WO2023074691A1 - Composition de résine, corps moulé l'utilisant et procédé de production d'une composition de résine - Google Patents

Composition de résine, corps moulé l'utilisant et procédé de production d'une composition de résine Download PDF

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WO2023074691A1
WO2023074691A1 PCT/JP2022/039743 JP2022039743W WO2023074691A1 WO 2023074691 A1 WO2023074691 A1 WO 2023074691A1 JP 2022039743 W JP2022039743 W JP 2022039743W WO 2023074691 A1 WO2023074691 A1 WO 2023074691A1
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group
acid
resin composition
cellulosic material
mixture
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PCT/JP2022/039743
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English (en)
Japanese (ja)
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滋 森下
浩之 矢野
有光 臼杵
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国立大学法人京都大学
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
    • C08L93/04—Rosin

Definitions

  • the present invention relates to a resin composition containing a cellulosic material, a molded article using the resin composition, and a method for producing a resin composition.
  • Fiber reinforced plastics are lightweight and have excellent mechanical strength, so they are used for exterior panels and interior materials for automobiles, housings for electrical equipment, construction materials, etc., in order to reduce greenhouse gas emissions. It is expected to be one of the means of building a decarbonized society. In particular, increasing the strength of fiber-reinforced plastic and its efficient production can reduce the amount of plastic used and the amount of energy used, and is one of the means for efficiently suppressing greenhouse gas emissions. Expected.
  • Patent Document 1 describes a modified microfibrillated plant fiber (A) esterified with an alkyl or alkenyl succinic anhydride, and a resin composition containing a thermoplastic resin (B). , a method for producing the same, and a molded article using the same are disclosed.
  • Patent Document 2 discloses a resin composition containing modified nanocellulose obtained by introducing an alicyclic hydrocarbon group to the surface of nanocellulose and a thermoplastic resin.
  • Patent Document 3 discloses a resin composition containing acetylated lignocellulose fibers having specific physical properties and a thermoplastic resin.
  • Patent Document 4 describes a resin composition containing a polymer compound having a primary amino group, a polymer compound modified with maleic anhydride, microfibrillated plant fibers, and a polyolefin. , moldings using the same, and methods for producing them are disclosed.
  • International Publication No. 2011/049162 Patent Document 4 describes a resin composition containing a polymer compound having a primary amino group, a polymer compound modified with maleic anhydride, microfibrillated plant fibers, and a polyolefin.
  • Patent Document 5 describes a composite material containing carboxymethylated cellulose fiber, a polymer compound having a primary amino group, an acid-modified polyolefin, and a polyolefin resin, and a method for producing the same. , and molded articles using the same are disclosed.
  • JP-A-2010-106251 Patent Document 6
  • a polyamide obtained from a C 2-4 alkylene polyamine and a C 4-8 aliphatic dicarboxylic acid is hydrophobized with a reaction product of epichlorohydrin.
  • a resin composition containing cellulosic fibers and a synthetic resin is disclosed.
  • molded articles made from conventional resin compositions containing cellulosic fibers do not necessarily have sufficiently high mechanical strength.
  • the present invention has been made in view of the above problems of the prior art, and provides a resin composition containing a cellulosic material and a thermoplastic resin and capable of forming a molded article having excellent mechanical strength, and
  • An object of the present invention is to provide a molded article and a method for producing a resin composition.
  • the present inventors have made intensive studies to achieve the above object, and found that at least one selected from the group consisting of cellulosic substances (A), polyamines (B), and monocarboxylic acids and rosin acids
  • A cellulosic substances
  • B polyamines
  • monocarboxylic acids and rosin acids By using a resin composition obtained by melt-kneading a mixture containing a carboxylic acid (C) and a thermoplastic resin (D), it is found that a molded article having excellent mechanical strength can be obtained, and the present invention is completed. reached.
  • the present invention provides the following aspects.
  • R represents an alkyl group, an alkenyl group, an alicyclic hydrocarbon group, an oxyalkyl group to which an alicyclic hydrocarbon group is bonded, or a phenoxyalkyl group, and the phenyl group of the phenoxyalkyl group may be bonded with an alkyl group or an alicyclic hydrocarbon group, the alkyl group and the alkenyl group may have a branched chain, and a plurality of the alicyclic hydrocarbon groups are crosslinked or condensed You may have ] and at least one selected from the group consisting of a monocarboxylic acid represented by and abietic acid, neoabietic acid, parastric acid, pimaric acid, isopimaric acid, dehydroabietic acid and derivatives thereof, in [1] The described resin composition.
  • the mixture further contains at least one carboxylic acid (E) selected from the group consisting of polycarboxylic acids and acid anhydrides thereof, acid anhydride-modified polyolefins and hydrolysates thereof, [1 ]
  • the resin composition according to any one of [3].
  • cellulosic material A
  • polyamines B
  • at least one carboxylic acid C
  • a solvent having a hydrophilic group and a hydrophobic group and a step of melt-kneading the mixture and the thermoplastic resin (D).
  • the cellulosic material (A) is added to a solution obtained by mixing the polyamines (B) and the carboxylic acids (C) in the solvent having a hydrophilic group and a hydrophobic group. to prepare the mixture, the method for producing a resin composition according to [6].
  • the resin composition of the present invention contains a cellulosic material (A), polyamines (B), and at least one carboxylic acid (C) selected from the group consisting of monocarboxylic acids and rosin acids. It is a melt-kneaded product of the mixture and the thermoplastic resin (D). In such a resin composition (melt kneaded product), as shown in FIG.
  • the cellulosic material (A) can be highly dispersed, and it is presumed that a molded article having excellent mechanical strength can be obtained.
  • the cellulosic material (A) in the mixture can be finely treated (for example, defibrillation treatment) or the thermoplastic resin ( It is possible to efficiently dehydrate the cellulosic material (A) during melt-kneading with D).
  • a molded article having excellent mechanical strength which is made of a resin composition containing a cellulosic material and a thermoplastic resin.
  • FIG. 1 is a graph showing the relationship between bending strain and bending stress of molded articles produced using the resin compositions obtained in Examples 1 to 2, 6 to 7, 13 to 14 and Comparative Example 1.
  • FIG. 1 is a graph showing the relationship between bending strain and bending stress of molded articles produced using the resin compositions obtained in Examples 1 to 2, 6 to 7, 13 to 14 and Comparative Example 1.
  • the resin composition of the present invention is a mixture containing a cellulosic material (A), polyamines (B), and at least one carboxylic acid (C) selected from the group consisting of monocarboxylic acids and rosin acids. , and the thermoplastic resin (D), and a molded article made of this resin composition has excellent mechanical strength.
  • A cellulosic material
  • B polyamines
  • C carboxylic acid
  • D thermoplastic resin
  • the mixture contains at least one carboxylic acid (E ) is further contained.
  • the molded article made of this resin composition has further excellent mechanical strength.
  • the cellulosic material (A) used in the present invention is not particularly limited as long as it can be used in fiber-reinforced plastics, and examples thereof include fine cellulosic materials, pulp, wood flour, and the like. .
  • the fine cellulosic material may contain lignin. Accordingly, examples of the fine cellulosic material include plant-derived fine cellulosic fibers, fine lignocellulosic fibers, cellulosic fine powders, and lignocellulosic fine powders.
  • microfibrillated (MF-ized) cellulose-based fibers MF-ized cellulose-based fibers
  • microfibrils A lignocellulose-based fiber that has been modified (MF-modified) (MF-modified lignocellulose-based fiber) is preferred.
  • the average fiber diameter of the MF cellulose fibers and MF lignocellulose fibers is preferably in the range of 1 nm to 10 ⁇ m, more preferably in the range of 1 nm to 1 ⁇ m, and in the range of 1 nm to 500 nm.
  • not all the cellulose fibers and lignocellulose fibers may be uniformly MF-modified.
  • cellulose-based fibers and lignocellulose-based fibers in which the surface of thick portions (for example, portions with a diameter of about 5 ⁇ m) of cellulose-based fibers and lignocellulose-based fibers are MF-ized to a diameter of about 10 nm It can be suitably used as the cellulosic material (A).
  • the average diameter of the cellulose-based fine powder and the lignocellulose-based fine powder is preferably in the range of 1 nm to 100 ⁇ m, more preferably in the range of 1 nm to 10 ⁇ m, and more preferably in the range of 1 nm to 1 ⁇ m. It is even more preferable to have
  • the fine cellulosic material may or may not be chemically modified.
  • the chemical modification means that the hydroxyl groups of the sugar chains and/or lignin that constitute the surface of the fine cellulosic material are esterified with carboxylic acid, half-esterified (monoesterified with carboxylic acid anhydride), or substituted means etherified with an alkyl group which may have
  • the chemically modified fine cellulosic material includes chemically modified fine cellulosic fibers that may contain lignin, chemically modified fine lignocellulosic fibers that may contain lignin, chemically modified cellulose-based fine powder, chemically modified lignocellulose-based fine powder that may contain lignin, and the like, and the sugar chains and/or hydroxyl groups of lignin that constitute the surface of the fine cellulose-based material are aliphatic Those esterified with a carboxylic acid or an alkyl or alkenyl succinic anhydride are preferred.
  • Such chemically modified fine cellulosic materials are preferably fibrous from the viewpoint of operability of chemical modification.
  • chemically modified cellulosic fibers which may contain lignin, and Chemically modified lignocellulose fibers are preferred, chemically modified MF cellulose fibers optionally containing lignin, and chemically modified MF lignocellulose fibers are more preferred, and MF cellulose fibers and MF lignocellulose fibers are more preferred.
  • Sugar chains and / or hydroxyl groups of lignin constituting the surface of are esterified with aliphatic carboxylic acid or alkyl or alkenyl succinic anhydride chemically modified MF cellulose fibers and chemically modified MF lignocellulose fibers More preferred.
  • the fine cellulosic material may be obtained by refining (defibrating) pulp (in particular, never-dry pulp).
  • the pulverized (defibrated) pulp may be one that has been pulverized (defibrated) in advance. In addition, it may be finely divided (fibrillated).
  • the pulp is not particularly limited as long as it can be used for fiber-reinforced plastics, and may be wood pulp or non-wood pulp.
  • the wood pulp may be derived from conifers (N material: Needle material) or broad-leaved trees (L material: Leaf material).
  • non-wood pulp include those derived from straw, bagasse, kenaf, and the like.
  • the pulp may be chemical pulp (CP) or mechanical pulp (MP).
  • Chemical pulps include, for example, kraft pulp (KP), sulfide pulp (SP), alkaline pulp (AP), and the like.
  • mechanical pulp include ground pulp (GP), refiner ground pulp (RGP), thermomechanical pulp (TMP), chemithermomechanical pulp (CTMP), and chemi-thermomechanical pulp (CTMP).
  • Mechanical Pulp and the like.
  • the pulp may be bleached with chemicals (BP: bleached pulp) or unbleached (UP: unbleached pulp).
  • NBCP needle bleached chemical pulp
  • NNKP needle bleached kraft pulp
  • NUKP needle unbleached kraft pulp
  • Softwood unbleached chemical pulp NUCP: Needle Unbleached Chemical Pulp
  • hardwood bleached kraft pulp LKP: Leaf Bleached Kraft Pulp
  • LBCP Hardwood bleached chemical pulp
  • LKP Leaf Unbleached Kraft Pulp
  • LUCP Leaf Unbleached Kraft Pulp
  • the never-dry pulp is a pulp that has no history of drying and is kept in a wet state, and is not particularly limited. After that, the disjointed fibers are washed to remove lignin and foreign substances, etc., and the remaining lignin is decomposed with oxygen. pulp), and those bleached with chemicals (for example, never dry pulp in NBCP such as NBKP and LBCP such as LBKP).
  • these cellulosic substances (A) may be used singly or in combination of two or more.
  • polyamines (B) used in the present invention include aliphatic polyamines and aromatic polyamines.
  • Examples of the aliphatic polyamine include polyethyleneimine (sometimes referred to as "polyaziridine"), poly(trimethyleneimine) [repeating unit: -NHCH 2 CH 2 CH 2 -], poly(aminomethylethylene ) [Repeating unit: -CH 2 CH (CH 2 NH 2 )-], poly(aminoethylene) [repeating unit: -CH 2 CH(NH 2 )-], poly(meth)acrylic acid aminoalkyleneamide (polyacrylic acid A polymer in which an acid or a carboxylic acid of polymethacrylic acid forms an amide bond with one amino group of an alkylenediamine), among which polyethyleneimine is preferred.
  • polyethyleneimine sometimes referred to as "polyaziridine”
  • poly(trimethyleneimine) [repeating unit: -NHCH 2 CH 2 CH 2 -]
  • poly(aminomethylethylene ) Repeating unit: -CH 2 CH (CH 2 NH 2 )-
  • the polyethylenimines include linear (all containing secondary amino groups), branched (containing primary, secondary and tertiary amino groups), and fully branched dendrimers.
  • branched polyethylenimine is preferred.
  • the branched polyethyleneimine for example, one commercially available under the trade name of Epomin (R) can be used.
  • the number average molecular weight (Mn) of polyethyleneimine is preferably 300 to 100,000, more preferably 300 to 70,000.
  • aromatic polyamine examples include 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl 1,3-bis(4-aminophenoxy)benzene, resorcinol bis(4-amino phenyl) ether (CAS number: 2479-46-1), 1,4-bis(4-aminophenoxy)benzene (CAS number: 3491-12-1), 4,4'-bis(4-aminophenoxy)biphenyl (CAS No.: 13080-85-8), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (CAS No.: 13080-86-9), bis(4-aminophenyl)sulfone (CAS No. : 80-08-0) and 2,2'-dimethylbiphenyl-4,4'-diamine (CAS number: 84-67-3) are preferred.
  • these polyamines (B) may be used singly or in combination of two or more.
  • the carboxylic acids (C) used in the present invention are at least one selected from the group consisting of monocarboxylic acids and rosin acids.
  • the carboxylic acid (C) together with the polyamine (B) it becomes possible to highly disperse the cellulosic material (A) in the thermoplastic resin (D), and the resin composition containing these components A molded article made of the material has excellent mechanical strength.
  • R represents an alkyl group, an alkenyl group, an alicyclic hydrocarbon group, an oxyalkyl group to which an alicyclic hydrocarbon group is bonded, or a phenoxyalkyl group.
  • An alkyl group or an alicyclic hydrocarbon group may be bonded to the phenyl group of the phenoxyalkyl group.
  • the alkyl group (including the alkyl group bonded to the phenyl group of the phenoxyalkyl group) and the alkenyl group may have a branched chain.
  • alicyclic hydrocarbon groups including an alicyclic hydrocarbon group bonded to the oxyalkyl group and an alicyclic hydrocarbon group bonded to the phenyl group of the phenoxyalkyl group) are crosslinked or condensed. You may have
  • an alkyl group having 1 to 17 carbon atoms eg, methyl group, ethyl group, iso-butyl group, t-butyl group, n-undecyl group, n-tridecyl group, n-pentadecyl group, n-heptadecyl group
  • alkyl groups having 1 to 12 carbon atoms e.g., methyl group, ethyl group, iso-butyl group, t-butyl group, n-undecyl group
  • alkyl groups having 1 to 5 carbon atoms eg, methyl group, ethyl group, iso-butyl group, t-butyl group
  • alkyl groups having 1 to 5 carbon atoms eg, methyl group, ethyl group, iso-butyl group, t-butyl group
  • the alkenyl group which may have a branched chain is preferably an alkenyl group having 2 to 17 carbon atoms from the viewpoint of further improving the mechanical strength of the molded article, and an alkenyl group having 2 to 12 carbon atoms is preferable. Alkenyl groups having 2 to 5 carbon atoms are more preferred.
  • Examples of the alicyclic hydrocarbon group which may be crosslinked or condensed in plurality, include an adamantyl group, a cyclohexyl group, and a 4-(t-butyl)cyclohexyl group.
  • An adamantyl group is preferred from the viewpoint of improvement.
  • Oxyalkyl groups to which alicyclic hydrocarbon groups are bonded include, for example, bornyloxymethyl groups, isobornyloxymethyl groups, and menthyloxymethyl groups.
  • Examples of the phenoxyalkyl group to which an alkyl group or an alicyclic hydrocarbon group may be bonded include a phenoxymethyl group, a 4-(t-butyl)phenoxymethyl group, a 4-(1,1,3,3 -tetramethyl)butylphenoxymethyl group, adamantylphenoxymethyl group, bornylphenoxymethyl group, bornylphenoxypentyl group, and menthylphenoxymethyl group.
  • a (t-butyl)phenoxymethyl group, a 4-(1,1,3,3-tetramethyl)butylphenoxymethyl group, an adamantylphenoxymethyl group, a bornylphenoxymethyl group, and a menthylphenoxymethyl group are preferred.
  • rosin acids examples include rosin acids such as abietic acid, neoabietic acid, parastric acid, pimaric acid, isopimaric acid, dehydroabietic acid, and derivatives of these rosin acids.
  • rosin acid derivative examples include condensates of rosin acid, acrylic acid-modified rosin acid, fumaric acid-modified rosin acid, maleic anhydride-modified rosin acid, and rosin acid-modified phenolic resin. is mentioned.
  • the rosin acid, maleic anhydride-modified rosin acid, and rosin acid-modified phenol resin are preferable, and abietic acid, dehydroabietic acid, and abietin.
  • Maleic anhydride-modified acid and abietic acid-modified phenolic resin are more preferred.
  • these carboxylic acids (C) may be used alone or in combination of two or more.
  • thermoplastic resin (D) used in the present invention is not particularly limited, but polyolefin, polyamide, aliphatic polyester, aromatic polyester, polyacetal, polycarbonate, polystyrene, acrylonitrile-butadiene-styrene copolymer coalescence (ABS resin), polycarbonate-ABS alloy (PC-ABS alloy), cellulosic resin, polylactic acid (PLA), polyhydroxybutyrate (PHBT), polyhydroxyhexanoate (PHAT), polyhydroxybutyrate and poly Copolymers with hydroxyhexanoate (PHBH), polybutylene succinate (PBS), modified polyphenylene ethers (m-PPE), and polyvinyl chloride.
  • ABS resin polycarbonate-ABS alloy
  • PC-ABS alloy polycarbonate-ABS alloy
  • cellulosic resin polylactic acid (PLA), polyhydroxybutyrate (PHBT), polyhydroxyhexanoate (PHAT), polyhydroxybutyrate and poly Copolymers with hydroxy
  • thermoplastic resins polyolefin, polyamide, aliphatic polyester, aromatic polyester, polyacetal, polycarbonate, polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS resin), Polycarbonate-ABS alloy (PC-ABS alloy), cellulose resin, polylactic acid (PLA), polyhydroxybutyrate (PHBT), polyhydroxyhexanoate (PHAT), polyhydroxybutyrate and polyhydroxyhexanoate Copolymer (PHBH), polybutylene succinate (PBS), and modified polyphenylene ether (m-PPE) are preferred, and biomass-derived polyethylene from the viewpoint of environmental conservation, thermal stability, strength characteristics, and weight reduction of molded products.
  • ABS resin polystyrene, acrylonitrile-butadiene-styrene copolymer
  • PC-ABS alloy Polycarbonate-ABS alloy
  • cellulose resin polylactic acid (PLA), polyhydroxybutyrate (PHBT), polyhydroxyhexano
  • biomass-derived polypropylene copolymer of biomass-derived ethylene and biomass-derived propylene, copolymer of at least one of biomass-derived ethylene and biomass-derived propylene and petrochemical-derived olefin, polylactic acid ( PLA), polyhydroxybutyrate (PHBT), polyhydroxyhexanoate (PHAT), copolymers of polyhydroxybutyrate and polyhydroxyhexanoate (PHBH), and polybutylene succinate (PBS) are more preferred. .
  • thermoplastic resins (D) may be used alone or in combination of two or more.
  • the mixture contains at least one selected from the group consisting of polycarboxylic acids, acid anhydrides thereof, acid anhydride-modified polyolefins and hydrolysates thereof. (hereinafter referred to as "other carboxylic acids (E)”) is further contained.
  • other carboxylic acids (E) By further including such other carboxylic acid (E) in the mixture, it becomes possible to highly disperse the cellulosic material (A) in the thermoplastic resin (D), and molding with further excellent mechanical strength you can get a body
  • polycarboxylic acid and its acid anhydride examples include aliphatic polycarboxylic acids having 2 to 3 carboxy groups in the molecule, and 2 to 4 (preferably 3 to 4) carboxy groups in the molecule.
  • Aromatic polycarboxylic acids having and acid anhydrides thereof By further including at least one of such aliphatic polycarboxylic acids, aromatic polycarboxylic acids, and acid anhydrides thereof in the mixture, the cellulosic material (A) is converted into a thermoplastic resin (D). It is possible to highly disperse it in the inside, and it is possible to obtain a molded article with further excellent mechanical strength.
  • aliphatic polycarboxylic acid examples include aliphatic polycarboxylic acids having a hydrocarbon group with 1 to 10 carbon atoms, and specific examples include adipic acid, azelaic acid, sebacic acid, and itaconic acid.
  • aromatic polycarboxylic acids examples include pyromellitic acid [1,2,4,5-benzenetetracarboxylic acid], trimellitic acid [1,2,4-benzenetricarboxylic acid], trimesic acid [1,3,5 -benzenetricarboxylic acid].
  • an aliphatic polycarboxylic acid having a branched hydrocarbon group and its acid anhydride can be used as the polyvalent carboxylic acid and its acid anhydride.
  • aliphatic polycarboxylic acids having branched hydrocarbon groups and acid anhydrides thereof include alkylsuccinic acid and acid anhydrides thereof and alkenylsuccinic acid and acid anhydrides thereof.
  • the number of carbon atoms in the branched alkyl group of alkylsuccinic acid and its acid anhydride and the alkenyl group of alkenylsuccinic acid and its acid anhydride is preferably 4 to 17 carbon atoms.
  • the cellulosic material (A) is highly dispersed in the thermoplastic resin (D). It is possible to obtain a molded article having a further excellent mechanical strength.
  • alkyl succinic acids and acid anhydrides thereof include octyl succinic acid, dodecyl succinic acid, tridecenyl succinic acid, tetrahexadecyl succinic acid, hexadecyl succinic acid, octadecyl succinic acid, and acid anhydrides thereof. mentioned.
  • alkenylsuccinic acids and acid anhydrides thereof include pentenylsuccinic acid, hexenylsuccinic acid, octenylsuccinic acid, decenylsuccinic acid, undecenylsuccinic acid, dodecenylsuccinic acid, tridecenylsuccinic acid, and tetradecenylsuccinic acid. acids, hexadecenylsuccinic acid, octadecenylsuccinic acid, iso-octadecenylsuccinic acid, and anhydrides thereof.
  • the acid anhydride-modified polyolefin and its hydrolyzate include, for example, maleic anhydride-modified polyolefin (that is, maleic anhydride grafted in the polyolefin molecule and/or at the molecular end, and maleic anhydride and olefin). copolymers) and hydrolysates thereof (that is, hydrolyzed acid anhydride groups in the maleic anhydride-modified polyolefin).
  • the cellulosic material (A) can be highly dispersed in the thermoplastic resin (D). As a result, it is possible to obtain a molded article having even better mechanical strength.
  • maleic anhydride-modified polyolefin and its hydrolyzate examples include those obtained by modifying a polymer and/or copolymer of an alkene having 2 to 6 carbon atoms with maleic anhydride, maleic anhydride and 2 to 6 carbon atoms.
  • copolymers with alkenes, and hydrolyzed acid anhydride groups thereof among them, polymers and/or copolymers of alkenes having 2 to 6 carbon atoms modified with maleic anhydride; And those obtained by hydrolyzing the acid anhydride group are preferable, specifically, maleic anhydride-modified polyethylene (abbreviation: MAPE), maleic anhydride-modified polypropylene (abbreviation: MAPP), maleic anhydride-modified ethylene-propylene copolymer coalesced, maleic anhydride-modified polybutene, maleic anhydride-modified polypentene, maleic anhydride-modified polyhexene, and hydrolyzed acid anhydride groups thereof; more preferred are MAPE, MAPP, and hydrolysates thereof. .
  • MAPE maleic anhydride-modified polyethylene
  • MAPP maleic anhydride-modified polypropylene
  • MAPP maleic anhydride-modified ethylene-propylene
  • the average molecular weight (MW) of the maleic anhydride-modified polyolefin is preferably 9,000 to 100,000, more preferably 9,000 to 70,000, and even more preferably 9,000 to 50,000.
  • maleic anhydride-modified polypropylene having an average molecular weight (MW) of 9,000 to 70,000 (preferably 9,000 to 50,000) obtained by grafting maleic anhydride to polypropylene fragments obtained by thermally decomposing polypropylene having a large average molecular weight It can be used as the acid anhydride-modified polyolefin.
  • the acid load (acid value) of the maleic anhydride-modified polyolefin is preferably 1.4 to 120 mgKOH/g, more preferably 3.5 to 60 mgKOH/g.
  • these other carboxylic acids (E) may be used alone or in combination of two or more.
  • the resin composition of the present invention comprises a mixture containing the cellulosic material (A), the polyamines (B), the carboxylic acids (C), and optionally the other carboxylic acids (E). , a melt-kneaded product with the thermoplastic resin (D).
  • the polyamines (B) contain a plurality of types of amino groups (primary amino groups, secondary amino groups, tertiary amino groups) that react with the carboxyl groups of the carboxylic acids (C) and a plurality of Therefore, the resin composition obtained by melt-kneading the mixture containing the polyamines (B) and the carboxylic acids (C) and the thermoplastic resin (D) has a complicated structure, It is impossible or impractical to express directly with a general formula (structural formula).
  • the content of the cellulosic material (A) is preferably 0.1 to 80% by mass, more preferably 0.5 to 50% by mass, based on the total resin composition. 1 to 10% by mass is more preferable. If the content of the cellulosic material (A) is less than the lower limit, it tends to be difficult to obtain a molded article excellent in mechanical strength, coefficient of linear expansion (CTE), heat resistance (e.g., heat distortion temperature), etc. On the other hand, if the above upper limit is exceeded, the surface smoothness and transparency of the molded product will be reduced, the flowability of the molten resin composition will be reduced, the molded product will be distorted, and adhesion failure will tend to occur.
  • CTE coefficient of linear expansion
  • heat resistance e.g., heat distortion temperature
  • the content of the thermoplastic resin (D) is preferably 20 to 99.9% by mass, more preferably 50 to 99.5% by mass, and still more preferably 90 to 99% by mass, based on the total resin composition. . If the content of the thermoplastic resin (D) is less than the lower limit, there is a tendency for molding failure and destruction/damage during use due to a decrease in impact resistance to occur. As the amount of the substance (A) decreases, it tends to become difficult to obtain a molded product excellent in physical properties such as mechanical strength.
  • the ratio of the polyamines (B) to 100 parts by mass of the cellulosic material (A) is preferably 0.1 to 70 parts by mass, more preferably 0.1 to 50 parts by mass, and 0.1 to 30 parts by mass. is more preferred. If the proportion of the polyamines (B) is less than the lower limit, sufficient hydrophobicity is not imparted to the cellulosic material (A), and the cellulosic material (A) is highly dispersed in the thermoplastic resin (D). However, if the above upper limit is exceeded, it tends to be necessary to recover excess polyamines.
  • the ratio of the acid value of the carboxylic acids (C) to the amine value of the polyamines (B) is preferably 0.01 to 2.0, more preferably 0.1 to 1.0. (equivalent) is more preferred. If the ratio (acid value/amine value) is less than the lower limit, sufficient hydrophobicity is not imparted to the cellulosic material (A), and the cellulosic material (A) is highly dispersed in the thermoplastic resin (D). On the other hand, when the above upper limit is exceeded, metal corrosion etc. tend to occur due to the acidity of excess carboxylic acids.
  • the resin composition of the present invention contains the other carboxylic acid (E), the sum of the acid values of the carboxylic acids including the carboxylic acid (C) and the other carboxylic acid (E) and the polyamine
  • the amine value ratio (total acid value/amine value) of the class (B) is preferably in the range of 0.01 to 2.0, and is in the range of 0.1 to 1.0 (equivalent). is more preferable.
  • the resin composition of the present invention may contain a compatibilizer (F) and/or a filler (G) as additives. This improves the dispersibility of the cellulosic material (A) in the thermoplastic resin (D).
  • the compatibilizer (F) has an affinity for both the cellulosic material (A) and the thermoplastic resin (D), and the cellulosic material into the thermoplastic resin (D) There is no particular limitation as long as it is a substance that improves the dispersibility of (A). Examples include modified polyolefins (excluding those corresponding to other carboxylic acids (E) above), grafts of polyolefins and other polymers. products (excluding those corresponding to the other carboxylic acids (E) above), and graft products of acrylic polymer chains that have affinity for polyolefins and acrylic polymer chains that have affinity for celluloses. These compatibilizers (F) may be used alone or in combination of two or more.
  • grafts of polyolefins and other polymers include copolymers of polyolefins such as polyethylene, polypropylene, and polybutene with polyvinyl acetate (PVAc), poly(meth)acrylic acid, or poly(meth)acrylate. is mentioned.
  • Examples of the grafted product of the acrylic polymer chain having affinity for polyolefin and the acrylic polymer chain having affinity for celluloses include, for example, the resin affinity segment and cellulose affinity described in Japanese Patent No. 6234037. and a block copolymer having a segment.
  • the content thereof is preferably 1 to 20 parts by mass, preferably 2 to 10 parts by mass, with respect to 100 parts by mass of the thermoplastic resin (D). parts is more preferred, and 5 to 10 parts by mass is even more preferred.
  • filler (G) Filler Examples of the filler (G) include talc, clay, zeolite, aluminum oxide, calcium carbonate, titanium oxide, silica, magnesium oxide, and mica, among which talc, clay, zeolite, and carbonate. Calcium is preferred. These fillers (G) may be used alone or in combination of two or more. By including such a filler (G), the cellulosic material (A) in the resin composition is easily fibrillated during melt-kneading, and the dispersibility of the cellulosic material (A) is improved.
  • the content thereof is preferably 1 to 20 parts by mass, and 2 to 10 parts by mass with respect to 100 parts by mass of the thermoplastic resin (D). More preferably, 5 to 10 parts by mass is even more preferable.
  • antioxidants Furthermore, in the resin composition of the present invention, antioxidants, surfactants, plasticizers, antistatic agents, ultraviolet absorbers, antistatic agents, ultraviolet absorbers, coloring agents, as long as the effects of the present invention are not impaired.
  • Various additives such as agents and deodorants may be contained.
  • the other carboxylic acids (E) may be added as necessary.
  • the step of adding the other carboxylic acid (E) may be either the mixture preparation step or the melt-kneading step, or both.
  • the cellulosic material (A), the polyamines (B), the carboxylic acids (C), the thermoplastic resin (D), and the other carboxylic acids (E) may be appropriately set so that the content of these in the obtained resin composition is within a predetermined range.
  • the raw material cellulosic material (A) a cellulosic material that is not pulverized such as pulp (especially never-dry pulp) or wood flour may be used.
  • pulp especially never-dry pulp
  • wood flour a cellulosic material that is not pulverized such as pulp (especially never-dry pulp) or wood flour
  • fine cellulosic materials such as fine cellulosic fibers may be used.
  • the pulp is not particularly limited as long as it can be used for fiber-reinforced plastics, and may be wood pulp or non-wood pulp.
  • the wood pulp may be derived from conifers (N material: Needle material) or broad-leaved trees (L material: Leaf material).
  • non-wood pulp include those derived from straw, bagasse, kenaf, and the like.
  • the pulp may be chemical pulp (CP) or mechanical pulp (MP).
  • Chemical pulps include, for example, kraft pulp (KP), sulfide pulp (SP), alkaline pulp (AP), and the like.
  • mechanical pulp include ground pulp (GP), refiner ground pulp (RGP), thermomechanical pulp (TMP), chemithermomechanical pulp (CTMP), and chemi-thermomechanical pulp (CTMP).
  • Mechanical Pulp and the like.
  • the pulp may be bleached with chemicals (BP: bleached pulp) or unbleached (UP: unbleached pulp).
  • NBCP needle bleached chemical pulp
  • NNKP needle bleached kraft pulp
  • NUKP needle unbleached kraft pulp
  • Softwood unbleached chemical pulp NUCP: Needle Unbleached Chemical Pulp
  • hardwood bleached kraft pulp LKP: Leaf Bleached Kraft Pulp
  • LBCP Hardwood bleached chemical pulp
  • LKP Leaf Unbleached Kraft Pulp
  • LUCP Leaf Unbleached Kraft Pulp
  • the never-dry pulp is a pulp that has no history of drying and is kept in a wet state, and is not particularly limited. After that, the disjointed fibers are washed to remove lignin and foreign substances, etc., and the remaining lignin is decomposed with oxygen. pulp), and those bleached with chemicals (for example, never dry pulp in NBCP such as NBKP and LBCP such as LBKP).
  • the solvent used in the method for producing the resin composition of the present invention has a hydrophilic group and a hydrophobic group.
  • a solvent By using such a solvent, it is possible to dissolve the carboxylic acids (C) and uniformly mix the cellulosic material (A) with a high moisture content and the hydrophobic carboxylic acids (C). Become. Further, the solvent adheres to the surface of the cellulosic material (A), thereby exposing the hydrophobic groups of the solvent to the outside, thereby highly dispersing the cellulosic material (A) in the thermoplastic resin (D). becomes possible.
  • the solvent penetrates into the cell walls of the cellulosic material (A), even if the water in the cellulosic material (A) evaporates during melt-kneading, the solvent remains and softens the cell walls. The properties are maintained, and the cellulosic material (A) can be defibrated by melt-kneading.
  • the penetration of the solvent into the cell walls of the cellulosic material (A) also causes the carboxylic acids (C) to penetrate into the cell walls.
  • Solvents having such a hydrophilic group and a hydrophobic group include, for example, ethylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, pentylene glycol, hexylene glycol, heptylene glycol, polyethylene glycol, caprolactam, tetrahydrofuran. , methylpyrrolidone, dimethylacetamide, acetone and the like. These solvents may be used alone or in combination of two or more.
  • a solvent having the hydrophilic group and the hydrophobic group from the viewpoint of high dispersibility and fibrillating property of the cellulosic material (A).
  • a solvent having the hydrophilic group and the hydrophobic group from the viewpoint of high dispersibility and fibrillating property of the cellulosic material (A).
  • carboxylic acid (C) or the other carboxylic acid (E) when a readily water-soluble carboxylic acid (for example, acetic acid) is used, a hydrophobic group is added instead of the solvent having the hydrophilic group and the hydrophobic group.
  • a water-free solvent eg, water
  • the cellulosic material (A) is added to a solution obtained by mixing the polyamines (B) and the carboxylic acids (C) in a solvent having a hydrophilic group and a hydrophobic group to form the mixture.
  • Method (1) after mixing the cellulosic material (A) and the polyamines (B), the carboxylic acids dissolved in a solvent having the hydrophilic group and the hydrophobic group (C) may be added to prepare the mixture [method (2)]. Further, after mixing the cellulosic material (A) and the carboxylic acid (C) dissolved in a solvent having a hydrophilic group and a hydrophobic group, the polyamine (B) is added to prepare the mixture. It is also possible [Method (3)].
  • the polyamines (B) may be mixed with the solvent having the hydrophilic group and the hydrophobic group, and then the carboxylic acids (C) may be added and dissolved.
  • (1-1) after dissolving the carboxylic acid (C) in a solvent having the hydrophilic group and the hydrophobic group, the polyamine (B) may be mixed [method (1-2) ], the polyamines (B) and the carboxylic acids (C) may be simultaneously mixed in the solvent having the hydrophilic group and the hydrophobic group [method (1-3)].
  • the temperature at which the mixture is prepared is preferably in the range of room temperature to the boiling point of the solvent. hours is preferred, and 0.1 to 5 hours is more preferred.
  • the mixture preparation step when mixing and dissolving the carboxylic acids (C) in the solvent having the hydrophilic group and the hydrophobic group, if necessary, polyvalent carboxylic acid and its acid anhydride It is preferable to further dissolve at least one carboxylic acid (E) selected from the group.
  • the method (1) when preparing a solution in which the polyamines (B) and the carboxylic acids (C) are mixed in a solvent having a hydrophilic group and a hydrophobic group (more specifically, In the method (1-1), after the polyamines (B) are mixed with the solvent having the hydrophilic group and the hydrophobic group, the carboxylic acids (C) are added and dissolved; In the method (1-2), when the carboxylic acid (C) is dissolved in the solvent having the hydrophilic group and the hydrophobic group; in the method (1-3), the polyamine (B) and When mixing the carboxylic acid (C) with the solvent having the hydrophilic group and the hydrophobic group at the same time), if necessary, at least one selected from the group consisting of polyvalent carboxylic acids and acid anhydrides thereof It is preferable to further dissolve the carboxylic acids (E) of.
  • carboxylic acids (C) dissolved in the solvent having the hydrophilic group and the hydrophobic group if necessary, a polyvalent carboxylic acid and its It is preferable to further dissolve at least one carboxylic acid (E) selected from the group consisting of acid anhydrides.
  • the mixture preparation step when adding and mixing the cellulosic material (A), if necessary, at least one selected from the group consisting of acid anhydride-modified polyolefins and hydrolysates thereof It is preferable to further dissolve the carboxylic acids (E).
  • the cellulosic material (A) is added to a solution obtained by mixing the polyamines (B) and the carboxylic acids (C) in the solvent having the hydrophilic group and the hydrophobic group.
  • the method (2) when mixing the cellulosic material (A) and the polyamines (B), if necessary, from the group consisting of acid anhydride-modified polyolefins and hydrolysates thereof It is preferable to further dissolve at least one selected carboxylic acid (E).
  • an acid it is preferable to further dissolve at least one carboxylic acid (E) selected from the group consisting of anhydride-modified polyolefins and hydrolysates thereof.
  • the mixture prepared in such a mixture preparation step contains a cellulosic material (A) having the polyamines (B) and the carboxylic acids (C) attached to the surface thereof, whereby the cellulose Hydrophobicity is imparted to the surface of the system material (A). Since the cellulosic material (A) having a hydrophobic surface is highly dispersed in the thermoplastic resin (D), the molded article made of the resin composition of the present invention has excellent mechanical strength. In addition, since the cellulosic material (A) whose surface is hydrophobic is excellent in dehydration, the cellulosic material (A) can be efficiently dehydrated during melt-kneading with the thermoplastic resin (D). can be done.
  • the mixture prepared in the mixture preparation step may be subjected to a refining treatment (for example, fibrillation treatment).
  • a refining treatment for example, fibrillation treatment
  • the surface of the cellulosic material (A) in the mixture is imparted with hydrophobicity, and the cellulosic material (A) has excellent dehydration properties.
  • the cellulosic material (A) can be efficiently dehydrated.
  • the method of mixing each component in such a mixture preparation step is not particularly limited, but examples include stirring with a stirring device such as a planetary mixer and kneading with a kneading device such as an extruder.
  • a stirring device such as a planetary mixer
  • kneading with a kneading device such as an extruder
  • a non-miniaturized cellulosic material pulp (particularly never-dry pulp), wood, etc.)
  • kneading is carried out using a kneading device such as an extruder.
  • the cellulosic material (A) can be made fine (fibrillated).
  • melt-kneading process In the melt-kneading step, the mixture obtained in the mixture preparation step and the thermoplastic resin (D) are mixed, and the obtained mixture is subjected to an extruder such as an extruder having a degassing function.
  • the mixture is supplied to a kneading device and melt-kneaded while or after removing the water and the solvent contained in the mixture.
  • the temperature at the time of melt kneading is preferably a temperature within the range of the softening point or higher and the melting point of the thermoplastic resin (D) + 20°C or lower, and a temperature within the range of the melting point or higher and the melting point of the thermoplastic resin (D) + 10°C or lower. is more preferred.
  • the other carboxylic acid (E) may be added in the melt-kneading step.
  • the resin composition of the present invention contains the compatibilizer (F), the filler (G), and other additives, these additives can be added in the melt-kneading step. .
  • an oxazoline compound may be added in the melt-kneading step in order to react with unreacted carboxyl groups in the resin composition.
  • the melt-kneading causes the polyamines (B) and the carboxylic acids (C) in the mixture to react, and the reaction products and the reaction products As shown in FIG. 1, the reaction product obtained by the further reaction of the polyamines (B) and the carboxylic acids (C) adheres to the surface of the cellulosic material (A), whereby the cellulosic material (A ) is imparted with hydrophobicity, it becomes possible to highly disperse the cellulosic material (A) in the thermoplastic resin (D).
  • the molded article of the present invention is made of the resin composition of the present invention.
  • the cellulosic material (A) is highly dispersed in the thermoplastic resin (D). has excellent mechanical strength.
  • the method for producing the molded article of the present invention is not particularly limited. It can be manufactured by molding into a desired shape by various known molding methods.
  • Example 1 First, after dissolving acetic acid in tripropylene glycol so that the amount in the resin composition becomes the amount shown in Table 1, polyethyleneimine (number average molecular weight: 300) is added and mixed at room temperature, and the carboxylic acid An ammonium solution was prepared, MF-modified cellulose fiber (“Celish KY110N” manufactured by Daicel Miraise Co., Ltd., water content: 85%) was added to this ammonium carboxylate solution, and the mixture was stirred and mixed for 1 hour using a planetary mixer. Tripropylene glycol was used in an amount of 50 parts by mass with respect to 30 parts by mass of MF-modified cellulose fibers.
  • MF-modified cellulose fiber (“Celish KY110N” manufactured by Daicel Miraise Co., Ltd., water content: 85%) was added to this ammonium carboxylate solution, and the mixture was stirred and mixed for 1 hour using a planetary mixer.
  • Tripropylene glycol was used in an amount of 50
  • polypropylene (“Novatec MA04A” manufactured by Japan Polypropylene Co., Ltd., melt index: 40) was mixed with the obtained mixture so that the amount in the resin composition was the amount shown in Table 1, and further, After adding 0.1 parts by mass of a phenolic antioxidant ("Irganox 1010" manufactured by BASF) to 100 parts by mass of the resulting mixture, the resulting mixture was quantitatively charged into an extruder, Melt-kneading was performed while water and tripropylene glycol were removed by drying to prepare a resin composition in the form of pellets.
  • a phenolic antioxidant (“Irganox 1010” manufactured by BASF)
  • Example 2 When adding the MF-modified cellulose fibers, maleic anhydride-modified polypropylene ("Toyotac H1000P" manufactured by Toyobo Co., Ltd., melt index: 110) was added so that the amount in the resin composition was the amount shown in Table 1.
  • a resin composition in the form of pellets was produced in the same manner as in Example 1, except that the blending amount of polypropylene was changed to that shown in Table 1.
  • Example 3 When adding polyethyleneimine, 2-dodecen-1-ylsuccinic anhydride is added so that the blending amount in the resin composition becomes the blending amount shown in Table 1, and when adding MF cellulose fiber. Then, maleic anhydride-modified polypropylene (manufactured by Toyobo Co., Ltd. "Toyo Tack H1000P", melt index: 110) is added so that the amount in the resin composition is the amount shown in Table 1, and the amount of polypropylene is added. A resin composition in the form of pellets was produced in the same manner as in Example 1, except that the blending amount was changed to that shown in Table 1.
  • Example 4 A resin composition in the form of pellets was produced in the same manner as in Example 3, except that stearic acid was used instead of acetic acid and the blending amounts of polyethyleneimine and polypropylene were changed to those shown in Table 1.
  • Example 5 A resin composition in the form of pellets was produced in the same manner as in Example 1, except that pivalic acid was used instead of acetic acid and the blending amounts of polyethyleneimine and polypropylene were changed to those shown in Table 1.
  • Example 6 A pellet-shaped resin composition was produced in the same manner as in Example 1, except that adamantanecarboxylic acid was used instead of acetic acid and the blending amounts of polyethyleneimine and polypropylene were changed to those shown in Table 1.
  • Example 7 The blending amount of polypropylene was changed to the blending amount shown in Table 1, and during melt kneading, maleic anhydride-modified polypropylene ("Toyotac” manufactured by Toyobo Co., Ltd. H1000P", melt index: 110) was added in the same manner as in Example 6 to prepare a resin composition in the form of pellets.
  • Toyotac maleic anhydride-modified polypropylene manufactured by Toyobo Co., Ltd. H1000P
  • melt index: 110 melt index
  • Example 8 A resin composition in the form of pellets was produced in the same manner as in Example 6, except that polyethyleneimine with a number average molecular weight of 70,000 was used instead of polyethyleneimine with a number average molecular weight of 300.
  • Example 9 A resin composition in the form of pellets was produced in the same manner as in Example 7, except that polyethyleneimine with a number average molecular weight of 70,000 was used instead of polyethyleneimine with a number average molecular weight of 300.
  • Example 10 When adding polyethyleneimine, 2-dodecen-1-ylsuccinic anhydride is added so that the blending amount in the resin composition becomes the blending amount shown in Table 1, and the blending amount of polypropylene is shown in Table 1.
  • a pellet-shaped resin composition was produced in the same manner as in Example 6, except that the amount was changed.
  • Example 11 When adding polyethyleneimine, 2-dodecen-1-ylsuccinic anhydride is added so that the blending amount in the resin composition becomes the blending amount shown in Table 1, and when adding MF cellulose fiber. Then, maleic anhydride-modified polypropylene (manufactured by Toyobo Co., Ltd. "Toyo Tack H1000P", melt index: 110) is added so that the amount in the resin composition is the amount shown in Table 1, and the amount of polypropylene is added. A resin composition in the form of pellets was produced in the same manner as in Example 6, except that the blending amount was changed to that shown in Table 1.
  • Example 12 The blending amount of polypropylene was changed to the blending amount shown in Table 1, and during melt kneading, maleic anhydride-modified polypropylene ("Toyotac” manufactured by Toyobo Co., Ltd. H1000P", melt index: 110) was added in the same manner as in Example 10 to prepare a resin composition in the form of pellets.
  • Toyotac maleic anhydride-modified polypropylene manufactured by Toyobo Co., Ltd. H1000P
  • melt index: 110 melt index
  • Example 13 A pellet-shaped resin composition was produced in the same manner as in Example 6, except that bornanephenoxyacetic acid was used instead of adamantanecarboxylic acid.
  • Example 14 When adding the MF-modified cellulose fibers, maleic anhydride-modified polypropylene ("Toyotac H1000P" manufactured by Toyobo Co., Ltd., melt index: 110) was added so that the amount in the resin composition was the amount shown in Table 1.
  • a resin composition in the form of pellets was produced in the same manner as in Example 13, except that the blending amount of polypropylene was changed to that shown in Table 1.
  • MF-modified cellulose fiber (“Celish KY110N” manufactured by Daicel Miraise Co., Ltd., moisture content: 85%) and polyethyleneimine (number average molecular weight: 300 ) were stirred and mixed using a planetary mixer at normal temperature for 1 hour, then adamantanecarboxylic acid dissolved in tripropylene glycol was added and further stirred and mixed for 1 hour.
  • Tripropylene glycol was used in an amount of 50 parts by mass with respect to 30 parts by mass of MF-modified cellulose fibers.
  • polypropylene (“Novatec MA04A” manufactured by Japan Polypropylene Co., Ltd., melt index: 40) was mixed with the obtained mixture so that the amount in the resin composition was the amount shown in Table 1, and further, After adding 0.1 parts by mass of a phenolic antioxidant ("Irganox 1010" manufactured by BASF) to 100 parts by mass of the resulting mixture, the resulting mixture was quantitatively charged into an extruder, Melt-kneading was performed while water and tripropylene glycol were removed by drying to prepare a resin composition in the form of pellets.
  • a phenolic antioxidant (“Irganox 1010” manufactured by BASF)
  • Example 16 The blending amount of polypropylene was changed to the blending amount shown in Table 1, and during melt kneading, maleic anhydride-modified polypropylene ("Toyotac” manufactured by Toyobo Co., Ltd. H1000P", melt index: 110) was added in the same manner as in Example 15 to prepare a resin composition in the form of pellets.
  • Toyotac maleic anhydride-modified polypropylene manufactured by Toyobo Co., Ltd. H1000P
  • melt index: 110 melt index
  • Example 17 Dehydroabietic acid was used instead of adamantanecarboxylic acid, and maleic anhydride-modified polypropylene (manufactured by Toyobo Co., Ltd. A pellet-shaped resin composition was produced in the same manner as in Example 6, except that "Toyotac H1000P", melt index: 110) was added and the blending amount of polypropylene was changed to the blending amount shown in Table 2.
  • Example 18 A pellet-shaped resin composition was produced in the same manner as in Example 11, except that dehydroabietic acid was used instead of adamantanecarboxylic acid.
  • Example 19 A rosin acid-modified phenolic resin was used instead of adamantanecarboxylic acid, and maleic anhydride-modified polypropylene (Toyobo Co., Ltd. A resin composition in the form of pellets was prepared in the same manner as in Example 6, except that "Toyotac H1000P" (manufactured by the company, melt index: 110) was added and the blending amount of polypropylene was changed to the blending amount shown in Table 2. .
  • “Toyotac H1000P” manufactured by the company, melt index: 110
  • Example 20 Maleic anhydride-modified abietic acid was used instead of adamantanecarboxylic acid, and maleic anhydride-modified polypropylene (Toyobo "Toyotac H1000P" manufactured by Co., Ltd., melt index: 110) was added, and a pellet-shaped resin composition was prepared in the same manner as in Example 6, except that the blending amount of polypropylene was changed to the blending amount shown in Table 2. bottom.
  • Toyobo "Toyotac H1000P" manufactured by Co., Ltd., melt index: 110 maleic anhydride-modified polypropylene
  • Example 21 First, dehydroabietic acid was dissolved in tripropylene glycol so that the amount in the resin composition was as shown in Table 2, and then polyethyleneimine (number average molecular weight: 300) and 2-dodecen-1-ylsuccinic acid were added. and anhydride were added and mixed at room temperature to prepare an ammonium carboxylate solution.
  • NBKP never dry pulp (obtained from Nippon Paper Industries Co., Ltd., moisture content: 85%) and maleic anhydride-modified polypropylene ("Toyo Tack H1000P" manufactured by Toyobo Co., Ltd., melt index: 110) are added. After that, the obtained mixture was put into an extruder quantitatively and mixed at room temperature for 1 hour to defibrate the never dry pulp.
  • Tripropylene glycol was used in an amount of 50 parts by mass with respect to 30 parts by mass of never dry pulp.
  • polypropylene (“Novatec MA04A” manufactured by Japan Polypropylene Co., Ltd., melt index: 40) was mixed with the obtained mixture so that the amount in the resin composition was the amount shown in Table 2, and further, After adding 0.1 parts by mass of a phenolic antioxidant ("Irganox 1010" manufactured by BASF) to 100 parts by mass of the resulting mixture, the resulting mixture was quantitatively charged into an extruder, Melt-kneading was performed while water and tripropylene glycol were removed by drying to prepare a resin composition in the form of pellets.
  • a phenolic antioxidant (“Irganox 1010” manufactured by BASF)
  • Example 22 A resin composition in the form of pellets was produced in the same manner as in Example 21, except that the amounts of never dry pulp and polypropylene were changed to those shown in Table 2.
  • Example 4 A resin composition in the form of pellets was prepared in the same manner as in Example 1, except that 2-dodecen-1-ylsuccinic anhydride was used instead of acetic acid, and the blending amounts of polyethyleneimine and polypropylene were changed to those shown in Table 2. was made.
  • a body (Comparative Example 1), a mixture containing a cellulosic material (A) and a polyamine (B), and a molded body (Comparative Examples 2 to 3), and from a resin composition which is a melt-kneaded product of a mixture containing a cellulosic material (A), a polyamine (B), and 2-dodecen-1-ylsuccinic acid, and a thermoplastic resin (D) It was confirmed that the flexural modulus and flexural strength were superior to those of the molded article (Comparative Example 4).
  • a thermoplastic resin (D) selected from the group consisting of polyvalent carboxylic acids and their acid anhydrides and acid anhydride-modified polyolefins and their hydrolysates
  • a molded article having excellent mechanical strength which is made of a resin composition containing a cellulosic material and a thermoplastic resin.
  • the resin composition of the present invention can be used in a smaller amount than the conventional resin composition containing a cellulosic material and a thermoplastic resin. It becomes possible to manufacture materials and the like, and the present invention is useful for suppressing greenhouse gas emissions. Moreover, by using the resin composition of the present invention, various molded articles can be produced at low cost. Furthermore, the molded article of the present invention can be used not only in the field of conventional fiber-reinforced plastics, but also in fields where higher mechanical strength (for example, bending strength) is required.

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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

Cette composition de résine est caractérisée en ce qu'elle est un matériau malaxé à l'état fondu comprenant : un mélange (A) d'un matériau à base de cellulose, (B) d'une polyamine et (C) d'au moins un acide carboxylique choisi dans le groupe constitué d'un acide monocarboxylique et d'acides résiniques ; et (D) une résine thermoplastique.
PCT/JP2022/039743 2021-10-25 2022-10-25 Composition de résine, corps moulé l'utilisant et procédé de production d'une composition de résine WO2023074691A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0011488A1 (fr) * 1978-11-17 1980-05-28 The Wiggins Teape Group Limited Papier lié par traitement thermique
JP2002294080A (ja) * 2001-03-30 2002-10-09 Arakawa Chem Ind Co Ltd 熱可塑性樹脂組成物
JP2010533799A (ja) * 2007-07-16 2010-10-28 アクゾ ノーベル ナムローゼ フェンノートシャップ 充填剤組成物
WO2011049162A1 (fr) * 2009-10-23 2011-04-28 国立大学法人京都大学 Composition contenant des fibres végétales microfibrillées
WO2012017772A1 (fr) * 2010-08-06 2012-02-09 日本電気株式会社 Résine à base de cellulose

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0011488A1 (fr) * 1978-11-17 1980-05-28 The Wiggins Teape Group Limited Papier lié par traitement thermique
JP2002294080A (ja) * 2001-03-30 2002-10-09 Arakawa Chem Ind Co Ltd 熱可塑性樹脂組成物
JP2010533799A (ja) * 2007-07-16 2010-10-28 アクゾ ノーベル ナムローゼ フェンノートシャップ 充填剤組成物
WO2011049162A1 (fr) * 2009-10-23 2011-04-28 国立大学法人京都大学 Composition contenant des fibres végétales microfibrillées
WO2012017772A1 (fr) * 2010-08-06 2012-02-09 日本電気株式会社 Résine à base de cellulose

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