WO2019221029A1 - Procédé de fabrication d'une composition de résine thermoplastique et composition de résine thermoplastique, et composition de fibre de cellulose - Google Patents

Procédé de fabrication d'une composition de résine thermoplastique et composition de résine thermoplastique, et composition de fibre de cellulose Download PDF

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Publication number
WO2019221029A1
WO2019221029A1 PCT/JP2019/018777 JP2019018777W WO2019221029A1 WO 2019221029 A1 WO2019221029 A1 WO 2019221029A1 JP 2019018777 W JP2019018777 W JP 2019018777W WO 2019221029 A1 WO2019221029 A1 WO 2019221029A1
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thermoplastic resin
cellulose fiber
resin composition
mass
amide
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PCT/JP2019/018777
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English (en)
Japanese (ja)
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隆三郎 中桐
雄也 寺尾
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星光Pmc株式会社
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Priority to JP2020519606A priority Critical patent/JP7001155B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • 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 method for producing a thermoplastic resin composition, a thermoplastic resin composition, and a cellulose fiber composition.
  • fibrous additives such as glass fiber, carbon fiber, aramid fiber, and cellulose fiber have been used for the purpose of improving the strength of the resin molded body.
  • cellulose fibers have characteristics such as low density, high elastic modulus, and low linear thermal expansion coefficient.
  • it is a “carbon neutral” and sustainable resource, it is expected to become a material that contributes to reducing the environmental burden.
  • the strength of the cellulose fiber is not sufficiently reflected in the composite because the cellulose fiber is hydrophilic and the resin is hydrophobic, and the adhesion between the cellulose fiber and the resin is poor.
  • the reinforcing effect due to the entanglement of the fibers may not be sufficiently obtained.
  • Patent Document 1 discloses a method of using urea or a urea derivative as an additive for the purpose of improving the dispersibility of fine cellulose and improving the mechanical properties of a composite material of fine cellulose fibers and a resin.
  • Patent Document 2 discloses a composite resin containing cellulose fibers defibrated to the nano level by adjusting a mixture by adding a resin and a defibrating aid to wood-derived pulp, and melt-kneading the mixture. Is disclosed. Examples of fibrillation aids include urea, urea derivatives, sugars and organic acids.
  • Patent Document 3 fine cellulose fibers, water, a polar group-containing polyolefin resin, a low molecular compound having one or more of each of a hydrophobic group and a hydrophilic group, and a polyolefin resin are heated and kneaded and devolatilized.
  • a method for producing a resin composition containing cellulose is disclosed. Aliphatic alcohols, fatty acid amides and the like are listed as low molecular weight compounds each having one or more of both a hydrophobic group and a hydrophilic group.
  • the manufacturing method described in Patent Document 3 includes a step of obtaining fine cellulose by performing a fiber fibrillation treatment by wet grinding before the resin and fiber kneading step. In this process, it is necessary to use a large amount of water and to prevent the aggregation of fine cellulose accompanying the removal of the water and the removal of the water. For industrialization, the productivity is low and the production cost is high.
  • JP 2014-227639 A JP 2017-105983 A JP2015-209439A
  • the present invention provides a method for producing a thermoplastic resin composition, a thermoplastic resin composition, and a cellulose fiber composition capable of dramatically improving the strength of a thermoplastic resin molded article at low cost and efficiently. The issue is to provide.
  • thermoplasticity obtained by kneading cellulose fibers and an amide compound with a thermoplastic resin when kneading and mixing cellulose fibers and a thermoplastic resin. It was found that the mechanical strength of the resin composition was excellent.
  • thermoplastic resin composition comprising nanocellulose fibers (A), an amide compound (B) having at least one hydrocarbon group, and a thermoplastic resin (C), and cellulose fibers (A ′) And a amide compound (B) are kneaded with a thermoplastic resin (C), and the cellulose fiber (A ′) is fibrillated into the nanocellulose fiber (A) in the thermoplastic resin.
  • Production method, ⁇ 2> The thermoplastic resin according to ⁇ 1>, wherein the amide compound (B) is at least one selected from amide compounds having 3 to 30 carbon atoms and (meth) acrylamide polymers.
  • thermoplastic resin composition ⁇ 3> The method for producing a thermoplastic resin composition according to ⁇ 1> or ⁇ 2>, wherein the amide compound (B) has a primary amide group or a secondary amide group, ⁇ 4> The production of the thermoplastic resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein the thermoplastic resin (C) has a melting point or a softening point of 100 to 220 ° C.
  • Method, ⁇ 5> The above ⁇ 1>, characterized by kneading with the thermoplastic resin (C) after the step of mixing the cellulose fiber (A ′) and the amide compound (B) in the presence of water and / or an organic solvent.
  • thermoplastic resin composition is an amide compound (B ′) having a primary amide group or a secondary amide group and having a carboxylate
  • ⁇ 5> A process for producing the thermoplastic resin composition according to claim 1, ⁇ 7> A cellulose fiber composition comprising a cellulose fiber (A ′) and an amide compound (B), wherein the amide compound (B) has a primary amide group or a secondary amide group and has a carboxylate.
  • a cellulose fiber composition which is an amide compound (B ′), ⁇ 8> A thermoplastic resin composition comprising the cellulose fiber composition according to ⁇ 7> and a thermoplastic resin (C), It is.
  • the amide compound having at least one hydrocarbon group is appropriately electrostatically bonded to the hydroxyl group on the cellulose surface to coat the cellulose surface. Aggregation of fibers can be suppressed, and cellulose fibers can be efficiently defibrated when kneaded with a thermoplastic resin. In addition, since the fibrillated cellulose fiber is coated with an amide compound on the surface, it is difficult to reaggregate. Therefore, cellulose fibers can be uniformly dispersed in the thermoplastic resin, and the strength of the molded article of the thermoplastic resin can be dramatically improved.
  • FIG. 3 is an SEM photograph of the thermoplastic resin composition (EH-1) of Comparative Example 1.
  • FIG. 3 is an SEM photograph of the thermoplastic resin composition (E-1) of Example 1.
  • FIG. 3 is an SEM photograph of the thermoplastic resin composition (E-1) of Example 1.
  • the method for producing a thermoplastic resin composition comprises kneading cellulose fiber (A ′) and an amide compound (B) having at least one hydrocarbon group with thermoplastic resin (C), and cellulose fiber in the resin. It can be obtained by defibrating (A ′) into nanocellulose fibers (A).
  • Cellulose fiber (A ′) is a plant (eg, wood, bamboo, hemp, jute, kenaf, agricultural land residue, cloth, pulp (conifer unbleached kraft pulp (NUKP), conifer bleach kraft pulp (NBKP), hardwood unbleached). Kraft pulp (LUKP), hardwood bleached kraft pulp (LBKP), softwood unbleached sulfite pulp (NUSP), softwood bleached sulfite pulp (NBSP), thermomechanical pulp (TMP), recycled pulp, waste paper, etc.), animals (for example, Squirrels), algae, microorganisms (for example, acetic acid bacteria (Acetobacter)), microbial products, etc.
  • NUKP conifer bleach kraft pulp
  • NKP conifer bleach kraft pulp
  • LKP hardwood bleached kraft pulp
  • NUSP softwood unbleached sulfite pulp
  • NBSP softwood bleached sulfite pulp
  • TMP thermo
  • cellulose fibers derived from plants or microorganisms More preferably, it is a plant-derived cellulose fiber.
  • pulp particularly softwood unbleached kraft pulp (NUKP), softwood bleached kraft pulp (NBKP)
  • NUKP softwood unbleached kraft pulp
  • NNKP softwood bleached kraft pulp
  • the cellulose fiber has a smaller fiber width, and when it becomes a so-called cellulose microfibril, the hydrogen bond between the cellulose microfibrils becomes strong and causes aggregation when dried. For this reason, it becomes difficult to uniformly disperse into the resin as nanocellulose fibers during subsequent kneading with the resin. Therefore, in the present invention, cellulose fibers (A ′) that are generally easily available and have a fiber width of 20 to 100 ⁇ m are used as raw materials.
  • the raw material cellulose fiber (A ′) may be modified cellulose in which a functional group of cellulose is substituted and modified.
  • a modified cellulose fiber in which the hydroxyl group of cellulose is esterified with maleic anhydride, acetic anhydride, carboxylic anhydride of alkenyl succinic anhydride, or the like may be used.
  • Examples of the amide compound (B) having at least one hydrocarbon group include acetamide, propylamide, isopropionic acid amide, butyramide, pivalamide, dimethylpropanamide, hexaneamide, decanoic acid amide, laurylamide, palmitic acid amide, Saturated fatty acid amides such as stearylamide, hydroxystearic acid amide, unsaturated fatty acid amides such as oleic acid amide, erucic acid amide, N, N diethylacetamide, N, N diethyldodecanamide, N stearyl stearic acid amide, N stearyl N-substituted amides such as oleic acid amide, N oleyl stearic acid amide, N stearyl erucic acid amide, N oleyl oleic acid amide, methylol amides such as methylol stearic acid amide, malon
  • succinic anhydride maleic anhydride, phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride Bicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride, 4-methylhexahydrophthalic anhydride, ethylene glycol bisanhydro trimellitate, tetrapropenyl succinic anhydride, octenyl succinic anhydride, 2,5-diketotetrahydrofuran, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, hexadecenyl succinic anhydride, 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro- 2,5-dioxo-3-furanyl) naphtho
  • a compound that is an amide group or a secondary amide group and that forms a carboxylate can also be used as the amide compound (B).
  • phthalic anhydride, hexahydrophthalic anhydride, tetrapropenyl succinic anhydride, octenyl succinic anhydride, and monoamide monocarboxylate obtained by reacting hexadecenyl succinic anhydride and ammonia are preferable.
  • the amide compound (B) may be a polymer having a skeleton having an amide group as a structural unit.
  • (meth) acrylamide polymers are preferred.
  • the (meth) acrylamide polymer may contain other polymerizable monomer components to such an extent that the effect thereof is not hindered, but from the viewpoint of improving affinity with cellulose, (meth) acrylamide in the copolymer is used.
  • the composition ratio of the monomer is preferably 70% by mass or more.
  • the above amide compound (B) may be used alone or in combination of two or more. Among these, at least one selected from amide compounds having 3 to 30 carbon atoms and (meth) acrylamide polymers is preferable.
  • amide compounds having 3 to 30 carbon atoms and (meth) acrylamide polymers is preferable.
  • the amide compound (B) is more preferably a primary amide compound or a secondary amide compound because electrostatic interaction with hydroxyl groups on the surface of the cellulose fiber is promoted and coating is easier than a tertiary amide compound.
  • Monoamide is most preferable because it does not mediate electrostatic interaction between cellulose fibers.
  • Maleamide, stearic acid dimethylaminopropylamide, stearic acid diethylaminoethylamide, behenamidopropyldimethylamine, and 2-aminomalonamide are preferred.
  • the amide compound (B) is preferably used in an amount of 1 to 100 parts by mass with respect to 100 parts by mass of the raw material cellulose fiber (A ′) from the viewpoint of the fibrillation of the cellulose fiber and the strength of the thermoplastic resin molded article.
  • thermoplastic resin (C) is not particularly limited as long as it is usually used as a resin composition for a molding material.
  • polyacetal resin polyamide resin such as nylon
  • polyolefin resin such as polyethylene, polypropylene and ethylene-propylene copolymer
  • polyester resin such as polyethylene terephthalate and polybutylene terephthalate
  • acrylic resin such as polymethyl methacrylate and polyethyl methacrylate
  • polystyrene Acrylonitrile-butadiene-styrene copolymer, acrylonitrile-acrylic rubber-styrene copolymer, acrylonitrile-ethylene rubber-styrene copolymer, (meth) acrylic ester-styrene copolymer, styrene-butadiene-styrene copolymer
  • Styrene resins such as hydrogenated resins, ionomer resins, polyacrylonitrile, ethylene-viny
  • thermoplastic resin whose melting
  • a polyacetal resin, a polyamide resin, a polyolefin resin, or a polyurethane resin is used.
  • the cellulose fiber (A ′) and the amide compound (B) may be uniformly dispersed in the thermoplastic resin (C). If possible, the order of addition is not particularly limited.
  • the cellulose fiber composition (D) is preferably prepared by previously mixing the cellulose fiber (A ′) and the amide compound (B). Then, the cellulose fiber composition (D) is kneaded with the thermoplastic resin (C).
  • the amide compound (B) is a amide compound (B ′) having a primary amide group or a secondary amide group and having a carboxylate
  • the cellulose fiber (A ′) and the amide compound (B ′) Are previously mixed to obtain a cellulose fiber assembly (D), and then the cellulose fiber composition (D) is preferably kneaded with the thermoplastic resin (C).
  • the cellulose fiber composition (D) when the cellulose fiber composition (D) is obtained, the cellulose fiber (A ′) and the amide compound (B) may be mixed in the presence of water and / or an organic solvent as necessary.
  • the organic solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-butanol and t-butanol, ethylene glycol, propylene glycol, 1,3-butanediol, Glycols such as 1,4-butanediol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol monobutyl ether, triethylene glycol
  • cellulose fiber (A ′) and amide compound (B) may be mixed with a stirring mixer such as a kettle with a stirring blade, a blender or a Henschel mixer in the presence of water and / or an organic solvent as necessary. Can do.
  • a stirring mixer such as a kettle with a stirring blade, a blender or a Henschel mixer in the presence of water and / or an organic solvent as necessary.
  • the obtained cellulose fiber composition (D) can be used for kneading with a thermoplastic resin as it is regardless of whether or not a solvent is used. However, when a solvent is used, it should be dried before kneading. preferable.
  • the drying method is not particularly limited as long as the cellulose fiber (A ′) and the amide compound (B) can be dried at a temperature that does not cause aggregation or decomposition. At this time, in order to suppress aggregation of the cellulose fibers (A ′) and the amide compound (B), it is preferable to dynamically dry the contents under stirring under a reduced pressure atmosphere.
  • the thermoplastic resin composition obtained in the present invention only needs to contain at least the nanocellulose fiber (A), the amide compound (B), and the thermoplastic resin (C), as long as the effects of the present invention are not impaired.
  • cellulose fibers (A ′) may be included.
  • the content ratio of the cellulose fiber (A ′) is preferably less than 50% by mass, more preferably less than 20% by mass, and still more preferably less than 10% by mass with respect to the total of the nanocellulose fiber (A) and the cellulose fiber (A ′). It is.
  • the total content of the nanocellulose fibers (A) and the cellulose fibers (A ′) in the thermoplastic resin composition is preferably 0.1 to 80% by mass from the viewpoint of the reinforcing effect and moldability.
  • thermoplastic resin (C) 0.1 to 80 / 0.001 to 50/10 to 99.899
  • thermoplastic resin (C) 0.1 to 90 / 10 to 99.9
  • cellulose fiber composition (D) / thermoplastic resin (C) 5 to 40 / 0.1 to 10/50 to 94.9
  • thermoplastic resin (C) 5.1 to 50/50 to 94.9
  • the thermoplastic resin composition can be obtained by kneading the cellulose fiber (A ′) and the amide compound (B) (or the cellulose fiber composition (D) which is a pre-mixture thereof) with the thermoplastic resin (C).
  • the kneading method is not particularly limited, and a conventionally known method can be used. For example, there are a uniaxial kneader, a biaxial kneader, a kneader, a Banbury mixer, a pressure kneader, a roll kneader and the like.
  • the kneading temperature may be higher than the melting point or softening point of the thermoplastic resin (C).
  • thermoplastic resin composition of the present invention includes maleic anhydride-modified polyolefin, a resin other than the thermoplastic resin (C), talc, clay, a crystallization nucleating agent, a crosslinking agent, as long as the effects of the present invention are not hindered. Hydrolysis inhibitors, antioxidants, lubricants, waxes, colorants, stabilizers and the like may be blended.
  • thermoplastic resin composition obtained as described above as a molded body
  • a general molding method can be used. Examples include injection molding, extrusion molding, blow molding, compression molding, and foam molding.
  • an interior / exterior material or a casing for a transport machine such as an automobile, a motorcycle, a bicycle, a railway, a drone, a rocket, an aircraft, a ship, etc., a wind power generator , Energy machines such as hydroelectric generators, air conditioners, refrigerators, vacuum cleaners, microwave ovens, AV equipment, digital cameras, personal computer housings such as personal computers, communication equipment housings such as electronic boards, mobile phones, smart phones, Matsubae, wheelchairs Medical equipment such as shoes, shoes such as sneakers and business shoes, tires, balls for ball sports, ski boots, snowboard boards, golf clubs, protectors, fishing lines, sports equipment such as artificial bait, outdoor equipment such as tents and hammocks, Construction materials such as wire covering materials, water pipes, gas pipes, etc., pillar materials, flooring materials, decorative panels, window frames, heat insulating materials, bookshelves, desks, chairs Furniture, industrial robots, home robots, hot melt adhesives, filaments and support agents for
  • cellulose fiber (A ′) For the cellulose fiber (A ′), (a1) and (a2) shown below were used.
  • Cellulose fiber (a1) As a raw material cellulose fiber (A ′) used in this example, commercially available softwood bleached kraft cellulose (a1) was used. When (a1) was dispersed in water and observed with an optical microscope, the average fiber diameter was 50 ⁇ m.
  • thermoplastic resin (C) high density polyethylene resin ("Suntech J320" manufactured by Asahi Kasei Co., Ltd., 86 ° C melting point) 86 parts by mass, cellulose fiber (A ') as cellulose fiber (a1) 10 parts by mass, amide compound (B) 4 parts by weight of pivalamide as a lab plast mill (manufactured by Toyo Seiki Co., Ltd.), melt-kneaded for 10 minutes at a kneading temperature of 140 ° C. and 50 rpm, and defibrated into nanocellulose fibers to be a thermoplastic resin composition (E-1) was obtained.
  • thermoplastic resin composition (E-2) was prepared in the same manner as in Example 1 except that the type of cellulose fiber (A ′), the type of amide compound (B) and the amount charged were changed as shown in Table 1. To 24).
  • thermoplastic resin composition (E-25) As thermoplastic resin (C), polypropylene resin ("Prime Polypro J108M” manufactured by Prime Polymer Co., Ltd., melting point 165 ° C) 86 parts by mass, cellulose fiber (A ') as cellulose fiber (a1) 10 parts by mass, amide compound (B) 4 parts by weight of butyramide as a lab plast mill (manufactured by Toyo Seiki Co., Ltd.), melt kneaded for 10 minutes at a kneading temperature of 170 ° C. and 50 rpm, and defibrated into nanocellulose fibers to be a thermoplastic resin composition (E-25) was obtained.
  • thermoplastic resin (C) polypropylene resin ("Prime Polypro J108M” manufactured by Prime Polymer Co., Ltd., melting point 165 ° C) 86 parts by mass, cellulose fiber (A ') as cellulose fiber (a1) 10 parts by mass, amide compound (B) 4 parts by weight of butyr
  • Example 26 [Production Example of Thermoplastic Resin Composition E-26] After charging 100 parts by weight of cellulose fiber (a1) as cellulose fiber (A ′), 400 parts by weight of water and 40 parts by weight of laurylamide and 400 parts by weight of isopropanol as the amide compound (B), and mixing at 70 ° C. Water and isopropanol were distilled off under reduced pressure to obtain a cellulose fiber composition comprising a1 and laurylamide.
  • thermoplastic resin composition 14 parts by mass of the cellulose fiber composition and 86 parts by mass of a high-density polyethylene resin (“Suntech J320”, melting point 130 ° C., manufactured by Asahi Kasei Co., Ltd.) as a thermoplastic resin (C) were added to Labo Plast Mill (Toyo Seiki Co., Ltd.). ), Melt kneaded for 10 minutes at a kneading temperature of 140 ° C. and 50 rotations / minute, and defibrated into nanocellulose fibers to obtain a thermoplastic resin composition (E-26).
  • a high-density polyethylene resin (“Suntech J320”, melting point 130 ° C., manufactured by Asahi Kasei Co., Ltd.)
  • C thermoplastic resin
  • Example 27 [Production Example of Thermoplastic Resin Composition E-27] 100 parts by mass of cellulose fiber (a1) as cellulose fiber (A ′), 400 parts by mass of water and 40 parts by mass of stearylamide as amide compound (B) are put into a container, mixed at 70 ° C., and then water is added under reduced pressure. Was distilled off to obtain a cellulose fiber composition comprising a1 and stearylamide.
  • thermoplastic resin composition 14 parts by mass of the cellulose fiber composition and 86 parts by mass of a high-density polyethylene resin (“Suntech J320”, melting point 130 ° C., manufactured by Asahi Kasei Co., Ltd.) as a thermoplastic resin (C) were added to Labo Plast Mill (Toyo Seiki Co., Ltd.). ), Melt-kneaded for 10 minutes at a kneading temperature of 140 ° C. and 50 rpm, and defibrated into nanocellulose fibers to obtain a thermoplastic resin composition (E-27).
  • a high-density polyethylene resin (“Suntech J320”, melting point 130 ° C., manufactured by Asahi Kasei Co., Ltd.)
  • C thermoplastic resin
  • Example 28 [Production Example of Thermoplastic Resin Composition E-28] After putting 100 parts by mass of cellulose fiber (a1) as cellulose fiber (A ′), 400 parts by mass of water and 40 parts by mass of stearylamide and 400 parts by mass of isopropanol as a amide compound (B), and mixing at 70 ° C. Water and isopropanol were distilled off under reduced pressure to obtain a cellulose fiber composition composed of a1 and stearylamide.
  • thermoplastic resin composition 14 parts by mass of the cellulose fiber composition and 86 parts by mass of a high-density polyethylene resin (“Suntech J320”, melting point 130 ° C., manufactured by Asahi Kasei Co., Ltd.) as a thermoplastic resin (C) were added to Labo Plast Mill (Toyo Seiki Co., Ltd.). ), Melt-kneaded for 10 minutes at a kneading temperature of 140 ° C. at 50 rpm, and defibrated into nanocellulose fibers to obtain a thermoplastic resin composition (E-28).
  • a high-density polyethylene resin (“Suntech J320”, melting point 130 ° C., manufactured by Asahi Kasei Co., Ltd.)
  • C thermoplastic resin
  • Example 29 [Production Example of Thermoplastic Resin Composition E-29] After putting 100 parts by mass of cellulose fiber (a1) as cellulose fiber (A ′), 400 parts by mass of water and 40 parts by mass of stearylamide and 400 parts by mass of isopropanol as a amide compound (B), and mixing at 70 ° C. Water and isopropanol were distilled off under reduced pressure to obtain a cellulose fiber composition composed of a1 and stearylamide.
  • thermoplastic resin composition 7 parts by mass of the cellulose fiber composition and 93 parts by mass of a high-density polyethylene resin (“Suntech J320”, melting point 130 ° C., manufactured by Asahi Kasei Co., Ltd.) as a thermoplastic resin (C) were added to Labo Plast Mill (Toyo Seiki Co., Ltd.). ), Melt-kneaded for 10 minutes at a kneading temperature of 140 ° C. at 50 rpm, and defibrated into nanocellulose fibers to obtain a thermoplastic resin composition (E-29).
  • a high-density polyethylene resin (“Suntech J320”, melting point 130 ° C., manufactured by Asahi Kasei Co., Ltd.)
  • C thermoplastic resin
  • Example 30 [Production Example of Thermoplastic Resin Composition E-30] 100 parts by mass of cellulose fiber (a1) as cellulose fiber (A ′) and 40 parts by mass of stearylamide and 800 parts by mass of isopropanol as amide compounds (B) were put into a container, mixed at 70 ° C., and then isopropanol under reduced pressure. Was distilled off to obtain a cellulose fiber composition comprising a1 and stearylamide.
  • thermoplastic resin (C) 14 parts by mass of the cellulose fiber composition and 86 parts by mass of a high-density polyethylene resin (“Suntech J320”, melting point 130 ° C., manufactured by Asahi Kasei Co., Ltd.) as a thermoplastic resin (C) were added to Labo Plast Mill (Toyo Seiki Co., Ltd.). ), Melt-kneaded for 10 minutes at a kneading temperature of 140 ° C. and 50 rpm, and defibrated into nanocellulose fibers to obtain a thermoplastic resin composition (E-30).
  • a high-density polyethylene resin (“Suntech J320”, melting point 130 ° C., manufactured by Asahi Kasei Co., Ltd.)
  • C thermoplastic resin
  • Example 31 [Production Example of Thermoplastic Resin Composition E-31]
  • Cellulose fiber (a1) 100 parts by weight as cellulose fiber (A ′), water 400 parts by weight and stearamide 40 parts by weight as amide compound (B), Nippon Zeon Co., Ltd.
  • aliphatic hydrocarbon resin “Quinton R -100 ", 10 parts by mass, 400 parts by mass of isopropanol, and 100 parts by mass of tetrahydrofuran (THF) were mixed. After mixing at 70 ° C, water and solvent were distilled off under reduced pressure, and a1, stearylamide, and aliphatic carbonization were performed.
  • a cellulose fiber composition made of a hydrogen resin was obtained.
  • thermoplastic resin composition 15 parts by mass of the cellulose fiber composition and 85 parts by mass of a high-density polyethylene resin (“Suntech J320”, melting point 130 ° C., manufactured by Asahi Kasei Co., Ltd.) as a thermoplastic resin (C) were added to Labo Plast Mill (Toyo Seiki Co., Ltd.). ), Melt-kneaded for 10 minutes at a kneading temperature of 140 ° C. and 50 rpm, and defibrated into nanocellulose fibers to obtain a thermoplastic resin composition (E-31).
  • a high-density polyethylene resin (“Suntech J320”, melting point 130 ° C., manufactured by Asahi Kasei Co., Ltd.)
  • C thermoplastic resin
  • Labo Plast Mill Toyo Seiki Co., Ltd.
  • Example 32 [Production Example of Thermoplastic Resin Composition E-32] 100 parts by weight of cellulose fibers (a1) as cellulose fibers (A ′), 400 parts by weight of water and 40 parts by weight of dimethylaminopropylamide stearate and 400 parts by weight of isopropanol as amide compounds (B) are put into a container, and 70 ° C. Then, water and isopropanol were distilled off under reduced pressure to obtain a cellulose fiber composition comprising a1 and dimethylaminopropylamide stearate.
  • thermoplastic resin composition 14 parts by mass of the cellulose fiber composition and 86 parts by mass of a high-density polyethylene resin (“Suntech J320”, melting point 130 ° C., manufactured by Asahi Kasei Co., Ltd.) as a thermoplastic resin (C) were added to Labo Plast Mill (Toyo Seiki Co., Ltd.). ), Melt-kneaded for 10 minutes at a kneading temperature of 140 ° C. and 50 rpm, and defibrated into nanocellulose fibers to obtain a thermoplastic resin composition (E-32).
  • a high-density polyethylene resin (“Suntech J320”, melting point 130 ° C., manufactured by Asahi Kasei Co., Ltd.)
  • C thermoplastic resin
  • thermoplastic resin compositions (E-33 to 35) were the same as those described in Examples 26 to 32 except that the types and ratios of the thermoplastic resin (C) and the amide compound (B) were different as shown in Table 2. Got.
  • Examples of Cellulose Fiber Composition (D) Next, the cellulose fiber (A ′) and the amide compound (B ′) are mixed in advance to obtain a cellulose fiber composition (D), and then kneaded with the thermoplastic resin (C) to obtain a thermoplastic resin composition.
  • An example is shown about an aspect.
  • Example 36 [Examples of Cellulose Fiber Composition (D-1)] 100 parts by mass of cellulose fiber (a1), 400 parts by mass of water and 160 parts by mass of amide compound (B′-1) (solid content of 40 parts by mass) are put into a container, mixed at 70 ° C., and then dehydrated under reduced pressure. Distilled off to obtain a cellulose fiber composition (D′-1).
  • thermoplastic resin (C) 86 parts by mass of high density polyethylene resin (“Suntech J320”, melting point 130 ° C., manufactured by Asahi Kasei Co., Ltd.) and 14 parts by mass of the cellulose fiber composition (D-1) ), And melt-kneaded at a kneading temperature of 140 ° C. at 50 rpm for 10 minutes to defibrate nanocellulose fibers to obtain a thermoplastic resin composition (E-43).
  • thermoplastic resin composition (E-44 to 49) [Production of thermoplastic resin composition (E-44 to 49)] Thermoplastic resin compositions (E-44 to 49) were obtained in the same manner as described in Example 43 except that the type and amount of the cellulose fiber composition (D) were changed as shown in Table 5.
  • thermoplastic resin composition (E-50) As a thermoplastic resin (C), 72 parts by mass of polypropylene resin (Prime Polypro J108M made by Prime Polymer Co., Ltd., melting point 165 ° C.) and 28 parts by mass of the cellulose fiber composition (D-1) were added to Labo Plast Mill (Toyo Seiki Co., Ltd.). ), And melt-kneaded at a kneading temperature of 170 ° C. at 50 rpm for 10 minutes to defibrate nanocellulose fibers to obtain a thermoplastic resin composition (E-50).
  • a thermoplastic resin (C) 72 parts by mass of polypropylene resin (Prime Polypro J108M made by Prime Polymer Co., Ltd., melting point 165 ° C.) and 28 parts by mass of the cellulose fiber composition (D-1) were added to Labo Plast Mill (Toyo Seiki Co., Ltd.). ), And melt-kneaded at a kneading temperature of 170
  • thermoplastic resin composition (E-51) As a thermoplastic resin (C), 54 parts by mass of a linear low-density polyethylene resin ("Ultzex 4020L” manufactured by Prime Polymer Co., Ltd., melting point 126 ° C.) and 46 parts by mass of the cellulose fiber composition (D-1) are obtained. (Toyo Seiki Co., Ltd.), melt-kneaded for 10 minutes at a kneading temperature of 140 ° C. and 50 rpm, and defibrated into nanocellulose fibers to obtain a thermoplastic resin composition (E-51).
  • Ultzex 4020L linear low-density polyethylene resin
  • D-1 melting point 126 ° C.
  • thermoplastic resin (C) As thermoplastic resin (C), 90 parts by mass of high-density polyethylene resin ("Suntech J320" manufactured by Asahi Kasei Co., Ltd., melting point 130 ° C) and 10 parts by mass of cellulose fiber (a1) are supplied to Labo Plast Mill (manufactured by Toyo Seiki Co., Ltd.). The mixture was melted and kneaded for 10 minutes at a kneading temperature of 140 ° C. and 50 rotations / minute, and fibrillated into nanocellulose fibers to obtain a thermoplastic resin composition (EH-1).
  • thermoplastic resin composition (EH-2) As a thermoplastic resin (C), 86 parts by mass of high-density polyethylene resin (“Suntech J320”, melting point 130 ° C., manufactured by Asahi Kasei Co., Ltd.), 10 parts by mass of cellulose fiber (a1), and 4 parts by mass of urea were added to Labo Plast Mill (Toyo Seiki ( And melt-kneaded for 10 minutes at a kneading temperature of 140 ° C. and 50 rotations / minute to defibrate nanocellulose fibers to obtain a thermoplastic resin composition (EH-2).
  • thermoplastic resin composition (EH-3) As thermoplastic resin (C), 90 parts by mass of polypropylene resin ("Prime Polypro J108M” manufactured by Prime Polymer Co., Ltd., melting point 165 ° C) and 10 parts by mass of cellulose fiber (a1) are supplied to Labo Plast Mill (manufactured by Toyo Seiki Co., Ltd.). The mixture was melted and kneaded at a kneading temperature of 170 ° C., and fibrillated into nanocellulose fibers to obtain a thermoplastic resin composition (EH-3).
  • thermoplastic resin compositions E-1 to 51, EH1 to 3 obtained in Examples 1 to 51 and Comparative Examples 1 to 3 were used using a manual injection molding machine (manufactured by Imoto Seisakusho Co., Ltd .; model 18D1).
  • a bar-type test piece described in JIS standard K7171 was molded, and in accordance with JIS K7171, the bending strength and flexural modulus were measured with a universal testing machine “Tensilon RTM-50” manufactured by Orientec Co., Ltd.
  • Tables 1, 2 and 5 show the results of comparing the strength improvement rate as an index.
  • Elastic modulus [index] (elastic modulus of examples and comparative examples) / (elastic modulus of resin alone)
  • Strength [index] (strength of examples and comparative examples) / (strength of resin alone)
  • amide compound (B) in Tables 1, 2, and 5 Details of the amide compound (B) in Tables 1, 2, and 5 are shown below.
  • PolyAAm acrylamide homopolymer (weight average molecular weight 1,000,000)
  • Poly NIPAM isopropylacrylamide homopolymer (weight average molecular weight 126,000)
  • Poly ACMO acryloyl morpholine homopolymer (weight average molecular weight 126,000))
  • PolyDEAA diethylacrylamide homopolymer (weight average molecular weight 792,000)
  • Poly HEAA hydroxyethylacrylamide homopolymer (weight average molecular weight 1,950,000)
  • HDPE High-density polyethylene resin ("Suntech J320", melting point 130 ° C, manufactured by Asahi Kasei Corporation)
  • HPP Polypropylene resin ("Prime Polypro J108M” manufactured by Prime Polymer Co., Ltd., melting point 165 ° C)
  • LLDPE Linear low density polyethylene resin ("U
  • thermoplastic resin compositions obtained in Examples and Comparative Examples are wrapped in 325 mesh stainless mesh, and the resin is dissolved and removed by treatment at 140 ° C. for 5 hours under reflux of xylene, and the nanocellulose fiber (A) is resin composition
  • the number average fiber diameter of the nanocellulose fiber (A) was calculated by observing with a scanning electron microscope (SEM) and measuring the width of the fiber. An example is shown in Table 6. Further, as is apparent from the SEM photographs of FIGS. 1 and 2, it can be seen that in Comparative Example 1 in which the cellulose fiber (a1) was kneaded alone with the thermoplastic resin, the cellulose fibers were not sufficiently defibrated. In contrast, in the sample of Example 1, it can be seen that the cellulose fibers (A ′) are uniformly nanocellulose fibers (A). Similar results were obtained for other samples.
  • thermoplastic resin compositions (E) obtained in the examples and comparative examples were measured for melt mass flow rate in accordance with JIS standard K7210 using an automelt indexer (manufactured by Tester Sangyo Co., Ltd .; model TP406). .
  • An example is shown in Table 7.
  • Comparative Example 1 the change (decrease) in MFR is small compared to the high density polyethylene resin (“Suntech J320” manufactured by Asahi Kasei Co., Ltd., melting point 130 ° C.), which is a matrix resin, whereas in Example 1, the MFR is extremely low. It has become.
  • the MFR of the resin in which nanofibers are highly dispersed is extremely lower than the MFR of the matrix resin. Therefore, in the cellulose fiber composite thermoplastic resin composition (E) produced in the examples, cellulose fibers ( A ′) is considered to be nanocellulose fibers (A) and in a highly dispersed state.
  • the cellulose fiber (A ′) in the thermoplastic resin composition (E) obtained by this production method is defibrated during kneading with the thermoplastic resin (C), and the nanocellulose fiber It is clear that it is (A).
  • thermoplastic resin moldings obtained by kneading cellulose fibers and amide compounds defined in the present invention with a thermoplastic resin are cellulose fibers that do not use amide compounds. It turns out that it has the outstanding mechanical strength with respect to the kneaded material of a thermoplastic resin.
  • Example 17 From the results of Example 2, Example 17 and Example 13, the amide compound (B) has a primary amide group or a secondary amide group, so that the machine is superior to the case where an amide compound having a tertiary amide group is used. It can be seen that it has a high strength.
  • thermoplastic resin (C) after the step of mixing the cellulose fiber (A ′) and the amide compound (B) in the presence of water and / or an organic solvent.
  • the thermoplastic resin molded body obtained by kneading with the thermoplastic resin molded body obtained by kneading the thermoplastic resin (C) without premixing the cellulose fiber (A ′) and the amide compound (B) It can be seen that it has excellent mechanical strength.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

La présente invention a pour objectif de fournir des procédés de fabrication d'une composition de résine thermoplastique et d'une composition de fibre de cellulose qui peuvent améliorer considérablement la résistance d'un article moulé en résine thermoplastique de manière efficace. L'invention concerne un procédé de fabrication d'une composition de résine thermoplastique qui contient une fibre de nanocellulose (A), un composé amide (B) et une résine thermoplastique (C). Le procédé est caractérisé en ce qu'il consiste : à mélanger une fibre de cellulose (A') et le composé amide (B) dans la résine thermoplastique (C), et à fibriller la fibre de cellulose (A') dans la fibre de nanocellulose (A) dans la résine thermoplastique.
PCT/JP2019/018777 2018-05-18 2019-05-10 Procédé de fabrication d'une composition de résine thermoplastique et composition de résine thermoplastique, et composition de fibre de cellulose WO2019221029A1 (fr)

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WO2020090711A1 (fr) * 2018-10-31 2020-05-07 大王製紙株式会社 Résine composite de cellulose fibreuse et son procédé de production
WO2020262344A1 (fr) * 2019-06-28 2020-12-30 大王製紙株式会社 Résine recyclée composite à base de fibres de cellulose et son procédé de production
JP7444669B2 (ja) 2020-03-25 2024-03-06 旭化成株式会社 微細セルロース繊維を含む複合粒子、及び複合粒子を含む樹脂組成物

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Publication number Priority date Publication date Assignee Title
JP2020070378A (ja) * 2018-10-31 2020-05-07 大王製紙株式会社 繊維状セルロース複合樹脂及びその製造方法
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JP7444669B2 (ja) 2020-03-25 2024-03-06 旭化成株式会社 微細セルロース繊維を含む複合粒子、及び複合粒子を含む樹脂組成物

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