WO2016010016A1 - Cnf dérivé, son procédé de fabrication, et composition de résine de polyoléfine - Google Patents

Cnf dérivé, son procédé de fabrication, et composition de résine de polyoléfine Download PDF

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Publication number
WO2016010016A1
WO2016010016A1 PCT/JP2015/070099 JP2015070099W WO2016010016A1 WO 2016010016 A1 WO2016010016 A1 WO 2016010016A1 JP 2015070099 W JP2015070099 W JP 2015070099W WO 2016010016 A1 WO2016010016 A1 WO 2016010016A1
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cnf
derivatized
reaction
vinyl
water
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PCT/JP2015/070099
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English (en)
Japanese (ja)
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森　智夫
洋美 橋場
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中越パルプ工業株式会社
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Priority to JP2016534435A priority Critical patent/JP6245779B2/ja
Publication of WO2016010016A1 publication Critical patent/WO2016010016A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/06—Cellulose acetate, e.g. mono-acetate, di-acetate or tri-acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/08—Preparation of cellulose esters of organic acids of monobasic organic acids with three or more carbon atoms, e.g. propionate or butyrate
    • C08B3/10—Preparation of cellulose esters of organic acids of monobasic organic acids with three or more carbon atoms, e.g. propionate or butyrate with five or more carbon-atoms, e.g. valerate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to derivatized CNF and a method for producing the same. From another point of view, the present invention relates to a polyolefin resin composition that is excellent in environmental characteristics by use of a biomass material, has a small decrease in impact strength, has a low specific gravity, a high rigidity, and an excellent molded appearance.
  • biomass materials have attracted attention from the viewpoint of environmental protection, and natural-derived organic fillers and composite materials with biopolymers have begun to be used as materials for automobiles, OA and electric / electronic fields.
  • natural-derived organic fillers and composite materials with biopolymers have begun to be used as materials for automobiles, OA and electric / electronic fields.
  • a method of adding an inorganic filler such as glass fiber to a resin composition has been studied.
  • these inorganic fillers need to be added in a large amount, there are problems that the specific gravity of the molded article is increased, and the residue that becomes dust at the time of incineration or disposal is increased, which imposes a burden on the environment.
  • CNF naturally-derived cellulose nanofibers
  • PP polypropylene
  • PE polyethylene
  • PS polystyrene
  • ACC method which is a physical preparation method of CNF
  • ACC method which is a physical preparation method of CNF
  • Patent Document 1 the underwater facing collision method
  • This method uses only water in addition to natural cellulose fibers, and is a nano-miniaturization method by cleaving only the interaction between fibers, so there is no structural change of the cellulose molecule and the degree of polymerization decreases with cleavage. It is possible to obtain a nano-miniaturized product with a minimum of.
  • CNF can be mechanically produced in an aqueous medium by treatment with a blender stirring, a grinder, a microfluidizer, a high-pressure homogenizer or the like described in Patent Document 6 and Patent Document 7.
  • Non-Patent Document 1 to Non-Patent Document 3 a method of laurylating or acetylating starch, pulp or wood flour using vinyl acetate in an aqueous solution is widely known.
  • Non-Patent Document 4 a method of hydrophobizing cellulose using chlorinated fatty acid is also known.
  • Patent Documents 2 and 3 provide fiber composite materials having excellent characteristics. A fiber composite material characterized by containing CNF modified with a substituent having a carboxyl group and an acyl group and a resin is described.
  • Patent Document 4 provides a method for producing a CNF dispersion that can be suitably used for complexing with a wide range of organic solvent-soluble polymer materials.
  • Patent Document 5 has an average degree of polymerization of 600 or more and 30000 or less, an aspect ratio of 20 to 10,000, an average diameter of 1 to 800 nm, an X-ray diffraction pattern having an I ⁇ type crystal peak, and a hydroxyl group.
  • Patent Document 8 jute is used as a natural organic filler in order to blend an aliphatic polyester and a natural organic filler into an aromatic polycarbonate resin to obtain a resin composition having excellent mechanical properties and flame retardancy.
  • Patent Document 9 (A) 99 to 60% by mass of a polycarbonate resin and (B) 1 to 40% by mass of cellulose fibers having an average fiber diameter of 5 to 50 ⁇ m and an average fiber length of 0.03 to 1.5 mm.
  • Patent Document 10 discloses a composition containing cellulose and a dispersant, the dispersant having a resin affinity segment A and a cellulose affinity segment B, and a block copolymer structure or a gradient copolymer. A composition manufacturing technique characterized by having a structure is described.
  • Patent Document 11 describes a technique for producing a hydrophilic nanofiber composite material, in which the hydroxyl group of a hydrophilic nanofiber having a hydroxyl group is solvated with a hydrophilic organic solvent and mixed with molten plastic.
  • Patent Document 12 describes a dispersion in which both CNF and resin are uniformly dispersed in a dispersion medium, and a resin composition in which CNF is uniformly contained in the resin.
  • JP 2005-270891 A JP2011-105799A JP2011-148914A JP2012-021081 JP 2013-44076 JP 2010-216021 WO2011118746 JP 2010-215791 A WO / 2013/133228 JP2014-162880 JP2013-170241A JP2013-166818A
  • Non-Patent Document 1 Although the acetylation method is widely known as described in Non-Patent Document 1 to Non-Patent Document 3, acetylation cannot sufficiently secure hydrophobicity for CNF, and polyolefin such as polypropylene having high hydrophobicity. There is a problem that it is necessary to impart stronger hydrophobicity in order to disperse uniformly in the resin.
  • Non-Patent Document 4 a method of hydrophobizing cellulose using chlorinated fatty acid is also known, but a non-aqueous reaction is required and there is a problem that a reaction containing water cannot be performed.
  • the fiber composite material of Patent Document 2 is a nanofiber obtained by oxidizing a hydroxyl group to a carboxyl group, and then dehydrated and then esterified using an acid anhydride, and a non-aqueous reaction is performed. Yes.
  • cellulose is modified under anhydrous conditions, and the degree of substitution is as high as 1.5 to 3.0. According to Non-Patent Document 4, the degree of substitution exceeds 0.55. Sufficient strength cannot be realized because the physical strength of nanofibers is reduced.
  • anhydrous conditions are essential.
  • Patent Document 4 manufactures CNF by changing the hydroxyl group of cellulose (glucose residue) to a carboxyl group, forms a highly hydrophobic amine and a carboxyl group salt, and imparts hydrophobicity to the nanofiber.
  • CNF obtained by a conventional defibrating method cannot be processed.
  • CNF of Patent Document 5 is acetylated with acetic anhydride at the same time as nanofiber pretreatment using an ionic liquid, and the resulting product is homogenized and nanonized, increasing the hydrophobicity and heat resistance of the nanofibers That's it.
  • the CNF obtained by the ACC method cannot be treated, and generally the derivatization reaction is performed in an anhydrous manner.
  • Patent Document 8 When CNF is handled in a water-containing state, the reactivity is significantly lowered. Moreover, since an expensive ionic liquid is used, it is difficult to use industrially at present. Although various attempts have been made for resin compositions as described above, satisfactory results have not been obtained in any case.
  • the resin composition obtained in Patent Document 8 has a large reduction in impact strength, an insufficient molded appearance, a large coloration, and insufficient thermal stability during molding.
  • the resin composition described in Patent Document 9 is said to have a low specific gravity, the specific gravity (g / cm 3) exceeds 1.20 in all examples, and the specific gravity is larger than that of water. It does not fully meet the problem of weight reduction.
  • CNF cannot be dispersed unless a maleic anhydride-modified resin is used in combination, and even if used together, there are many aggregates of 10 ⁇ m or more.
  • Cellulose is chemically modified, and unmodified cellulose cannot be used.
  • terpene resins are not used. Even at the strength level, the elastic modulus is improved, but the impact strength is remarkably lowered.
  • the present invention provides a derivatized CNF in which a hydroxyl group present on the CNF surface is esterified and a method for producing the same.
  • a derivatized CNF maintains the crystal structure and does not impair the mechanical properties, while canceling the high hydrophilicity that water-containing CNF had, such as polyethylene and polypropylene.
  • Compatibility with hydrophobic resins such as polyolefins is improved. Further, it can be completely dried, and the influence of moisture during kneading and transportation costs can be reduced.
  • the present invention is a resin that is excellent in environmental characteristics due to the use of biomass material, has a low decrease in impact strength, has a low specific gravity, high rigidity, and excellent molded appearance.
  • a composition is provided.
  • the composite resin is imparted with a higher reinforcing effect and transparency.
  • the polyolefin-CNF composite resin of the present invention is produced by using a surface-hydrophobized CNF instead of CNF as a reinforcing material, and compounding with polyolefin by high-speed stirring mixing and biaxial extrusion kneading.
  • the present invention is a method for hydrophobizing CNF using vinyl organic acid, and for example, surface modification of esterifying hydroxyl groups exposed on the surface of CNF using vinyl acetate, vinyl benzoate, vinyl laurate or the like. It is a technique. That is, in the method for producing derivatized CNF of the present invention, organic acid vinyl is added to a solution in which hydrous CNF is dispersed in a hydrophilic organic solvent, and a precipitate is generated in the reaction solution after completion of the reaction, and the precipitate is recovered and dried. It is characterized by that. Or you may extract and collect
  • a hydrophobic derivative By mixing water-containing CNF and an organic solvent, a hydrophobic derivative can be easily maintained while maintaining the nanostructure of CNF in the reaction solution. CNF can be dissolved uniformly.
  • water-containing CNF is added to an organic solvent having sufficient dispersibility with respect to CNF together with potassium carbonate, organic acid vinyl is added, and the reaction product after completion of the reaction is recovered. And drying.
  • the present invention relates to the following polyolefin resin composition. That is, (A) an average thickness of 10 to 200 nm, derivatized CNF obtained by derivatizing a polysaccharide with a high-pressure water stream and derivatized CNF 1 to 10% by mass, and (B) a polyolefin resin 99 to 90% by mass.
  • This is a polyolefin resin composition.
  • the derivatized CNF may be hydrophobically derivatized with an organic acid vinyl, and examples thereof include derivatized CNF which is hydrophobically derivatized with vinyl laurate.
  • the CNF is preferably obtained by colliding high pressure water of about 50 to 400 MPa with a polysaccharide in a water mixture of 0.5 to 10% by mass.
  • the polyolefin can be polypropylene, polyethylene, polybutadiene, polyisoprene, and this technology is not only applicable to polyolefins, but can also be applied to other general-purpose plastics that can be molded at 300 ° C. or lower. . In the case of 300 ° C. or higher, decomposition of cellulose occurs.
  • the method for producing a composite resin of the present invention is characterized in that a hydrophobic derivatized CNF swollen with an organic solvent is melt-kneaded after a pretreatment step of stirring at high speed with a polyolefin.
  • the high hydrophilicity of CNF can be canceled and hydrophobicity can be imparted.
  • the derivatized CNF of the present invention obtained by the method for producing the derivatized CNF of the present invention can be completely dried, has improved compatibility with a hydrophobic resin such as polyolefin, and has water content during kneading with plastic. Impact and transportation costs can be reduced.
  • examples of CNF include polysaccharide-derived CNF including natural plants such as wood fiber, bamboo fiber, sugarcane fiber, seed hair fiber, and leaf fiber. These CNFs may be used alone or in combination of two or more. May be used in combination.
  • the polysaccharide it is preferable to use pulp having an ⁇ -cellulose content of 60% to 99% by mass. If the purity is ⁇ -cellulose content 60% by mass or more, the fiber diameter and fiber length can be easily adjusted, and entanglement between fibers can be suppressed, and the ⁇ -cellulose content less than 60% by mass is used.
  • the thermal stability at the time of melting is high, the impact strength is not lowered, the coloration suppressing effect is good, and the effect of the present invention can be further improved.
  • 99% by mass or more it becomes difficult to defibrate the fibers to the nano level.
  • CNF in the present invention is obtained by fibrillating polysaccharides with a high-pressure water stream.
  • Degradation of polysaccharides by high-pressure water flow is carried out by colliding high-pressure water of about 50-400 MPa against polysaccharides in a water mixture of 0.5-10% by mass. This can be performed using, for example, the CNF manufacturing apparatus 1 shown in FIG.
  • the CNF manufacturing apparatus 1 includes a polysaccharide slurry supply path 3 that is a first liquid medium supply path arranged so as to be able to supply a polysaccharide slurry to one chamber 2 and a non-polysaccharide slurry that is, for example, water. And a second liquid medium supply path 4 that is circulated through the chamber 2.
  • an orifice injection unit 5 that performs orifice injection of the non-polysaccharide slurry in the second liquid medium supply path 4 in a direction intersecting the polysaccharide slurry supply direction from the polysaccharide slurry supply path 3.
  • the polysaccharide slurry supply path 3 is configured such that the polysaccharide slurry can be circulated through the one chamber 2.
  • the polysaccharide slurry supply path 3 and the second liquid medium supply path 4 have a mutual intersection 6 in one chamber 2.
  • the polysaccharide slurry supply path 3 is a polysaccharide slurry supply unit, and is configured by arranging a tank 7 and a pump 8 for storing the polysaccharide slurry in the circulation path 9, while the second liquid medium supply path 4 is a tank 10, a pump 11, a heat
  • the exchanger 12 and the plunger 13 are arranged in the liquid medium supply path 4 which is a circulation path.
  • the non-polysaccharide slurry is, for example, water, and is initially stored in the tank 10, and then the nano-sized polysaccharide stored in the tank 10 through the intersection 6 with the operation of the CNF manufacturing apparatus 1 is operated. Those in a state where they are contained at a concentration corresponding to the degree are also referred to generically.
  • the circulation path 9 of the polysaccharide slurry supply path 3 is arranged so as to penetrate the chamber 2, and the non-polysaccharide slurry can be injected through the orifice in a direction crossing the polysaccharide slurry supply path 3 so as to penetrate the circulation path 9.
  • the orifice injection port 14 of the orifice injection unit 5 connected to the plunger 13 of the second liquid medium supply path 4 opens inside the chamber 2.
  • a discharge port 15 of the chamber 2 is provided at a position facing the orifice injection port 14 of the chamber 2, and a circulation path of the second liquid medium supply path 4 is connected to the discharge port 15 of the chamber 2, so that the second liquid state A medium supply path 4 is configured.
  • the circulation path 9 of the polysaccharide slurry supply path 3 is formed using, for example, a vinyl hose, a rubber hose or the like, and the one-way valve 16 opened only in the direction of the chamber 2 on the entry side of the circulation path 9 into the chamber 2. Is attached. Furthermore, a one-way valve 17 that is opened only in the direction of discharge from the chamber 2 is attached to the exit side of the circulation path 9 from the chamber 2. In addition, an air suction valve 18 is attached to the circulation path 9 between the chamber 2 and the one-way valve 17, and the air suction valve 18 is opened only in the direction of sucking air from the outside into the circulation path 9.
  • CNF is manufactured as follows.
  • the non-polysaccharide slurry is circulated through the second liquid medium supply path 4 through the chamber 2.
  • the non-polysaccharide slurry in the tank 10 is circulated through the liquid medium supply path 4 by passing through the heat exchanger 12 and the plunger 13 using the pump 11.
  • the polysaccharide slurry is circulated through the polysaccharide slurry supply path 3 through the chamber 2.
  • the polysaccharide slurry in the tank 7 is circulated through the circulation path 9 formed using a vinyl hose, a rubber hose, or the like, using the pump 8.
  • the non-polysaccharide slurry circulating in the second liquid medium supply path 4 is orifice-injected with respect to the polysaccharide slurry circulating in the polysaccharide slurry supply path 3 and flowing in the chamber 2.
  • high-pressure water is supplied from the plunger 13 to the orifice injection port 14 connected to the plunger 13, and this is orifice-injected from the orifice injection port 14 toward the circulation path 9 at a high pressure of about 50 to 400 MPa.
  • the slurry is discharged toward the discharge port 15 of the chamber 2 while entraining the polysaccharide slurry circulating in the circulation path 9 and flows into the second liquid medium supply path 4.
  • the non-polysaccharide slurry is circulated again in the second liquid medium supply path 4.
  • the polysaccharide in the polysaccharide slurry supply path 3 and the polysaccharide in the non-polysaccharide slurry circulating in the second liquid medium supply path 4 are gradually defibrated.
  • CNF having a high degree of defibration according to the application can be obtained.
  • a dispersion liquid in which raw fibers are dispersed in a solvent is treated with a homogenizer equipped with a crushing type homovalve sheet described in JP 2012-36518 A.
  • a homogenization method As shown in FIG. 3, according to this homogenization treatment method, when the raw material fiber 101 pumped through the homogenizer at a high pressure passes through the small diameter orifice 102 which is a narrow gap, the wall surface of the small diameter orifice 102 (particularly the impact ring 103). And microfibrillation having a uniform fiber diameter is performed by being subjected to shear stress or cutting action.
  • the device shown in FIG. 4 is of a liquid circulation type, and has a tank (FIG. 4: 109), a plunger (FIG. 4: 110), two opposing nozzles (FIG. 4: 108a, 108b), and heat as necessary.
  • An exchanger (FIG. 4: 111) is provided, and fine particles dispersed in water are introduced into two nozzles and sprayed from the nozzles (FIG. 4: 108a, 108b) facing each other under high pressure to collide against each other in water.
  • this method only water is used in addition to natural cellulose fibers, and only the interaction between the fibers is cleaved. CNF can be obtained in a minimized state.
  • the CNF obtained as described above has a solid content concentration in an aqueous dispersion state of 20% or more, so that the familiarity with the dispersant is improved and it is difficult to produce an aggregate. Therefore, it can disperse
  • the solid content concentration is less than 20%, the compatibility with a dispersant having a hydrophobic property in a part of the structure is poor, and it is easy to generate aggregates between CNFs. It becomes a factor of deterioration of dispersibility.
  • a decrease in the resin temperature during kneading results in non-uniform shearing force during kneading, which is an undesirable obstacle to uniform dispersion during the kneading process.
  • the temperature rise of the kneading apparatus is hindered, a loss of heat energy is caused.
  • the method for producing a derivatized CNF of the present invention is characterized in that an organic acid vinyl is added to cellulose fiber, and for example, an organic acid vinyl such as vinyl acetate, vinyl benzoate and vinyl laurate is added to hydrous CNF.
  • an organic acid vinyl such as vinyl acetate, vinyl benzoate and vinyl laurate is added to hydrous CNF.
  • an organic acid vinyl such as vinyl acetate, vinyl benzoate and vinyl laurate is added to hydrous CNF.
  • CNF may be obtained by nano-miniaturization of a fibrous polysaccharide by physical treatment, and the ACC method can be applied as this physical treatment.
  • the CNF obtained by this ACC method is obtained by cleaving only the interaction between fibers and performing nano-miniaturization.
  • the chemical modification is not performed, the cellulose molecular structure is damaged and the degree of polymerization is reduced.
  • it was obtained only in a state suspended in water, and this was a factor that hindered utilization.
  • CNF obtained in a suspended state in water can be hydrophobized as it is, so that the industrial applicability of CNF obtained by the ACC method or the like is dramatically improved.
  • Pulp can be used as the fibrous polysaccharide, and as the pulp, woody plants such as hardwoods and conifers, chemical pulps made from herbaceous plants such as bamboo and bamboo, mechanical pulps and waste paper can be used.
  • Water-containing CNF is obtained, for example, by ACC treatment of bamboo BKP with the required number of passes, press dewatering, and has a water content of 90% or less, but is not limited to this, pulp obtained from woods and plants CNF prepared by mechanical processing such as a grinder or a homogenizer can also be used. Further, the water content may be 90% or less by a method such as centrifugation or dry concentration. However, if the water content exceeds 90%, the amount of water brought into the reaction system becomes excessive, and the production efficiency decreases, so that industrial production is difficult.
  • the water content is preferably 85% or less, more preferably 80% or less.
  • potassium carbonate such water-containing CNF is added to an organic solvent capable of being sufficiently dispersible, and then at least one of organic acid vinyls such as vinyl acetate and vinyl benzoate and vinyl laurate is added, The reaction is performed at 100 ° C. for 2 hours or longer, preferably at 80 ° C. for 2 hours. After the reaction is complete, the product is recovered and dried.
  • Potassium carbonate works as a reaction catalyst, but a buffering effect that keeps the inside of the reaction system alkaline is important. If there is a certain concentration or more, the effect can be sufficiently maintained.
  • the amount of potassium carbonate added is preferably about 5 to 30% in terms of the CNF ratio.
  • NMP N-methylpyrrolidone
  • DMAc dimethylacetamide
  • DMF dimethylformamide
  • DMSO dimethyl sulfoxide
  • ionic polar solvents and especially DMSO dissolves highly hydrophobic derivatized CNF in addition to high dispersibility of CNF. That is, laurylation of CNF proceeds in various hydrous nonionic polar solvents, but the reaction efficiency is highest when DMSO is used.
  • toluene can be used as a model of molten polypropylene (PP) or polyethylene (PE). By verifying whether CNF can be easily dispersed in toluene from a dry state, it can be predicted whether it can be in a good kneaded state with polypropylene (PP) or polyethylene (PE). .
  • the dried laurylated CNF can be redispersed in toluene. It can also swell and disperse in decahydronaphthalene (polyolefin resin solvent).
  • the number of primary hydroxyl groups protruding on the cellulose crystal surface is 0.5 per glucose unit, and it can be replaced by TEMPO oxidation treatment that selectively oxidizes only the primary hydroxyl group (C-6 position) on the CNF surface.
  • the degree is around 0.5.
  • the degree of substitution is 0.5 or more, there is a possibility that the molecular bond of cellulose is broken. From the analysis result of non-crystallinity in Non-Patent Document 4, reaction conditions such that the degree of substitution is 0.4 to 0.55 are preferable in order to achieve both sufficient crystallinity and hydrophobicity.
  • the content of derivatized CNF obtained by the above method is 1 to 10 Mass% is preferred. If it is less than 1% by mass, the effect of improving the mechanical properties such as the elastic modulus is not sufficiently exhibited, and if it exceeds 10% by mass, the impact strength and the like are greatly reduced and excessive costs are required.
  • thermoplastic resin of the present invention is the main component of the composite resin composition of the present invention, but the molded product obtained by molding the composition has a rigidity and resistance to resistance. Mechanical properties such as impact properties, molding processability, solvent resistance, heat resistance, and other characteristics need to be expressed well.
  • thermoplastic resin include vinyl chloride resin, styrene resin, (meth) acrylic resin, vinyl ether resin, etc.
  • the reinforcing effect by the derivatized CNF of the present invention is particularly remarkable. is there.
  • the polyolefin resin is preferably a polyolefin resin obtained by homopolymerization or copolymerization of one or more monomers selected from ⁇ -olefins having 2 to 6 carbon atoms in view of the above-described characteristics.
  • ⁇ -olefins having 2 to 6 carbon atoms in view of the above-described characteristics.
  • an ⁇ -olefin having 7 or more carbon atoms can also be used as a comonomer within a range that does not hinder the above-mentioned characteristic expression.
  • polyolefin resins include ethylene homopolymers, homopolymers of ⁇ -olefins having 2 to 6 carbon atoms such as propylene, butene-1, pentene-1, hexene-1, and 4-methylpentene-1, and ethylene.
  • copolymer examples include ⁇ -olefin copolymers having 3 to 6 carbon atoms, copolymers of two or more ⁇ -olefins having 2 to 6 carbon atoms, and ionomer resins.
  • the copolymer may be a random or block copolymer.
  • a mixture of various polyolefin resins such as polyethylene resin and polypropylene resin can be used.
  • polyolefin-based resins polypropylene-based resins mainly composed of propylene are excellent in rigidity, impact resistance, solvent resistance, and heat resistance, and therefore can be used particularly suitably for the composite resin composition of the present invention.
  • polypropylene resin examples include a block composed of a propylene homopolymer, a propylene-ethylene copolymer, a propylene-butene copolymer, and a copolymer of propylene and ethylene and / or the above ⁇ -olefin.
  • examples thereof include copolymers, random copolymers, and modified polypropylene having a polar functional group.
  • high-density polyethylene HDPE
  • low-density polyethylene LDPE
  • biopolyethylene examples thereof include polyethylene resin (PE) and polypropylene resin (PP).
  • component (B) a polymer alloy obtained by blending the above-described polyolefin resin with rubber as exemplified below may be used.
  • specific examples of such rubber include ethylene-propylene-nonconjugated diene copolymer rubber, ethylene-butene-1 copolymer rubber, ethylene-hexene copolymer rubber, ethylene-octene copolymer rubber, polybutadiene, and styrene-butadiene.
  • Block copolymer rubber styrene-butadiene copolymer rubber, partially hydrogenated styrene-butadiene-styrene block copolymer rubber, styrene-isoprene block copolymer rubber, partially hydrogenated styrene-isoprene block copolymer rubber, polyurethane rubber, styrene graft Ethylene-propylene-nonconjugated diene copolymer rubber, styrene-graft-ethylene-propylene copolymer rubber, styrene / acrylonitrile-graft-ethylene-propylene-nonconjugated diene copolymer rubber, styrene / acrylonitrile-graft- Styrene - propylene copolymer rubber and the like.
  • the rubber content in the polymer alloy is preferably 50% by mass or less from the viewpoint of adding new characteristics to the characteristics of the
  • Examples of the method for producing the polyolefin resin composition of the present invention include a method of melt-kneading each component by a conventionally known method. For example, after each component is dispersed and mixed by a high speed mixer represented by a tumble mixer, a Henschel mixer, a ribbon blender, or a super mixer, a method of melt kneading with an extruder, a Banbury mixer, a roll or the like is appropriately selected.
  • a high speed mixer represented by a tumble mixer, a Henschel mixer, a ribbon blender, or a super mixer
  • CNF which is a biomass material as a resin composition
  • CNF can suppress the cohesiveness of cellulose by using CNF having a specific average fiber diameter and average fiber length, and can suppress a decrease in impact strength. Furthermore, since CNF can improve rigidity while having a lower specific gravity than inorganic fibers such as glass fibers, it can be a resin composition having high rigidity and low specific gravity.
  • the CNF in the present invention has an average thickness of 10 to 200 nm, and is obtained by fibrillating polysaccharides with a high-pressure water stream.
  • the average thickness was measured by a field emission scanning electron microscope JSM-7001FTTLS manufactured by JEOL Ltd.
  • JSM-7001FTTLS manufactured by JEOL Ltd.
  • By defibration to an average thickness of 10 to 200 nm it is possible to obtain a resin composition having fluidity, little impact strength reduction, low specific gravity, high rigidity, and excellent molded appearance.
  • the average thickness is less than 10 nm, the dehydrating property is deteriorated, so that it is difficult to increase the solid concentration, which is not preferable.
  • the average thickness exceeds 200 nm, fibers having a fiber width of several tens of ⁇ m where defibration has not progressed are included, and fluidity is remarkably lowered and dispersibility is deteriorated.
  • the molding method using the polyolefin resin composition of the present invention is not particularly limited, and molding methods such as injection molding, injection compression molding, blow molding, vacuum molding, extrusion molding, and hollow molding can be applied. Since the molded article using the polyolefin resin composition of the present invention has the above-mentioned properties, for example, OA equipment, information / communication equipment, fiber material, film material, coating film, paint component, automobile component or building material field Etc. can be suitably used.
  • the impact strength is hardly lowered, and the rigidity can be increased to a low specific gravity (MPa), and the surface roughness can be increased.
  • MPa specific gravity
  • the polyolefin resin composition of the present invention generally satisfies the following performance in terms of the tensile elastic modulus (MPa) and tensile elongation (%) of the molded product obtained, and has a molded appearance. It has the feature of being excellent.
  • Example 5 Laurylated CNF was produced in the same manner as in Example 4. However, the amount of potassium carbonate was 20% relative to CNF, and the amount of water in the reaction system or the reaction temperature was changed. In addition to CNF (rCNF) similar to that in Example 4, CNF (fCNF) having a smaller fiber diameter was also used. The reaction time was 2 hours.
  • FIG. 11 shows the rate of weight increase in a DMSO solution having a water content of 6 to 10 vol% at a reaction temperature of 80 ° C.
  • fCNF is more reactive than rCNF, and the specific surface area is expected to affect the reactivity.
  • the rate of weight increase gradually decreased as the amount of water in the reaction system increased.
  • DS0.25 having the smallest WPG
  • the addition of water produced aggregates, so that the hydrophobization proceeded.
  • the hydrophobicity of CNF proceeds sufficiently.
  • the weight increase rate when the reaction temperature is set from 70 ° C. to 100 ° C. is shown in FIG. At 80 ° C. and 100 ° C., there is no significant difference in the weight increase rate, and the reactivity is equivalent. On the other hand, the weight increase rate decreased by about 35% at 70 ° C. compared to the case of 80 ° C. or higher.
  • the reaction temperature should just be 80 degreeC or more.
  • FIG. 12A A state in which laurylated CNF having an estimated substitution degree of about 0.5 is dispersed in toluene and decalin at a concentration of 1% is shown in FIG. 12A, and the results of SEM observation of each dispersion state are shown in FIGS. 12B and 12C. It was well dispersed in toluene. In addition, even the decalin dispersion is cloudy but is sufficiently well dispersed by visual observation. When the dispersion state of laurylated CNF in the dispersion is observed by SEM, although fiber aggregation tendency is somewhat observed in decalin, the fibers can be observed independently with either solvent, so that the degree of substitution is about 0.5.
  • CNF can be dispersed in toluene and decalin. Both toluene and decalin are known to dissolve polyolefin resins, and particularly hot decalin dissolves polypropylene, so that laurylated CNF can be uniformly dispersed in polypropylene.
  • Example 6 Laurylated CNF was synthesized in the same manner as in Example 4. However, fCNF was used, the water content in the system was 6% or 10%, and the reaction temperature was 80 ° C. Moreover, it reacted by changing the amount of potassium carbonate. The reaction time was 2 hours.
  • the weight increase rate is the maximum when the potassium carbonate addition ratio is 20% in terms of the CNF ratio, and the reactivity gradually decreases in the potassium carbonate concentration region beyond that.
  • the rate of increase in weight also decreases rapidly depending on the decrease in the concentration of potassium carbonate (FIG. 12).
  • Example 7 In the same manner as in Example 4, laurylated CNF was synthesized using DMSO, DMF, DMAc, and NMP as solvents. Also, laurylated CNF was synthesized using fCNF produced from kraft pulp derived from hardwood (LB), conifer (NB), and bamboo (BB). Potassium carbonate was 20% relative to CNF, the reaction temperature was 80 ° C., the water content was 6%, and the reaction time was 2 hours.
  • LB hardwood
  • NB conifer
  • BB bamboo
  • Table 2 summarizes the rate of increase in specific weight, assuming that the rate of increase in weight when LB-CNF was laurylated in DMSO was 100%.
  • aprotic polar solvents were used, the reactivity of DMF, DMAc, and NMP was about one-third that of DMSO.
  • Any solvent including DMSO is a nonionic polar solvent used for dissolving cellulose.
  • all solvents are amine solvents and have a carbonyl oxygen and nitrogen atom resonance structure, both of which are more hydrophobic than DMSO. There are differences such as high. Differences in reactivity can be attributed to such differences in properties.
  • Example 8 In the same manner as in Example 1, acetylated CNF was synthesized. However, the amount of water in the reaction system was 5%.
  • Example 9 In the same manner as in Example 4, laurylated CNF was synthesized. However, the amount of water in the reaction system was 5%.
  • Example 10 In the same manner as in Example 9, CNF derivatization with vinyl laurate was performed for 1.5 hours, and then vinyl acetate was continuously added and reacted for an additional 1.5 hours to obtain lauryl-acetylated CNF. .
  • Example 11 Various derivatized CNFs (acetylated CNF, laurylated CNF, lauryl-acetylated CNF) produced in Examples 8 to 10 and non-derivatized CNF were converted into dry powders after washing by Soxhlet extraction, and infrared absorption spectra were obtained. It was measured.
  • Lauryl-acetylated CNF shows almost the same spectrum as laurylated CNF.
  • an acetyl group is also given, and it is considered that both lauryl group and acetyl group are introduced into CNF.
  • CrI specific crystallinity
  • FIG. 14 shows X-ray diffraction spectra of various derivatized CNFs and CNFs before and after hydrolysis.
  • the spectrum of derivatized CNF is greatly changed from that of cellulose type I crystals, and it is difficult to obtain an accurate specific crystallinity (before hydrolysis).
  • X-ray diffraction analysis of derivatized CNF after hydrolysis was performed, all samples showed almost similar spectra, and all retained cellulose I-type crystals (after hydrolysis). Even if CNF is hydrolyzed, the degree of crystallinity does not change, and hydrolyzing treatment in a 0.5% NaOH methanol solution at 50 ° C. for 2 hours does not affect the cellulose crystal form.
  • Example 13 To 75 mg of CNF, 1.2 times mole of vinyl laurate was added as AGU and reacted at 70 ° C. for 1.5 to 6 hours.
  • FIG. 15 shows the change over time in the degree of substitution estimated from the change in weight at that time. The substitution reaction was almost completed from 1 hour to 1.5 hours after the start of the reaction, and then the degree of substitution gradually improved.
  • Example 14 The micronized nanocellulose retains a high specific surface area, and at the same time has extremely high hydrophilicity due to the influence of hydroxyl groups exposed on the surface, and thus is easily aggregated by hydrogen bonding. Therefore, the high hydrophilicity causes aggregation in a highly hydrophobic resin such as polyolefin, and the strength property cannot be sufficiently exhibited. Therefore, in order to solve the problem, the surface of the nanocellulose fiber is esterified to impart hydrophobicity and improve dispersibility in the polyolefin, thereby improving the reinforcing function for the polyolefin.
  • CNF was created by the underwater facing collision method.
  • nanofibers (CNFfine) with further miniaturization were also prepared.
  • CNF and CNFfine were laurylated according to [Example 1] to [Example 10] (LauCNF and LauCNFfine), and the degree of substitution of hydroxyl groups by laurylation was 0.45 ( ⁇ 0.01).
  • Water-containing CNF or acetone-derivatized CNF was premixed with medium density polyethylene (Lupolen 3621 MRM, PE) so that the cellulose part was 5% or 10%.
  • the premixing of the hydrous CNF here may be carried out by hand, or a fluid mixer, a high-speed stirring mixer, or the like may be used.
  • the acetone may be suspended together with PE and stirred well, and then the acetone may be distilled off, or may be premixed using a fluid mixer as in the case of the water-containing CNF. Good.
  • PE and derivatized CNF may be mixed uniformly, but once the derivatized CNF is dried, a strong aggregate is formed and redispersion becomes extremely difficult. As a result, derivatized CNF is agglomerated in a large amount even by twin-screw extrusion kneading, and the strength is adversely affected. Therefore, drying of the derivatized CNF must be avoided.
  • the mixture with the premixed PE had a screw system used for a twin-screw extruder (Toyo Seiki, Labo Plast Mill) having a diameter of ⁇ 25 mm and an effective length (screw length L to diameter D ratio) of 30.
  • a dumbbell test piece 1BA and a strip-shaped test piece were prepared using a small injection molding machine (Nissei Plastic Industries, NPX7-1F). The test piece was allowed to stand for 4 days or more at a temperature of 23 ° C. and a humidity of 50%, and then subjected to analysis of mechanical properties.
  • FIG. 15 shows the tensile strength of the composite resin of CNF or derivatized CNF and PE
  • FIG. 16 shows the bending strength.
  • Statistical comparison of composite resin (PE + 10% CNF) with 10% CNF blended with PE and composite resin (PE + 10% CNFfine) with 10% CNFfine by t-test results in maximum tensile stress, flexural modulus, maximum bending PE + 10% CNF was significantly higher in stress (p ⁇ 0.05), but no significant difference was observed in tensile modulus, tensile and bending maximum strain.
  • PE + 5% CNF a composite resin (PE + 5% CNF) containing 5% CNF in PE and PE + 10% CNF
  • PE + 10% CNF has a significantly higher strength in terms of maximum tensile stress, flexural modulus, and maximum bending stress.
  • PE + 5% CNF showed a significantly higher value only with tensile strain.
  • PE + 5% LauCNF is more than PE + 10% CNF composite resin.
  • the tensile modulus, maximum tensile stress, and maximum bending strain showed significantly high strength characteristics, and PE + 10% CNF exhibited significantly high elongation at the maximum tensile strain, bending modulus, and maximum bending modulus.
  • PE + 5% LauCNF showed significantly better properties in terms of tensile modulus, maximum tensile stress, flexural modulus, and maximum bending stress.
  • the reinforcement effect on PE by laurylating CNF is equal to or greater than the flexural modulus, tensile modulus, maximum tension and The bending stress is twice or more.
  • the maximum tensile strain is reduced by laurylation, giving strong and hard properties.
  • the strength of CNF as a raw material also affects the strength of LauCNF.
  • a composite resin sheet having a thickness of about 150 ⁇ m was prepared. Aggregates in the sheet were observed with an optical microscope (DSX500, OLYMPUS). Further, the light transmission spectrum was measured with a visible-infrared spectrophotometer (integrated sphere, UV-2600, Shimadzu Corporation).
  • the blending ratio of laurylated CNF is preferably less than 5%. Further, a blending ratio of 3% or less is desirable from the viewpoint of cost effectiveness.
  • the tensile and bending properties are shown for the reinforcing effect on PE (tensile: solid line, bending: broken line).
  • tensile modulus a reinforcing effect was observed when 0.5% of laurylated CNF was blended.
  • a reinforcing effect was observed in the flexural modulus from the time of blending 1.5%.
  • the tensile modulus did not fluctuate (decrease) greatly even when the tensile modulus took the maximum value and the blending rate was 10%. .
  • the laurylated CNF 7.5% blended polypropylene composite resin showed a value of 155% in terms of tensile modulus and 135% in terms of maximum tensile stress relative to polyethylene.
  • the maximum point strain was 75%.
  • the reinforcing effect of the flexural modulus increased depending on the blending concentration until 10% was blended.
  • the flexural modulus at this blending concentration was 155% of polyethylene and the maximum bending stress was 130%.

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Abstract

L'invention vise à fournir : un CNF dérivé qui permet d'annuler l'hydrophilie élevée du CNF hydraté et de lui conférer une hydrophobicité, ce qui permet d'améliorer la compatibilité avec les résines hydrophobes telles que les polyoléfines, et de permettre la redispersion dans un solvant hydrophobe, même lorsqu'il est complètement séché, le CNF dérivé réduisant les effets de l'humidité pendant un malaxage avec des matières plastiques, réduisant les coûts de transport, et analogue ; un procédé de production de celui-ci ; et une composition de résine ayant d'exceptionnelles caractéristiques environnementales, une faible réduction de la résistance aux chocs, une rigidité élevée même avec une faible gravité spécifique, et un aspect moulé exceptionnel grâce à l'utilisation d'une matière de biomasse. La présente invention concerne une composition de résine ayant d'exceptionnelles caractéristiques environnementales, une faible réduction de la résistance aux chocs, une rigidité élevée même avec une faible gravité spécifique, et un aspect moulé exceptionnel grâce à l'utilisation d'une matière de biomasse comprenant : de 0,5 à 10 % en masse de (A) un CNF dérivé ayant une épaisseur moyenne de 10 à 200 nm, obtenu par un procédé de production permettant la dispersion de CNF hydraté avec du carbonate de potassium dans un solvant polaire aprotique tel que le DMSO, l'ajout d'au moins un acide organique vinylique, par exemple un parmi l'acétate de vinyle, le benzoate de vinyle et le laurate de vinyle, et ensuite l'ajout d'un acide organique vinylique, la mise en réaction pendant deux heures ou plus à 70 à 80 °C, de préférence pendant deux heures à 80 °C, et la récupération et le séchage du produit de réaction après la fin de la réaction ; et 99,5 à 90 % en masse de (B) une résine de polyoléfine.　
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