alkenyl group is converted to an alkyl group). Acid anhydrides) can be used.
  • alkyl succinic anhydrides such as octyl succinic anhydride, dodecyl succinic anhydride, hexadecyl succinic anhydride and octadecyl succinic anhydride can be preferably used.
  • each compound may be used alone, or two or more kinds may be used in combination. Further, the alkyl succinic anhydride and the alkenyl succinic anhydride can be used together.
  • the reaction between the raw material CP and the acid anhydride of formula (3) is preferably carried out in an anhydrous aprotic polar solvent (organic solvent) in the presence of a base in order to accelerate the reaction.
  • a base amines such as pyridine and dimethylaniline, alkali metal salts of acetic acid such as potassium acetate and sodium acetate, and carbonate salts of alkali metals such as lithium carbonate, potassium carbonate and sodium carbonate can be preferably used.
  • the reaction temperature depends on the boiling point of the solvent used, but is preferably about 20 to 150 ° C, more preferably about 30 to 120 ° C, even more preferably about 40 to 100 ° C.
  • the reaction time is adjusted appropriately according to the type of acid anhydride of formula (3).
  • the degree of half-esterification was determined by collecting a part of the lignocellulosic fiber during the reaction, measuring its infrared (IR) absorption spectrum, and tracing the IR absorption peak based on the carbonyl stretching vibration of the half-ester produced by the reaction. Adjustment can be performed while checking (substitution degree).
  • MFC microfibrillated cellulose
  • CP cellulosic pulp
  • degree of Modification of Chemically Modified CP or Chemically Modified MFC with Substituent R refers to the above formula (1 ) The degree to which the hydrogen atom of the hydroxyl group present in one unit (repeating unit) of the residue [(Lg) Cell-] of the chemically modified cellulosic polymer is substituted with the substituent R.
  • the chemically modified cellulosic polymer is composed entirely of cellulose (in the case of cellulose), this repeating unit is a glucopyranose residue, and the number of hydroxyl groups per unit is 3, so the upper limit of the degree of substitution is Is 3.
  • the cellulosic polymer is lignocellulose
  • the lignocellulose contains hemicellulose and lignin together with cellulose.
  • the xylose residue in xylan contained in hemicellulose or the galactose residue in arabinogalactan has 2 hydroxyl groups, and the standard lignin residue also has 2 hydroxyl groups. Therefore, the number of these hydroxyl groups is smaller than 3.
  • the upper limit of the degree of substitution with the substituent R in lignopulp is less than 3.
  • the upper limit of this substitution degree is about 2.7 to 2.8 depending on the contents of hemicellulose and lignin contained in the lignopulp.
  • the cellulosic polymer is holocellulose
  • helocellulose contains hemicellulose together with cellulose, so the average number of hydroxyl groups in this repeating unit is less than 3. Therefore, the upper limit of the degree of substitution is smaller than 3.
  • the degree (DS) is preferably about 0.3 to 2.55. By setting the substitution degree (DS) to about 0.3 to 2.55, it is possible to obtain a chemically modified MFC having an appropriate crystallinity and SP (solubility parameter).
  • the degree of substitution is more preferably 0.4 to 2.55, further preferably 0.5 to 2.5.
  • DS is preferably 0.4 to 2.5, more preferably 0.5 to 2.5, still more preferably 0.56 to 2.5. If the DS is within that range, the crystallinity can be maintained at about 42.7% or more.
  • the degree of substitution is higher than that of a highly hydrophilic raw material CP fiber that is more hydrophobic than that. From the necessity of being uniformly dispersed in the thermoplastic resin, it is preferably about 0.05 to 2.0, more preferably about 0.1 to 2.0, still more preferably about 0.1 to 0.8.
  • the degree of substitution (DS) can be analyzed by various analysis methods such as elemental analysis, neutralization titration method, FT-IR, and two-dimensional NMR ( 1 H and 13 C-NMR).
  • the chemically modified CP is made into a suspension or slurry, and refiner, high pressure homogenizer, grinder, uniaxial or multi-axis It can be carried out by using a known means such as mechanical milling or beating with a shaft kneader (preferably a multi-axis kneader) or a bead mill.
  • the chemically modified CP is a uniaxial or multiaxial kneading machine (preferably a multiaxial kneading machine) together with a thermoplastic resin, which is melted and kneaded under heating.
  • the chemically modified CP can be fibrillated by the shearing force during kneading to form microfibrils, and can be chemically modified MFC in the thermoplastic resin. Therefore, according to the method of melt-kneading the chemically modified CP together with the thermoplastic resin, the thermoplastic resin composition containing the chemically modified MFC can be advantageously produced by a simple operation.
  • the raw material cellulosic pulp (raw material CP) is made into a suspension or slurry, and refiner, high pressure homogenizer, grinder, uniaxial or multiaxial kneader (preferably a twin
  • a non-chemically modified MFC can be produced by defibration and fibrillation using a known means such as mechanical milling or beating with a shaft kneader) or a bead mill.
  • this can be chemically modified by a method similar to the method for producing the chemically modified CP to produce a chemically modified MFC.
  • Non chemically modified MFC and chemical modification MFC fiber diameter non-chemically modified MFC which has loosened the fibers in the aforementioned cellulosic pulp (e.g. Rigunoparupu) to nanosize level (the defibrated), chemically modified MFC is
  • the fibers in the above-mentioned chemically modified cellulosic pulp for example, chemically modified ligno pulp
  • the average fiber diameter (fiber width) of the non-chemically modified MFC and the chemically modified MFC contained in the fiber reinforced resin composition is usually about 4 to 1000 nm, preferably about 4 to 800 nm, more preferably about 4 to 200 nm.
  • the average fiber length is preferably about 5 ⁇ m or more.
  • the chemically modified CP When a fiber-reinforced resin composition is produced using the chemically modified CP, the chemically modified CP can be melt-kneaded with a thermoplastic resin, and the chemically modified CP can be defibrated into the chemically modified MFC simultaneously with the kneading. ..
  • the defibration of the chemically modified CP is insufficient, and even if the fiber composition after defibration contains a chemically modified MFC larger than the fiber diameter in the resin composition, the object of the present invention is achieved. As long as it is included in the present invention, a resin composition containing such a chemically modified MFC.
  • the chemically modified MFC-containing resin composition shows a flexural modulus of 1.1 times or more with respect to the flexural modulus of a resin containing no cellulosic fibers
  • this is the chemically modified MFC-containing resin of the present invention. It is a composition.
  • the preferable ranges of the average fiber diameter and the average fiber length of the non-chemically modified MFC are the same as those of the above chemically modified MFC.
  • Fiber diameter and fiber length of non-chemically modified MFC and chemically modified MFC can be measured using a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the average value of the fiber diameter (average fiber diameter) and the average value of the fiber length (average fiber length) are obtained as an average value when measured for at least 30 MFCs or chemically modified MFCs in the field of view of a scanning electron microscope. be able to.
  • the specific surface area of the non-chemically modified MFC and chemical modification MFC specific surface area non-chemically modified MFC and chemical modification MFC is preferably about 70 ⁇ 300m 2 / g, more preferably about 70 ⁇ 250m 2 / g, 100 ⁇ 200m 2 / About g is more preferable.
  • the contact area can be increased when the composition is combined with a resin (matrix), thereby improving the strength of the resin molded body. be able to.
  • the chemically modified MFC is preferable because it can be easily dispersed in the resin of the resin composition and can improve the strength of the resin molded body.
  • the non-chemically modified MFC and the chemically modified MFC are preferably in a state where the crystal structure of cellulose existing in the raw material pulp is maintained as much as possible.
  • the hydroxyl groups existing on the surface of the raw material fiber such as the hydroxyl group of cellulose and the hydroxyl group of hemicellulose, are chemically modified so that the cellulose crystal structure originally present in the raw material pulp is not broken.
  • the fiber-reinforced resin composition of the present invention preferably has a crystallinity of the non-chemically modified MFC and the chemically modified MFC contained in the composition of about 42.7% or more, and the crystal form thereof has a cellulose type I crystal.
  • the “crystallinity” is an abundance ratio of crystals (mainly cellulose type I crystals) in all cellulose.
  • the crystallinity of the non-chemically modified MFC and the chemically modified MFC (preferably cellulose I type crystals) is preferably about 50% or more, more preferably about 55% or more, further preferably about 55.6% or more, about 60% or more. Is even more preferable, and about 69.5% or more is particularly preferable.
  • the upper limit of crystallinity of non-chemically modified MFC and chemically modified MFC is about 80%.
  • the cellulose type I crystal structure is, for example, as described in “Dictionary of Cellulose”, first edition, new edition, 81-86 pages, or 93-99 pages, published by Asakura Shoten. Most natural celluloses have a cellulose type I crystal structure.
  • a cellulose fiber having, for example, a cellulose II, III, or IV structure rather than a cellulose I crystal structure is derived from cellulose having a cellulose I crystal structure.
  • the I-type crystal structure has a higher crystal elastic modulus than other structures.
  • the ratio of crystalline regions in cellulose is about 50-60% for wood pulp and about 70% for bacterial cellulose, which is higher than this.
  • Cellulose not only has a high elastic modulus due to its extended chain crystal, but also exhibits a strength five times that of steel and a linear thermal expansion coefficient of 1/50 or less that of glass.
  • Plant fiber The plant fiber (B) contained in the fiber-reinforced resin composition of the present invention satisfies the requirement (b) described above.
  • a part of hydrogen atoms of a hydroxyl group of cellulose constituting the plant fiber of (B-1) is an acyl group having 2 to 4 carbon atoms, and the following formula (2):
  • R 1 and R 2 are the same as above.
  • Lamy is also known as “ramie”
  • hemp is also known as “cannabis”
  • linen is also known as “flax”
  • jute is also known as “burlap”
  • Abaca is also known as “manila hemp”
  • sisal is also known as “sisal”.
  • Kenaf is also referred to as "Hemp”.
  • ramie, hemp, linen, jude, and kenaf are bast fibers
  • abaca and sisal are vein fibers
  • cotton is seed hair fibers.
  • the average fiber diameter of vegetable fibers is preferably about 10-70 ⁇ m.
  • the average fiber length of vegetable fibers is preferably about 2 to 200 mm.
  • the non-chemically modified plant fiber is preferably one or more plant fibers selected from the group consisting of ramie, linen, abaca, and kenaf.
  • one or two kinds of vegetable fibers selected from the group consisting of ramie and linen are more preferable, and ramie is most preferable.
  • the chemically modified plant fiber a part of hydrogen atoms of a hydroxyl group of cellulose, which constitutes a plant fiber selected from the group consisting of ramie, hemp, linen, jute, abaca, sisal, kenaf, and cotton, has 2 to 4 carbon atoms.
  • the one or more chemically modified plant fibers modified with the acyl group of 1 are preferable because they are easily produced.
  • More than one kind of chemically modified plant fiber is preferable, more preferably a chemically modified plant fiber in which a part of hydrogen atoms of the hydroxyl group of cellulose constituting the ramie is modified with an acyl group having 2 to 4 carbon atoms, and cellulose constituting the ramie
  • ramie or acetylated ramie suitably contributes to improvement or maintenance of impact resistance of the molded article of the fiber-reinforced resin composition of the present invention. Therefore, it is particularly preferable.
  • degree of modification of chemically modified plant fiber (hereinafter also referred to as “degree of substitution” or “DS”) consists of ramie, hemp, linen, jute, abaca, sisal, kenaf, and cotton.
  • a part of the hydrogen atoms of the hydroxyl group of cellulose constituting the plant fiber selected from the group has an acyl group having 2 to 4 carbon atoms, a carboxy group-containing acyl group represented by the formula (2), or the carboxy group-containing The degree of modification with a salt of an acyl group.
  • the upper limit of the substitution degree is theoretically close to 3, but the preferable substitution degree (DS) is about 0.05 to 1.5, more preferably about 0.1 to 1.2.
  • the substitution degree (DS) is more preferably about 0.2 to 1.2, further preferably 0.3 to 1.0.
  • the preferred DS is 0.3 to 1.2, more preferably 0.3 to 0.7.
  • Chemically modified plant fiber is obtained by using plant fiber instead of cellulose pulp (CP), and acylating or half-esterifying the plant fiber according to the method for producing chemically modified cellulose pulp (chemically modified CP) described above. It can be manufactured.
  • thermoplastic resins among various resins are preferably used because of their excellent productivity and versatility. ..
  • thermoplastic resin polyamide, polyolefin, aliphatic polyester, aromatic polyester, polyacetal, polycarbonate, polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS resin), polycarbonate-ABS alloy (PC-ABS alloy), and modified polyphenylene Ether (m-PPE) is mentioned.
  • thermoplastic resin the above resins may be used alone or as a mixed resin of two or more kinds.
  • PA polyamide
  • polyamide 6 polyamide 6
  • polyamide 66 nylon 66, PA66
  • polyamide 610 PA610
  • polyamide 612 PA612
  • polyamide 11 PA11
  • polyamide 12 PA12
  • polyamide 46 Polyamide XD10 (PAXD10), polyamide MXD6 (PAMXD6) and the like can be preferably used.
  • polypropylene PP
  • PP polypropylene
  • PE polyethylene
  • PP polypropylene
  • MAPP maleic anhydride modified polypropylene
  • PE polyethylene
  • HDPE high density polyethylene
  • polypropylene isotactic polypropylene (iPP), syndiotactic polypropylene (sPP), etc.
  • iPP isotactic polypropylene
  • sPP syndiotactic polypropylene
  • a polymer or copolymer of a diol and an aliphatic dicarboxylic acid such as succinic acid or valeric acid (for example, polybutylene succinate (PBS)), or a hydroxycarboxylic acid such as glycolic acid or lactic acid alone.
  • PBS polybutylene succinate
  • a hydroxycarboxylic acid such as glycolic acid or lactic acid alone.
  • Polymers or copolymers for example, polylactic acid, poly ⁇ -caprolactone (PCL), etc.
  • PCL poly ⁇ -caprolactone
  • polymers of diols such as ethylene glycol, propylene glycol and 1,4-butanediol and aromatic dicarboxylic acids such as terephthalic acid can be preferably used.
  • polyethylene terephthalate (PET) polypropylene terephthalate (PPT), polybutylene terephthalate (PBT) and the like can be preferably used.
  • polyacetal also referred to as polyoxymethylene, POM
  • a copolymer of paraformaldehyde and oxyethylene can be preferably used.
  • PC polycarbonate
  • a reaction product of bisphenol A or a bisphenol derivative thereof and phosgene or phenyldicarbonate can be preferably used.
  • PS polystyrene
  • HIPS acrylonitrile-butadiene-styrene copolymer
  • ABS resin acrylonitrile-butadiene-styrene copolymer
  • PC polycarbonate
  • ABS PC-ABS alloy
  • a blended product of PPE and PS is a type of modified polyphenylene ether (PPE) (m-PPE).
  • PPE-PS blended product is a type of modified polyphenylene ether (PPE) (m-PPE).
  • PPE-PS blend product is preferably used because it has high heat resistance and is lightweight.
  • thermoplastic resins PA, POM, PP, MAPP, PE, polylactic acid, lactic acid copolymer resin, PBS, PET, PPT, PBT, from the viewpoint of excellent mechanical properties, heat resistance, surface smoothness and appearance. It is preferable to use at least one resin selected from the group consisting of PS, ABS resin and PC-ABS alloy.
  • resins other than the above for example, polyvinyl chloride, polyvinylidene chloride, fluororesin, (meth) acrylic resin, (thermoplastic) polyurethane, vinyl ether resin, polysulfone resin, cellulose resin (eg triacetylated cellulose, (Diacetylated cellulose, etc.) can also be preferably used.
  • the content ratio of (A) MFC in the fiber-reinforced resin composition of the present invention is (C) thermoplastic resin.
  • the amount is preferably about 2 to 50 parts by mass, more preferably about 2 to 40 parts by mass, still more preferably about 3 to 35 parts by mass, relative to 100 parts by mass.
  • the content ratio of (A) MFC in the fiber reinforced resin composition is most preferably about 5 to 30 parts by mass with respect to 100 parts by mass of the (C) thermoplastic resin.
  • the content ratio of the (B) vegetable fiber in the fiber-reinforced resin composition of the present invention is preferably about 1 to 40 parts by mass, more preferably about 2 to 30 parts by mass, relative to 100 parts by mass of the (C) thermoplastic resin. It is preferably about 2.5 to 25 parts by mass and more preferably about 2.5 to 25 parts by mass.
  • the content ratio of the (B) vegetable fiber (preferably ramie or acetylated ramie) in the fiber reinforced resin composition is most preferably about 3 to 15 parts by mass relative to 100 parts by mass of the (C) thermoplastic resin. preferable.
  • the ratio of (A) MFC to (B) vegetable fiber in the fiber-reinforced resin composition of the present invention is a mass ratio. Is preferably 0.2 to 4, more preferably 0.5 to 3, and even more preferably 0.5 to 2.
  • thermoplastic resin By blending (B) vegetable fibers with (A) MFC in (C) thermoplastic resin, a lightweight fiber-reinforced resin composition with excellent mechanical properties can be obtained. Also, by blending (B) vegetable fiber with (A) MFC in (C) thermoplastic resin, the impact resistance of the composite (molded body) produced is improved or maintained, and the strength and elastic modulus are improved. Can be improved. In particular, by blending the ramie fiber and / or the chemically modified ramie fiber with the chemically modified MFC in the thermoplastic resin, not only the elastic modulus and strength of the composite (molded body) but also impact resistance can be improved.
  • the fiber-reinforced resin composition of the present invention even if containing (A) MFC, and (B) vegetable fiber, as well as general-purpose plastic, because it is softened and easily molded when heated, good moldability Can be expressed.
  • thermoplastic resin for example, a compatibilizer; a surfactant; an antioxidant; a flame retardant; Inorganic compounds such as tannin, zeolite, ceramics, metal powder; colorants; plasticizers; fragrances; pigments; flow control agents; leveling agents; conductive agents; antistatic agents; UV absorbers; UV dispersants; deodorants, etc. You may mix
  • the fiber-reinforced resin composition of the present invention contains (A-1) chemically modified MFC as (A) MFC, self-aggregation of these fibers due to hydrogen bond can be suppressed. Therefore, when (A-1) chemically modified MFC, (B) vegetable fiber, and (C) thermoplastic resin are mixed, (A-1) aggregation of chemically modified MFCs is suppressed, and (A-1) chemical The modified MFC and the (B) vegetable fiber show good dispersibility in the (C) thermoplastic resin. As a result, the fiber-reinforced resin composition of the present invention is excellent in mechanical properties, heat resistance, surface smoothness and appearance.
  • the solubility parameter (SP) of (A-1) chemically modified MFC is closer to that of (C) thermoplastic resin. Is preferred.
  • (C) a highly polar resin is used as the thermoplastic resin
  • (A) MFC when the substituent R is, for example, an acetyl group, its substitution degree (DS) is about 0.4 to 1.2 and its solubility is It is preferred to use acetylated MFCs with parameters around 12-15.
  • the highly polar resin for example, PA, POM, polylactic acid and the like are preferable.
  • (C) When using a resin with a small polarity as the thermoplastic resin, use (A) MFC that is a chemically modified MFC having a substitution degree (DS) of about 1.2 or more and a solubility parameter of about 8 to 12 It is preferable.
  • the resin having a small polarity for example, PP, PE and the like are preferable.
  • the chemically modified MFC an acetylated MFC having a substitution degree (DS) of about 1.2 or more is preferable.
  • the fiber-reinforced resin composition of the present invention comprises (A) MFC, (B) plant fiber, and (C) thermoplastic resin (matrix material) melt-kneaded to obtain (A) MFC and (B) plant fiber ( C) It can be produced by dispersing it in a thermoplastic resin.
  • the fiber-reinforced resin composition of the present invention contains a chemically modified cellulosic pulp (chemically modified CP), (B) plant fiber, and (C) a thermoplastic resin at once. Then, it is preferable to melt-knead and manufacture using a kneader or the like. In this case, it is possible to combine the chemically modified CP with the chemically modified MFC while defibrating it during melt-kneading. Therefore, prepare the chemically modified MFC separately, and use the (B) plant fiber and (C) thermoplastic It can be produced more easily than the method of producing a fiber-reinforced resin composition by kneading with a resin.
  • chemically modified cellulosic pulp chemically modified CP
  • B plant fiber
  • C thermoplastic resin
  • the manufacturing method 2 is a manufacturing method using (AP) chemically modified CP as a raw material when (A) MFC is a chemically modified MFC.
  • This production method is specifically a method for producing a fiber-reinforced resin composition containing (A-1) chemically modified microfibrillated cellulosic fibers, (B) plant fibers, and (C) thermoplastic resin.
  • the method includes a step of melt-kneading (AP) the chemically modified cellulosic pulp, (B) plant fiber, and (C) a thermoplastic resin, and micro-fibrillating the chemically modified cellulosic pulp during the melt-kneading.
  • (AP) chemically modified cellulosic pulp has the following formula (1-1): (Lg) Cell-OR (1-1) [In the formula (1-1), (Lg) Cell- represents a residue obtained by removing a hydroxyl group from the polysaccharide and lignin that constitute cellulose, holocellulose, and / or lignocellulose in the cellulosic polymer.
  • R 1 and R 2 are the same or different and each represents a hydrogen atom, a methyl group, an ethyl group, or an optionally branched alkenyl group or alkyl group having 3 to 20 carbon atoms. Provided that when one of R 1 and R 2 has 4 to 20 carbon atoms, the other of R 1 and R 2 is a hydrogen atom.), Or a carboxy group-containing acyl group represented by A salt of a group-containing acyl group is shown. ] It is a chemically modified cellulosic pulp composed of a chemically modified cellulosic polymer.
  • a part of hydrogen atoms of a hydroxyl group of cellulose constituting the plant fiber of (B-1) is an acyl group having 2 to 4 carbon atoms, and the following formula (2):
  • R 1 and R 2 are the same or different and each represents a hydrogen atom, a methyl group, an ethyl group, or an optionally branched alkenyl group or alkyl group having 3 to 20 carbon atoms. Provided that when one of R 1 and R 2 has 4 to 20 carbon atoms, the other of R 1 and R 2 is a hydrogen atom.
  • the (A-1) chemically modified microfibrillated cellulosic fiber is a microfibrillated fiber composed of the chemically modified cellulosic polymer represented by the formula (1-1).
  • fibrillation of chemically modified CP proceeds well due to shear stress during kneading.
  • the chemically modified CP is well defibrated in the resin into the (A) chemically modified MFC.
  • the production method 2 it is possible to produce a fiber-reinforced resin composition in which (A) the chemically modified MFC and (B) vegetable fiber are favorably dispersed in the (C) thermoplastic resin.
  • Manufacturing method 3 The fiber-reinforced resin composition of the present invention, when (A) MFC is a chemically modified MFC, (AP) chemically modified CP and (C) a thermoplastic resin are kneaded to chemically modify the chemically modified CP during melt kneading. A kneaded product is obtained by defibration into a modified MFC, and then the obtained kneaded product and (B) a vegetable fiber or a resin composition containing a vegetable fiber and a thermoplastic resin can be produced by a method of melt kneading. it can.
  • the production method 3 is another production method using (AP) chemically modified CP as a raw material when (A) MFC is a chemically modified MFC.
  • This method is a method in which, after melt-kneading the chemically modified CP and the thermoplastic resin together, the kneaded material is melt-kneaded by adding the resin composition containing the plant fiber or the plant fiber and the thermoplastic resin. is there.
  • this method is a method for producing a fiber-reinforced resin composition containing (A-1) chemically modified microfibrillated cellulosic fiber, (B) plant fiber, and (C) thermoplastic resin.
  • Process (1) (AP) a chemically modified cellulosic pulp and (C) a thermoplastic resin are kneaded to microfibrillize the chemically modified cellulosic pulp during the melt-kneading, and step (2): A production method comprising a step of compounding the kneaded product obtained in the step (1) with (B) vegetable fiber or a resin composition containing a vegetable fiber and a thermoplastic resin.
  • (AP) chemically modified cellulosic pulp has the following formula (1-1): (Lg) Cell-OR (1-1) [In the formula (1-1), (Lg) Cell- represents a residue obtained by removing a hydroxyl group from the polysaccharide and lignin that constitute cellulose, holocellulose, and / or lignocellulose in the cellulosic polymer.
  • R 1 and R 2 are the same or different and each represents a hydrogen atom, a methyl group, an ethyl group, or an optionally branched alkenyl group or alkyl group having 3 to 20 carbon atoms. Provided that when one of R 1 and R 2 has 4 to 20 carbon atoms, the other of R 1 and R 2 is a hydrogen atom.), Or a carboxy group-containing acyl group represented by A salt of a group-containing acyl group is shown. ] It is a chemically modified cellulosic pulp composed of a chemically modified cellulosic polymer.
  • a part of hydrogen atoms of a hydroxyl group of cellulose constituting the plant fiber of (B-1) is an acyl group having 2 to 4 carbon atoms, and the following formula (2):
  • R 1 and R 2 are the same or different and each represents a hydrogen atom, a methyl group, an ethyl group, or an optionally branched alkenyl group or alkyl group having 3 to 20 carbon atoms. Provided that when one of R 1 and R 2 has 4 to 20 carbon atoms, the other of R 1 and R 2 is a hydrogen atom.
  • the (A-1) chemically modified microfibrillated cellulosic fiber is a microfibrillated fiber composed of the chemically modified cellulosic polymer represented by the formula (1-1).
  • thermoplastic resin composition containing plant fibers and a thermoplastic resin used in the production method 3 (I) a melt mixture of (B) plant fibers and (C) thermoplastic resins, and (II) (B) plant fibers Both (C) powder mixtures with thermoplastics can be used.
  • the heating set temperature at the time of melt kneading in each manufacturing method is a temperature (A + 20) higher than the recommended processing temperature (A + 20) from the minimum processing temperature (A ° C) recommended by the supplier that supplies the thermoplastic resin used in the present invention. C.) range is preferred.
  • the heating set temperature during melt kneading is preferably 225 to 240 ° C.
  • the heating set temperature during melt kneading is preferably 170 ° C to 190 ° C.
  • the heating set temperature during melt kneading is preferably 160 to 180 ° C.
  • thermoplastic resin By setting the mixing temperature in this temperature range, (A) chemically modified MFC or chemically modified CP, (B) plant fiber and (C) thermoplastic resin can be uniformly mixed.
  • manufacturing method 2 and manufacturing method 3 since the undefibrated chemically modified CP is mixed with the resin and defibration is performed by the shear stress of the kneading machine, the manufacturing cost can be reduced.
  • the molded product of the present invention comprises a fiber reinforced resin composition.
  • a molded product can be produced using the fiber-reinforced resin composition of the present invention.
  • a molding material having a shape such as a film shape, a sheet shape, a plate shape, a pellet shape, and a powder shape is prepared, and this molding material is used for manufacturing a molded body. be able to.
  • the fiber-reinforced resin composition or molding material of the present invention can be molded by various known molding methods to produce molded products of various shapes such as plate-like, rod-like, and three-dimensional structures.
  • the molding method include a mold molding method, an injection molding method, an extrusion molding method, a hollow molding method, and a foam molding method.
  • the injection molding method is excellent in productivity and manufacturing cost because the molding speed is high and molding of a complicated shape is easy.
  • the molded article of the present invention is molded from a fiber reinforced resin composition containing (A) MFC, (B) plant fiber, and (C) thermoplastic resin, a fiber containing a fiber having a large specific gravity such as glass fiber. It is lighter than a molded product molded from the reinforced resin composition.
  • thermal recycling is easier than that of a molded product molded from a fiber-reinforced resin composition containing an inorganic fiber such as glass fiber or carbon fiber.
  • the molded product of the present invention is advantageous in reducing carbon dioxide emissions in LCCO2 (life cycle CO2).
  • the molded article of the present invention as an interior material, an exterior material, a structural material of a transportation machine such as an automobile, an electric train, a ship, an airplane, etc., it is possible to achieve improvement of energy efficiency of a transportation machine and reduction of exhaust gas. it can.
  • the molded product of the present invention for housings, structural materials, internal parts, etc. of electric appliances such as personal computers, televisions, and telephones, it is possible to reduce their weight. By reducing the weight, it is possible to reduce energy consumption during transportation of the electric appliances, and it is possible to comfortably use the electric appliances.
  • the molded product of the present invention as a building material, it becomes possible to improve the earthquake resistance of the building.
  • the content of various components such as cellulosic pulp, chemically modified cellulosic pulp, unmodified MFC, chemically modified MFC, plant fiber, chemically modified plant fiber, and thermoplastic resin is% by mass unless otherwise specified. indicate.
  • the content ratio of the cellulosic fiber in the composition is represented by the mass ratio of the fiber component (cellulose + hemicellulose) in the total mass of the composition. That is, the content rate of the chemically modified cellulosic fiber in the composition is indicated by the content rate (percentage) of the mass converted into the non-chemically modified fiber.
  • PA6 Polyamide 6
  • a Polyamide 6
  • b Chemically modified Todomatsu fiber
  • b Chemically modified Todomatsu equivalent percentage
  • c Chemically modified ramie
  • test Method The test method used in Examples and Comparative Examples is as follows.
  • reaction solution After allowing to cool, 100 ⁇ L of the reaction solution was diluted with ultrapure water and subjected to ion chromatographic analysis manufactured by Thermo Fisher Scientific Co., Ltd. to analyze the sugar component contained in the sample.
  • the back titration filtrate contains sodium acetate resulting from hydrolysis and NaOH added in excess.
  • the neutralization titration of this NaOH was carried out using 1N HCl and phenolphthalein, and the number of moles of the acetyl group ester-bonded to the hydroxyl group of cellulose and the like from the following formula (C), and the number of moles of repeating units of cellulose Calculate (D).
  • Izod Impact Test An Izod impact test was performed using an Izod impact tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.). A notch having a depth of 2 mm was inserted in the center of the test piece. In the 2.75JN test, the notch side was hit with a 2.75J hammer to propagate a crack from the notch, and the impact strength was calculated.
  • PA6 nylon 6
  • a test piece of 4x2x1.2 mm was cut out from the injection molded product.
  • the test piece was added to 400 ml of NMP and immersed at 190 ° C for 2 to 4 hours to elute PA6.
  • 2-3) The residue (fiber) after elution of PA6 was put in a glass vial containing ethanol, and ultrasonically stirred to suspend the fiber in ethanol. After that, a sample for microscopic observation was prepared according to 1-2) and 1-3) above.
  • composition (mass%) was cellulose 84.4%, hemicellulose 14.5%, and lignin 1.1%.
  • the degree of acetylation substitution was calculated by measuring the IR spectrum in accordance with the above-mentioned (3-2) DS measurement method by infrared (IR) absorption spectrum. Also, the following Ac-DS of Ac-Todomatsu P-2 and P-3, Ac-ramie, Ac-kenaf, Ac-flax, and Ac-abaca were calculated by the same method.
  • This sheet-shaped Ac Todomatsu P-1 was used to prepare the compositions of Example 1 (Test No. PA6-629) and Comparative Example 1 (Test No. PA6-628) below.
  • This sheet-like Ac Todomatsu P-2 was prepared from the compositions of Example 2 (Test No. PA6-568), Example 3 (Test No. PA6-558), and Comparative Example 2 (Test No. PA6-561) described below. Used for.
  • This sheet-like Ac Todomatsu P-3 was prepared as Example 4 (Test No. PA6-645), Example 5 (Test No. PA6-642), Example 6 (Test No. PA6-646), and Example 7 (Test). No. PA6-644) and Comparative Example 5 (test number PA6-640) were used for the production of the compositions.
  • ramie (trade name: 6T TOP fineness 4.63 dtex) manufactured by Tosco Corp. was cut to a length of 1 to 3 cm and used.
  • Acetylated ramie 400 ml of acetic anhydride (5 times equivalent of cellulose) and 240 ml of acetic acid were added to 120 g of ramie (water content 8.42%) cut to a length of 1 to 3 cm and reacted at 100 ° C. for 20 hours. After ethanol was added to the reaction mixture to stop the reaction, the reaction mixture (solid content) was collected by filtration. This was washed with water (3 times), washed with isopropyl alcohol (IPA) 3 times, and dried to obtain Ac ramie (Ac-modified DS 0.33).
  • IPA isopropyl alcohol
  • kenaf (B-grade fiber bundle from Bangladesh, about 20 to 100 ⁇ m) purchased from OCM GROUP Co., Ltd. was used.
  • Acetylated kenaf (Ac kenaf)
  • the Ac kenaf of Ac-modified DS 0.25 used in Example 9 (Test No. PA6-687) described below was produced as follows. 16 g of acetic anhydride and 288 g of acetic acid were added to 32 g of kenaf fiber, and heated in an oil bath at 100 ° C. for 5 hours. The reaction mixture was collected by filtration, washed with water, washed with IPA, and the fibers were cut to a size of 1 to 2 cm and dried.
  • the Ac kenaf of Ac-modified DS0.64 used in Example 10 (Test No. PA6-688) described below was manufactured as follows. 51 g of acetic anhydride and 243 g of acetic acid were added to 32 g of kenaf fiber, and the mixture was heated in an oil bath at 100 ° C. for 5 hours. The reaction mixture was collected by filtration, washed with water, washed with IPA, and the fibers were cut to a size of 1 to 2 cm and dried.
  • the abaca manufactured by Nippon Paper Papyria Co., Ltd. was used as the abaca.
  • Acetylated abaca (Ac abaca)
  • the Ac abaca of Ac-modified DS 0.5 used in each of Example 6 (Test No. PA6-646), Example 7 (Test No. PA6-644), and Comparative Example 7 (Test No. PA6-643) described below is as follows. As manufactured. NMP was added to abaca pulp and dehydrated under reduced pressure with heating. Acetic anhydride (0.6 molar equivalent) and K 2 CO 3 (0.2 molar equivalent) were added to this NMP suspension of abaca pulp (solid content 15%), and the mixture was heated and stirred at 80 ° C. for 2 hours to cause reaction. After the reaction was completed, the solid matter was washed with acetone and water to obtain a slurry of acetylated abaca pulp, which was dehydrated.
  • Polyamide (powder type, grade: A1020LP) manufactured by Unitika Ltd. was used as the resin (1) powdery polyamide 6 (sometimes referred to as “PA6 powder”).
  • pelletized polyamide 6 (sometimes referred to as “PA6 pellets”), pelletized polyamide 6 (grade: A1020BRL) manufactured by Unitika Ltd. was used.
  • a mixer FM10C: Nippon Coke Industry Co., Ltd.
  • the melt kneading set temperature was 200 to 215 ° C. (upstream to downstream of the kneading machine).
  • Example 2 (Test No. PA6-568): Production of a PA6 composition containing fibrillated Ac Todomatsu (Ac-compound DS 0.7) and Ac ramie (Ac-compound DS 0.33), and a molded article thereof.
  • Example 3 (Test No. PA6-558): Preparation of PA6 Composition Containing Fibrillated Ac Todomatsu (Ac Derivative DS 0.7) and Ac Ramie (Ac Derivative DS 0.33), and Molded Article Thereof Without passing through the master batch of Todomatsu / PA6 powder (powdered MB-2), create the master batch of Ac Todomatsu / PA6 powder / Ac ramie (powdered MB-3), melt and knead it with PA6, It is a method for producing a PA6 composition containing fibrillated Ac Todomatsu and Ac ramie having the same composition as in Example 2 above. Ac Todomatsu P-2 and Ac ramie were the same as in Example 2.
  • the sheet-shaped Ac Todomatsu P-2 was immersed overnight in distilled water to swell it, then roughly crushed by the mixer, and the crushed product was put in distilled water and stirred. Next, the water was replaced with IPA, PA6 powder and Ac ramie dipped in IPA were added and mixed, and filtered to obtain a mixture of Ac Todomatsu P / PA6 powder / Ac ramie. This was agitated and dried at about 60 ° C. by the agitator / dryer. The composition ratio of the obtained powdery MB-3 was Ac Todomatsu P / PA6 powder / Ac ramie 11.94 / 32.59 / 5.47.
  • a PA6 composition containing fibrillated Ac Todomatsu and Ac ramie of the same composition as in Example 2 was obtained. Then, this was injection-molded in the same manner as in Example 1 to obtain a molded body.
  • Comparative Example 1 (Test No. PA6-628): Preparation of a PA6 composition containing fibrillated Ac Todomatsu and its moldings This is the control composition of Example 1.
  • the same sheet-like Ac Todomatsu P-1 (Ac-modified DS 0.56) as in Example 1 was used, and was produced by the following method.
  • Comparative Example 2 (Test No. PA6-561): Preparation of a PA6 composition containing fibrillated Ac Todomatsu and its molded body This is a control composition of Examples 2 and 3. The same sheet-like Ac Todomatsu P-2 (Ac-modified DS 0.7) as in Examples 2 and 3 was used, and was produced by the following method.
  • Comparative Example 3 (Test No. PA6-560): Preparation of PA6 Composition Containing Ac Ramie, and Moldings Thereof This is the control composition of Examples 2 and 3. As in Examples 2 and 3, using Ac ramie (Ac-modified DS 0.33) cut to 1 to 1.5 cm, the following method was used.
  • Comparative Example 4 Manufacture of Control Molded Product (PA6 Molded Product)
  • PA6 Molded Product PA6 Molded Product
  • width ⁇ length ⁇ thickness 10
  • a strip-shaped test piece (molded body) of ⁇ 80 ⁇ 4 mm was obtained.
  • composition content ratios in Table 1 the composition content ratios of the chemically modified fibers (Ac Todomatsu and Ac ramie) are shown in terms of mass percentages of the corresponding unmodified fibers (Todomatsu and Ramie).
  • a molded body of the PA6 composition of Example 1 containing fibrillated cellulosic fibers modified with acetyl groups (fibrillated Ac Todomatsu) and ramie, and the fiber of Comparative Example 4 were not included.
  • the flexural modulus, bending strength, and flexural modulus of the molded body of Example 1 were 2.4 times, 1.6 times, and 1.1 times that of the PA6 molded body of Comparative Example 4, respectively.
  • the flexural modulus, flexural strength, and flexural modulus of the molded body of Example 2 were 2.6 times, 1.7 times, and 1.7 times that of the PA6 molded body of Comparative Example 4, respectively. It was 1.3 times.
  • FIG. 1 shows an electron micrograph image of acetylated Todomatsu pulp.
  • FIG. 2 shows an electron micrograph image of the acetylated Todomatsu fiber in the sample prepared from the composition of Example 2.
  • the diameter of the fibers was about 20 ⁇ m for thin fibers and about 60 ⁇ m for thick fibers.
  • the fiber length was over 1900 ⁇ m.
  • the sheet-like Ac Todomatsu P-3 was treated in the same manner as in the preparation of the powdery MB-1 of Example 1 to obtain a powdery masterbatch containing Ac Todomatsu P-3 and PA6 powder (powder).
  • Example 5 (Test No. PA6-642): PA6 composition containing fibrillated Ac todomatsu (Ac-compound DS 0.67) and Ac flax (Ac-comprising DS 0.57), and production of a molded article thereof Same composition as in Example 4 A PA6 composition containing a ratio of fibrillated Ac Todomatsu and Ac flax, and a molded article thereof were manufactured in the same manner as in Example 3 as described below.
  • Example 5 In place of Ac todomatsu P-2 (Ac-modified DS 0.7) and Ac ramie (Ac-modified DS 0.33) used in Example 3, the same Ac Todomatsu P-3 and Ac flax as in Example 4 were used in Example 5. used.
  • the sheet-shaped Ac Todomatsu P-3 was treated and coarsely pulverized, powdered PA6 powder and Ac flax were added, mixed and dried.
  • powdered MB-7 was prepared.
  • Comparative Example 5 (Test No. PA6-640): Preparation of PA6 Composition Containing Fibrillated Ac Todomatsu, and Molded Articles Thereof This is the control composition of Examples 4 and 5.
  • the same sheet-like Ac Todomatsu P-3 (Ac-modified DS 0.67) used in Examples 4 and 5 and the powdered MB-6 (composition ratio: Ac Todomatsu / PA6 powder 12.11 / 21.23) used in Example 4 were used. Then, the composition and the molded body were prepared by the following procedures.
  • Comparative Example 6 (Test No. PA6-641): Production of PA6 composition containing Ac flax and its molded article This is a control composition of Examples 4 and 5. Using the same Ac flax (Ac-modified DS0.57) as in Examples 4 and 5, PA6 compositions and molded articles containing Ac flax were produced by the following method.
  • composition content ratios in Table 2 the composition content ratios of the chemically modified fibers (Ac Todomatsu and Ac flax) are converted into the mass percentages of the corresponding unmodified fibers (Todomatsu and flax).
  • the strength and elastic modulus of the molded products of Examples 4 and 5 are large and superior to those of the molded products of Comparative Examples 4 to 6. And, although the molded products of Examples 4 and 5 have an increased fiber content, their impact resistance is not much lower than that of the molded products of Comparative Examples 4 to 6.
  • Example 6 (Study No. PA6-646): Preparation of PA6 Composition Containing Fibrillated Ac Todomatsu (Ac-DS 0.67) and Ac Abaca (Ac-DS 0.5), and Molded Product Thereof A PA6 composition containing Ac abaca and a molded product thereof were manufactured in the same manner as in Example 2 as described below.
  • the sheet-like Ac Todomatsu P-3 (Ac-modified DS0.67) was treated in the same manner as in the preparation of the powdery MB-1 of Example 1 to contain Ac Todomatsu P-3 and PA6 powder.
  • Example 7 (Test No. PA6-644): PA6 composition containing fibrillated Ac Todomatsu (Ac-DS 0.67) and Ac-Abaca (Ac-DS 0.5), and manufacture of its molded article Same composition as in Example 6 A PA composition containing a ratio of fibrillated Ac Todomatsu and Ac abaca, and a molded article thereof were manufactured in the same manner as in Example 3 as described below.
  • This production method was carried out by preparing a master batch of Ac Todomatsu / PA6 powder / Ac Abaca, melting and kneading this with PA6, and PA6 containing the fibrillated Ac Todomatsu and Ac Abaca of the same composition as in Example 6 above. A method of producing a composition.
  • Comparative Example 7 (Test No. PA6-643): Preparation of PA6 Composition Containing Ac Abaca and Molded Articles Thereof This is the control composition of Examples 6 and 7. Using the Ac abaca used in Examples 6 and 7 (Ac-modified DS 0.5), a PA6 composition containing an Ac abaca was prepared by the following method.
  • composition content ratios in Table 3 the composition content ratios of the chemically modified fibers (Ac Todomatsu and Ac Abaca) are shown in terms of the mass percentages of the corresponding unmodified fibers (Todomatsu and Abaca).
  • the strength and elastic modulus of the molded bodies of Examples 6 and 7 are large and excellent as compared with those of the molded bodies of Comparative Examples 4, 5, and 7.
  • the impact resistance of the molded products of Examples 6 and 7 is not much lower than that of the molded products of Comparative Examples 4, 5, and 7 even though the fiber content is increased.
  • Example 8 (Test No. PA6-631): Preparation of PA6 Composition Containing Fibrillated Ac Todomatsu (Ac Derivative DS 0.56) and Kenaf, and Molded Article Thereof Instead of ramie (no chemical modification), kenaf (no chemical modification) ) was used in the same manner as in Example 1 to prepare a PA6 composition containing fibrillated Ac todomatsu (DS 0.56 Ac) and kenaf, and molding this to prepare a fibrillated Ac todomatsu (Ac) And a kenaf (without chemical modification) was prepared.
  • a PA6 composition Containing Fibrillated Ac Todomatsu (Ac Derivative DS 0.56) and Kenaf, and Molded Article Thereof
  • kenaf no chemical modification
  • Example 9 (Test No. PA6-687): Production of PA6 composition containing fibrillated Ac Todomatsu (Ac-compound DS 0.67) and Ac kenaf (Ac-compound DS 0.25), and molded article thereof Ac-Todomatsu sheet P-2 Example 3 using sheet Ac Ac Todomatsu P-3 (Ac compound DS 0.67) instead of (Ac compound DS 0.7) and Ac kenaf (Ac compound DS 0.25) instead of Ac ramie (Ac compound DS 0.33) A PA6 composition containing fibrillated Ac todomatsu (Ac-modified DS 0.67) and Ac kenaf (Ac-modified DS 0.25) was prepared in the same manner as in 1., and molded to obtain a molded product.
  • Example 10 (Study No. PA6-688): Preparation of a PA6 composition containing fibrillated Ac todomatsu (Ac-compound DS 0.67) and Ac kenaf (Ac-comprising DS 0.64), and moldings thereof Ac kenaf (Ac-comprising DS 0.25) PA6 containing fibrillated Ac todomatsu (Ac-modified DS 0.67) and Ac kenaf (Ac-modified DS 0.64) in the same manner as in Example 9 except that Ac-kenaf (Ac-modified DS 0.64) was used instead of).
  • a composition was prepared and molded to obtain a molded body.
  • Comparative Example 8 (Test No. PA6-682): Production of PA6 composition containing fibrillated Ac todomatsu (Ac-compound DS 0.67) and molded article thereof Instead of sheet-like Ac todomatsu P-2 (Ac-compound DS 0.7)
  • a PA6 composition containing PA6 and fibrillated Ac Todomatsu P (Ac-modified DS 0.66) was prepared in the same manner as in Comparative Example 2 except that sheet-like Ac Todomatsu P-3 (Ac-modified DS 0.67) was used. This was molded to obtain a molded body.
  • composition content ratios in Table 4 the composition content ratios of the chemically modified fibers (Ac Todomatsu and Ac Kenaf) are converted into the mass percentages of the corresponding unmodified fibers (Todomatsu and Kenaf).
  • the strength and elastic modulus of the molded bodies of Examples 8 to 10 are large and superior to those of the molded bodies of Comparative Examples 1, 4 and 8.
  • the impact resistances of the molded products of Examples 8 to 10 are not much lower than those of the molded products of Comparative Examples 1, 4 and 8 even though the fiber content is increased.

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Abstract

La présente invention concerne un composite renforcé par des fibres ayant une résistance et une rigidité excellentes et des performances d'absorption des chocs supérieures. La présente invention concerne une composition de résine renforcée par des fibres contenant (A) des fibres de cellulose microfibrillées, des fibres végétales (B) et (C) une résine thermoplastique, les fibres de cellulose microfibrillées (A) comprennent un polymère de cellulose modifié chimiquement ou chimiquement modifié (exigence (a)), et les fibres végétales (B) sont des fibres végétales non modifiées chimiquement ou des fibres végétales chimiquement modifiées (exigence (b)).
PCT/JP2019/043079 2018-11-05 2019-11-01 Composition de résine renforcée par des fibres et son procédé de production WO2020095845A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009029927A (ja) * 2007-07-26 2009-02-12 Toyota Boshoku Corp 熱可塑性樹脂組成物の製造方法及び成形体の製造方法
JP2014220345A (ja) * 2013-05-07 2014-11-20 太陽ホールディングス株式会社 プリント配線板材料およびそれを用いたプリント配線板
WO2016148233A1 (fr) * 2015-03-19 2016-09-22 国立大学法人京都大学 Composition de résine renforcée par des fibres comprenant des nanofibres de cellulose chimiquement modifiées et résine thermoplastique
WO2018123150A1 (fr) * 2016-12-28 2018-07-05 旭化成株式会社 Composition de résine contenant de la cellulose et ingrédient cellulosique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009029927A (ja) * 2007-07-26 2009-02-12 Toyota Boshoku Corp 熱可塑性樹脂組成物の製造方法及び成形体の製造方法
JP2014220345A (ja) * 2013-05-07 2014-11-20 太陽ホールディングス株式会社 プリント配線板材料およびそれを用いたプリント配線板
WO2016148233A1 (fr) * 2015-03-19 2016-09-22 国立大学法人京都大学 Composition de résine renforcée par des fibres comprenant des nanofibres de cellulose chimiquement modifiées et résine thermoplastique
WO2018123150A1 (fr) * 2016-12-28 2018-07-05 旭化成株式会社 Composition de résine contenant de la cellulose et ingrédient cellulosique

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