WO2012111408A1 - Agent de renforcement de résine fibreux et son procédé de production, et composition de résine l'utilisant - Google Patents

Agent de renforcement de résine fibreux et son procédé de production, et composition de résine l'utilisant Download PDF

Info

Publication number
WO2012111408A1
WO2012111408A1 PCT/JP2012/051809 JP2012051809W WO2012111408A1 WO 2012111408 A1 WO2012111408 A1 WO 2012111408A1 JP 2012051809 W JP2012051809 W JP 2012051809W WO 2012111408 A1 WO2012111408 A1 WO 2012111408A1
Authority
WO
WIPO (PCT)
Prior art keywords
reinforcing agent
resin
fibrous
cellulose fiber
resin composition
Prior art date
Application number
PCT/JP2012/051809
Other languages
English (en)
Japanese (ja)
Inventor
林　寿人
智春 多喜田
小澤　雅昭
Original Assignee
日産化学工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日産化学工業株式会社 filed Critical 日産化学工業株式会社
Priority to JP2012557869A priority Critical patent/JP5975222B2/ja
Publication of WO2012111408A1 publication Critical patent/WO2012111408A1/fr

Links

Images

Classifications

    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/045—Reinforcing macromolecular compounds with loose or coherent fibrous material with vegetable or animal fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • 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
    • C08L1/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils

Definitions

  • the present invention relates to a composition containing cellulose and an additive and a method for producing the same, and in particular, a cellulose fiber-containing fibrous resin reinforcing agent in which cellulose fibers are uniformly dispersed in the additive,
  • the present invention relates to a resin composition and a molded article in which the uniform dispersibility and impact resistance of cellulose fibers in a resin are improved by addition to a thermoplastic resin.
  • cellulose is abundant in existing quantities, is a resource that is biodegradable and has a low environmental impact, has excellent properties as a material, such as high crystallinity, high tensile strength, and low coefficient of thermal expansion. It is a material expected from the future.
  • the crystal elastic modulus of cellulose in the molecular chain axis direction is 138 GPa, which is comparable to the elastic modulus of aramid fiber and liquid crystal polyester.
  • Cellulose has a linear thermal expansion coefficient on the order of 10 ⁇ 7 K ⁇ 1 and has a very low coefficient of thermal expansion that surpasses that of glass and diamond.
  • One method for effectively utilizing cellulose is to use it as a reinforcing material for improving the strength of the resin molded body.
  • inorganic fibers such as carbon fibers and glass fibers are generally used as reinforcing materials in order to increase the mechanical strength of the resin molded body.
  • composite resin containing inorganic fibers will wear the inside of the molding machine such as molds, etc., and since residues derived from inorganic fibers are generated during incineration, it must be disposed of by landfill processing, etc. Is a problem.
  • polylactic acid which is a biodegradable resin derived from plants, has the disadvantage that it is inferior in impact resistance although it has a higher elastic modulus than conventional polypropylene resin, polystyrene resin, and polyethylene terephthalate resin. It is necessary to use a reinforcing material together to compensate. Since polylactic acid itself is a plant-derived material, it is preferable to use plant natural fibers in the reinforcing material. From this viewpoint, several patents relating to composite resins of cellulose and polylactic acid have been proposed. .
  • thermoplastic resin such as polylactic acid
  • the cellulose refined into nano-sizes has its own flexibility and high aspect ratio, and hydrogen bonding between fibers due to hydroxyl groups present on the surface
  • a solid agglomerate is formed when it goes through a dry state alone.
  • a sheet-shaped composite resin is formed by impregnating a polymerizable component or a resin solution into a material composed of microfibrillated plant fibers formed in a sheet shape. Attempts to fabricate the sheet, and after kneading the sheet-shaped composite resin, melting and kneading, and then fabricating a molded body by press molding or the like have been studied (Patent Document 1).
  • Patent Document 2 Also reported is a method for producing a composite resin of resin and fine cellulose fiber by mixing polypropylene resin and hydrophobized cellulosic fiber in an aqueous medium under heating with stirring and melt-kneading with dehydration.
  • Patent Document 3 a method has been reported in which a polymerization component is graft-polymerized into fine cellulose fibers in an aqueous system to obtain cellulose fibers whose surfaces are covered with a thermoplastic resin. Since the surface of the refined cellulose fiber obtained by this technique is coated with a resin, the formation of aggregates due to hydrogen bonding between fibers can be suppressed even through a dry state.
  • the present invention has been made in view of the above circumstances, and suppresses the occurrence of agglomerates, which are problematic when using cellulose as a reinforcing material for thermoplastic resins, and is uniformly dispersed in the blended resin. It aims at providing the reinforcing agent which can fully exhibit the performance as a reinforcing material.
  • the present invention is a thermoplastic resin as a reinforcing agent for polylactic acid, and can exhibit high impact resistance while maintaining a high elastic modulus of the resin itself. However, it aims at providing the resin reinforcement which can be applied.
  • an object of the present invention is to provide a method for producing a resin reinforcing agent that can produce the above-mentioned resin reinforcing agent by a simple method without requiring a special apparatus or a complicated production process. And this invention aims at providing the molded object formed from the resin composition which contained the above-mentioned resin reinforcement agent and aimed at the improvement of mechanical strength, and this resin composition.
  • the present inventor prepared a suspension by adding a hydrophilic additive to a finely divided aqueous dispersion of cellulose fiber, and then removed the water. By doing so, it is possible to obtain a fibrous resin reinforcing agent in which the refined cellulose fibers are uniformly dispersed in the additive, and by adding the reinforcing agent to the thermoplastic resin, the impact resistance is excellent.
  • the present inventors have found that a resin composition and a molded body can be easily obtained, and have reached the present invention.
  • the present invention is a fibrous resin reinforcing agent for reinforcing a matrix resin, which is hydrophilic with the refined cellulose fiber (A) and has an HLB value (hydrophilic / lipophilic balance) of 10 to 20. It is related with the fibrous resin reinforcing agent characterized by including the additive (B) and the refined cellulose fiber (A) being dispersed in the additive (B).
  • the HLB value of 10 to 20 means a range including 10 as a lower limit and 20 as an upper limit.
  • not only the HLB value but also a notation indicating a numerical range using ⁇ is interpreted in the same manner for the lower limit value and the upper limit value.
  • the refined cellulose fiber (A) has a particle diameter (median diameter) of 0.01 ⁇ m to 40 ⁇ m at a cumulative volume of 50% measured using a laser diffraction / scattering particle size distribution meter with water as a dispersion medium. It is preferable.
  • the refined cellulose fiber (A) is preferably prepared by any wet pulverization method selected from the group consisting of a high-pressure homogenizer, a grinder (stone mill) type mill, and a medium stirring mill. Furthermore, it is preferable that the refined cellulose fiber (A) is prepared from plant-derived cellulose or bacterial cellulose.
  • the additive (B) is contained in an amount of 70 to 99.9 parts by mass with respect to a total of 100 parts by mass of the refined cellulose fiber (A) and the additive (B). It is preferable. Further, it is more preferable that the additive (B) has an HLB value of 12 to 16.
  • the present invention includes a step of preparing a suspension by dissolving, emulsifying or dispersing the additive (B) in an aqueous dispersion of finely divided cellulose fibers (A), and removing water from the suspension.
  • the process relates to a method for producing the fibrous resin reinforcing agent.
  • the present invention relates to a resin composition containing the fibrous resin reinforcing agent.
  • the resin composition preferably further contains a thermoplastic resin, more preferably polylactic acid.
  • this invention relates also to the molded object formed from the said resin composition.
  • the fibrous resin reinforcing agent of the present invention is easy to disperse in a matrix resin such as polylactic acid, that is, use of an organic solvent that has been essential in the past when dispersing finely divided cellulose fibers into a matrix resin, And there is no need to go through complicated processes.
  • the fibrous reinforcing agent of the present invention can form a composition in which cellulose fibers are uniformly dispersed in a matrix resin simply by melt-kneading the reinforcing agent and the matrix resin.
  • the above-mentioned fibrous resin reinforcing agent can be manufactured simply and efficiently. Moreover, it can manufacture on an industrial scale, without using a special apparatus. Furthermore, as described above, the fibrous reinforcing agent of the present invention can be produced without using an organic solvent, and can solve problems such as disposal associated with inorganic fibers. It will be improved.
  • miniaturized cellulose fiber is disperse
  • the content of the cellulose fiber is low, the molding processability is remarkably improved, and the mechanical strength of the resin composition and the molded body can be greatly improved.
  • FIG. 1 is a polarized light micrograph observing the dispersion state of finely divided cellulose fibers in the fibrous resin reinforcing agent produced in Example 1.
  • FIG. 2 is a polarized light micrograph observing the dispersion state of the refined cellulose fibers in the fibrous resin reinforcing agent produced in Example 2.
  • FIG. 3 is a polarizing micrograph observing the dispersion state of the finely divided cellulose fibers in the fibrous resin reinforcing agent produced in Example 3.
  • FIG. 4 is a polarization micrograph observing the dispersion state of the finely divided cellulose fibers in the fibrous resin reinforcing agent produced in Example 4.
  • FIG. 1 is a polarized light micrograph observing the dispersion state of finely divided cellulose fibers in the fibrous resin reinforcing agent produced in Example 1.
  • FIG. 2 is a polarized light micrograph observing the dispersion state of the refined cellulose fibers in the fibrous resin reinforcing agent produced in Example 2.
  • FIG. 5 is a polarizing microscope photograph observing the dispersion state of the finely divided cellulose fibers in the fibrous resin reinforcing agent produced in Comparative Example 1.
  • FIG. 6 is a polarization micrograph observing the dispersion state of the refined cellulose fibers in the resin composition containing the fibrous resin reinforcing agent produced in Example 1.
  • FIG. 7 is a polarized light micrograph observing the dispersion state of the refined cellulose fibers in the resin composition containing the fibrous resin reinforcing agent produced in Example 2.
  • FIG. 8 is a polarization micrograph observing the dispersion state of the refined cellulose fibers in the resin composition containing the fibrous resin reinforcing agent produced in Example 3.
  • FIG. 9 is a polarization micrograph observing the dispersion state of the refined cellulose fibers in the resin composition containing the fibrous resin reinforcing agent produced in Example 4.
  • FIG. 10 is a polarizing microscope photograph observing the dispersion state of the refined cellulose fibers in the resin composition containing the fibrous resin reinforcing agent produced in Comparative Example 1.
  • FIG. 11 is a polarizing microscope photograph observing the dispersion state of commercially available cellulose powder in the resin composition produced in Comparative Example 2.
  • FIG. 12 is a polarization micrograph observing the dispersion state of the coarsely pulverized pulp in the resin composition containing the fibrous resin reinforcing agent produced in Comparative Example 3.
  • FIG. 13 is a polarization micrograph observing the dispersion state of coarsely pulverized bacterial cellulose in the resin composition containing the fibrous resin reinforcing agent produced in Comparative Example 4.
  • the fibrous resin reinforcing agent of the present invention is obtained by removing moisture from a suspension containing a finely divided aqueous dispersion of cellulose fibers and a hydrophilic additive having an HLB value of 10 to 20.
  • a hydrophilic additive having an HLB value of 10 to 20.
  • the reinforcing agent can be easily dispersed in a matrix resin such as polylactic acid by a conventional resin molding technique, and the cellulose fiber is uniformly dispersed in the obtained resin composition.
  • characteristics hereinafter, the present invention will be described in detail.
  • the fibrous resin reinforcing agent of the present invention is prepared by dissolving, emulsifying or dispersing the additive (B) in an aqueous dispersion of finely divided cellulose fibers (A) to prepare a suspension, and water from the suspension. Is obtained.
  • ⁇ Refined cellulose fiber (A)> As the cellulose used as the raw material for the aqueous dispersion of cellulose fiber used in the present invention, raw materials used in the production of conventional cellulose fibers can be widely used. For example, plant-derived cellulose such as wood, bamboo, hemp, jute, kenaf, agricultural products and food residues, cellulose produced by microorganisms such as bacterial cellulose and squirt can be used as raw materials. These celluloses may be used alone or in combination of two or more. Of these, it is preferable to use plant-derived cellulose or bacterial cellulose as a raw material.
  • these cellulose raw materials are pulverized and refined cellulose fibers are used.
  • the method for pulverizing cellulose is not limited, but in order to make the fiber diameter suitable for the purpose of the present invention, a strong shearing force such as a high-pressure homogenizer, a grinder (millstone) type mill, or a medium stirring mill such as a bead mill is obtained. Is preferred. Further, among these, it is preferable to use a high-pressure homogenizer, and for example, a wet pulverization method as disclosed in, for example, JP-A-2005-270891, that is, a dispersion in which cellulose is dispersed is discharged from a pair of nozzles.
  • Cellulose is pulverized by being injected and collided at a high pressure, and can be implemented by using, for example, a starburst system (high pressure pulverizer manufactured by Sugino Machine Co., Ltd.).
  • the degree of refinement and homogenization depends on the pressure fed to the ultra-high pressure chamber of the high-pressure homogenizer, the number of passes through the ultra-high pressure chamber (number of treatments), and water. It will depend on the cellulose concentration in the dispersion.
  • the pumping pressure (treatment pressure) is usually 50 MPa to 250 MPa, preferably 150 MPa to 245 MPa. When the pumping pressure is less than 50 MPa, the cellulose fiber is not sufficiently refined, and the effect expected by the refinement cannot be obtained.
  • the cellulose concentration in the aqueous dispersion during the micronization treatment is 0.1% by mass to 30% by mass, preferably 1% by mass to 10% by mass.
  • the productivity is remarkably low, and when it is higher than 30% by mass, the pulverization efficiency is low, and the desired finely divided cellulose fiber cannot be obtained.
  • the number of times of refinement depends on the cellulose concentration in the aqueous dispersion, but when the cellulose concentration is 0.1% by mass to 1% by mass, the number of treatments can be sufficiently refined in about 10 to 50 passes. However, about 1 to 10% by mass requires about 50 to 200 passes. Moreover, in the case of a high concentration exceeding 30% by mass, the number of treatments is several hundred times or more, which is unrealistic from an industrial viewpoint.
  • a laser diffraction / scattering particle size distribution analyzer can be used for evaluation of the refinement of the refined cellulose fiber used in the present invention in an aqueous dispersion.
  • the cellulose fiber has a particle diameter (median diameter) of 0.01 ⁇ m to 40 ⁇ m, particularly preferably 0.05 ⁇ m to 10 ⁇ m at a total volume of 50%. Is preferably used.
  • the addition effect cannot be obtained because the cellulose fiber is too fine, that is, the resin composition containing the fibrous resin reinforcing agent obtained next, or the mechanical property of the molded body thereof Does not lead to improvement in strength. Further, if the particle size is larger than 40 ⁇ m, the cellulose fiber is not sufficiently refined, the mechanical strength of the resin composition containing the fiber or the molded product thereof, and the mechanical strength when the unground cellulose raw material is contained. There is no difference in strength, and the expected effect cannot be obtained.
  • the finely divided cellulose fiber used in the present invention is not particularly limited with respect to the fiber diameter, but is 0.001 ⁇ m to 10 ⁇ m, preferably 0.01 ⁇ m to 1 ⁇ m.
  • the aspect ratio (L / D) is not particularly limited, but is 10 to 100,000, and preferably 100 to 10,000.
  • the additive (B) in the present invention is hydrophilic, has an HLB (Hydrophile-Lipophile-Balance) value of 10 to 20, and can uniformly disperse the cellulose fiber (A) described above.
  • Any known material can be used without particular limitation. Examples thereof include monoglyceride, acetic acid monoglyceride, lactic acid monoglyceride, citric acid monoglyceride, succinic acid monoglyceride, diacetyltartaric acid monoglyceride, polyglycerin ester, sugar ester, sorbitan ester, stearoyl calcium lactate and lecithin.
  • the mechanical strength of the blended resin composition or molded body thereof can be improved as compared with the case where the refined cellulose fiber is used alone.
  • the cellulose fiber and the additive are once constituted as a fibrous resin reinforcing agent and blended with the thermoplastic resin, so that they are blended independently (without the form of the fibrous resin reinforcing agent).
  • the aggregate formation of the refined cellulose fibers in the obtained resin composition can be suppressed, and the cellulose fibers can be dispersed in the resin composition while maintaining the refined state. This is advantageous.
  • an HLB value represented by a numerical value from 0 to 20 is used depending on the balance between the hydrophilic group and the lipophilic group.
  • the HLB value is smaller as the lipophilic substance is higher, and as the hydrophilicity is higher, it means that the solubility or dispersibility in water changes depending on the HLB value.
  • the Griffin method, the Atlas method, the Davis method, the Kawakami method, and the like are known, and can be calculated by the following Griffin equation, for example.
  • HLB 20 ⁇ (chemical formula amount of hydrophilic group / total molecular weight)
  • the additive used in the present invention has an HLB value of 10 to 20, more preferably an HLB value of 12 to 16.
  • HLB value is less than 10
  • the affinity between the cellulose fiber and the additive in water is low, and the cellulose fiber forms an agglomerate at the stage of producing the fibrous resin reinforcing agent, and then the resulting fibrous resin reinforcing agent is obtained.
  • the improvement of the mechanical strength of the resin composition containing this, or its molded object is not obtained.
  • the amount of additive (B) to be added to the fibrous resin reinforcing agent is, for example, 50 parts by mass to 99.99 parts per 100 parts by mass of the total amount of refined cellulose fiber (A) and additive (B). 9 parts by mass, more preferably 70 parts by mass to 99.0 parts by mass.
  • the amount of the additive is less than 50 parts by mass, the cellulose fiber is uniformly dispersed in the resin composition containing the fibrous resin reinforcing agent composed of the refined cellulose fiber and the additive, or in the molded body thereof. Therefore, the mechanical strength cannot be improved.
  • Examples of commercially available additives that can be used in the fibrous resin reinforcing agent of the present invention include, but are not limited to: Poem (registered trademark) J-0021, L-021, J-0081HV, J-0381V, C-781, Riquemar (registered trademark) C-250, B-205, O-852 (above, Riken Vitamin Co., Ltd.); Sunsoft (registered trademark) Q-12S, M-12J, Q-14S, Q-17S, Q-18S, Q-182S, A-121E, A -141E, A-171E, A-181E (above, manufactured by Taiyo Chemical Co., Ltd.); S-1170, S-1570, S-1670, P-1570, P-1670, M-1695, O-1570 L-1695, LWA-1570, L-10D, L-7D, M-10D, M-7D, P-8D, S-28D, S-24D, SWA-20D, SWA-15D, SWA-10D, O -15D
  • the fibrous resin reinforcing agent is a suspension prepared by dissolving, emulsifying or dispersing the additive (B) in the aqueous dispersion of the finely-divided cellulose fiber (A). By removing moisture from the fiber, a fibrous resin reinforcing agent in which the cellulose fiber (A) is uniformly dispersed in the additive (B) can be produced.
  • the refined cellulose fiber (A) and the additive (B) may be in a state where at least each of them is simply coexisted in water. It is preferable that the cellulose fiber (A) and the additive (B) are uniformly emulsified or dispersed in water to form a suspension.
  • the method for emulsifying or dispersing in water is not particularly limited.
  • the cellulose raw material and the additive (B) are allowed to coexist.
  • the suspension may be prepared by simultaneously carrying out the refinement of the cellulose raw material and the emulsification or dispersion treatment of the additive (B).
  • a general-purpose stirrer for example, a propeller / paddle blade, a homomixer, a disperser, etc., in a state where an aqueous dispersion of finely divided cellulose fiber (A) and an additive (B) coexist.
  • a suspension may be prepared using a mixer, an ultrasonic disperser, or the like.
  • the concentration of the finely divided cellulose fiber (A) and the additive (B) in the aqueous suspension is 0.5% to 99% by mass, preferably 5% to 60%, as the total amount of both. % By mass.
  • concentration of the total amount of the cellulose fiber (A) and the additive (B) in the suspension is less than 0.5% by mass, the water removal efficiency is low, which is impractical when actual production is assumed. is there.
  • a conventional concentration and drying method for example, heating concentration, concentration under reduced pressure, hot air drying, vacuum drying, spray drying, freeze vacuum drying. These processes may be used in combination as appropriate.
  • the temperature at the time of removing moisture is 100 ° C. to 200 ° C. at normal pressure, preferably 110 ° C. to 150 ° C. Regardless of the reduced pressure or the normal pressure, yellowing of the cellulose becomes remarkable under the temperature condition of 200 ° C. or higher, which is not preferable because there is a possibility that the appearance of the resin composition or the molded body obtained next is impaired.
  • the moisture content contained in the fibrous resin reinforcing agent of the present invention is 5% by mass or less, preferably 3% by mass or less.
  • the moisture content can be measured with a 150 ° C. mass loss in a thermal analyzer (TG-DTA) measurement or with Karl Fischer.
  • TG-DTA thermal analyzer
  • Karl Fischer Karl Fischer
  • the fibrous resin reinforcing agent of the present invention may contain other additives as necessary.
  • inorganic fillers eg talc, mica, silica, kaolin, clay, wollastonite, glass beads, glass flakes, potassium titanate, calcium carbonate, calcium phosphate, magnesium sulfate, titanium oxide
  • flame retardants eg bromine
  • halogen flame retardants such as chlorine compounds, melamine flame retardants, antimony flame retardants such as antimony trioxide and antimony pentoxide
  • inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide and silicone compounds, red phosphorus, Phosphoric esters, phosphorous flame retardants such as ammonium polyphosphate, phosphazene, etc.
  • fluororesins such as PTFE
  • heat stabilizers light stabilizers, UV absorbers, antioxidants, impact modifiers, antistatic agents, pigments, Colorant, mold release agent, lubricant, additive, compatibil
  • the shape of these additives may be any of fiber, granule, plate, needle, sphere, and powder. These additives can be used within 500 parts by mass with respect to 100 parts by mass of the fibrous resin reinforcing agent comprising the refined cellulose fiber (A) and the additive (B).
  • the resin composition of the present invention comprises a fibrous resin reinforcing agent and a thermoplastic resin, preferably polylactic acid, and conventional melt-kneading is used for production and molding of the resin composition.
  • the polylactic acid used in the resin composition of the present invention includes a polylactic acid homopolymer or copolymer.
  • the arrangement pattern of the copolymer may be any of random copolymer, alternating copolymer, block copolymer, and graft copolymer. Further, it may be a blend polymer with other resin mainly composed of polylactic acid homopolymer or copolymer.
  • the other resin include biodegradable resins other than polylactic acid, general-purpose thermoplastic resins, and general-purpose thermoplastic engineering plastics.
  • Polylactic acid is not particularly limited, and examples thereof include those obtained by ring-opening polymerization of lactide, and those obtained by direct polycondensation of D-form, L-form, racemate, etc. of lactic acid.
  • Poly-L-lactic acid, a copolymer of D-lactic acid and L-lactic acid, or a mixture of poly-D-lactic acid and poly-L-lactic acid may be used.
  • stereocomplex type polylactic acid exhibits higher heat resistance than poly-D-lactic acid or poly-L-lactic acid.
  • the weight average molecular weight of polylactic acid is generally about 10,000 to 500,000.
  • polylactic acid obtained by crosslinking with a crosslinking agent using heat, light, radiation or the like can be used.
  • the blending ratio of the fibrous resin reinforcing agent and the thermoplastic resin (polylactic acid) in the resin composition of the present invention is the blending of the fibrous resin reinforcing agent with respect to 100 parts by mass of the total amount of the fibrous resin reinforcing agent and the resin.
  • the amount is, for example, 0.1 to 50 parts by mass, preferably 1 to 30 parts by mass, more preferably 1 to 20 parts by mass.
  • the blending amount of the fibrous resin reinforcing agent is less than 0.1 parts by mass, the content of the refined cellulose fiber is low, so that the mechanical strength of the resin cannot be improved.
  • the plasticization effect of a fibrous resin reinforcement becomes remarkable and the mechanical strength of resin falls.
  • Resin of a fibrous resin reinforcing agent and a thermoplastic resin by a known method as melt kneading in the production of a resin composition, for example, a kneader, a roll mixer, a Banbury mixer, or an extruder (single screw or twin screw extruder).
  • a composition is obtained.
  • a fibrous resin reinforcing agent, a resin, and other components are used by using an arbitrary one such as a Henschel mixer, a super mixer, a V-type blender, or a nauter mixer. Premixing may be performed.
  • the melt kneading temperature is 50 ° C. to 300 ° C., preferably 100 ° C. to 250 ° C.
  • various molded products can be easily formed by using a conventional molding method such as general injection molding, blow molding, vacuum molding, compression molding, etc. Can be manufactured.
  • the molded body thus obtained is also an object of the present invention.
  • the fibrous resin reinforcing agent of the present invention is in a state where the finely divided cellulose fibers are dispersed in the additive (B), and is extremely excellent in dispersibility in the resin as a matrix.
  • the resin composition and the molded body in which the fibrous resin reinforcing agent is blended with the matrix resin are in a state where the finely divided cellulose fibers are uniformly dispersed, and the mechanical strength of the resin composition or the molded body is excellent. It is considered to show characteristics.
  • the molded article of the present invention can be usefully applied to automobile parts, electrical / electronic equipment casings, machine parts, and the like because the impact strength is particularly improved.
  • ⁇ Laser diffraction / scattering particle size distribution measurement> For measuring the particle size of cellulose, laser diffraction (Malvern Co., Ltd., apparatus name: Mastersizer 2000) was used. The measurement was performed in water, at room temperature, with stirring at 3,500 rpm, and under ultrasonic irradiation. ⁇ Differential thermobalance> Using TG-DTA (Thermo Plus, Thermo Plus, TG-8120, manufactured by Rigaku Corporation), the temperature was increased from room temperature to 500 ° C. at 10 ° C./min, and the mass loss at 150 ° C. was measured.
  • TG-DTA Thermo Plus, Thermo Plus, TG-8120, manufactured by Rigaku Corporation
  • Example 1 Production of fibrous resin reinforcing agent and resin composition and molded body from commercially available cellulose powder (1)
  • 5 parts by mass of commercially available cellulose powder (Fibra-Cell BH-100 manufactured by Celite) was dispersed in 495 parts by mass of pure water, and refined (Starburst System, manufactured by Sugino Machine Co., Ltd.) (200 MPa, 50 Pass).
  • a refined cellulose fiber aqueous dispersion was obtained.
  • the obtained cellulose fiber aqueous dispersion was measured in a petri dish, dried at 110 ° C. for 5 hours, moisture was removed, the amount of residue was measured, and the concentration was measured.
  • the micronized cellulose fiber concentration in water was 0.74% by mass.
  • FIG. 1 shows a polarizing microscope photograph observing the dispersion state of the refined cellulose fibers in the obtained fibrous resin reinforcing agent.
  • Polylactic acid (Ingeo (registered trademark) 3001D manufactured by Nature Works) is added to the obtained fibrous resin reinforcing agent so that the cellulose fiber becomes 1% by mass, and a twin screw extruder (manufactured by Toyo Seiki Seisakusho Co., Ltd.) Melting and kneading was performed at a barrel temperature of 190 ° C. using a plastmill micro, twin screw extruder 2D15W) to obtain a resin composition containing 1% by mass of cellulose fiber in polylactic acid.
  • FIG. 6 shows a polarizing microscope photograph of the dispersion state of the finely divided cellulose fibers in the obtained resin composition.
  • the obtained resin composition was melted at a cylinder temperature of 200 ° C. using an injection molding machine (Thermo Fisher Scientific Co., Ltd., Thermo Scientific HAAKE MiniJet II), and injected into a 30 ° C. mold. After holding the resin for 30 seconds to cure the resin, a molded body (length 80 mm ⁇ width 10 mm ⁇ thickness 4 mm) was taken out from the mold.
  • Example 2 Production of fibrous resin reinforcing agent and resin composition and molded body from commercially available cellulose powder (2)
  • the moisture content of the obtained fibrous resin reinforcing agent was 2.29% by mass as measured by the mass loss at 150 ° C.
  • FIG. 2 shows a polarization micrograph of the dispersion state of the refined cellulose fiber in the obtained fibrous resin reinforcing agent.
  • FIG. 2 shows the dispersion state of the refined cellulose fiber in the resin composition containing the fibrous resin reinforcement agent. The polarization micrograph which observed this is shown in FIG. 7, respectively.
  • Example 3 Production of fibrous resin reinforcing agent and resin composition and molded body from refined pulp
  • 50 parts by mass of purified pulp was dispersed in 400 parts by mass of pure water and subjected to a homogenizer treatment (Hiscotron manufactured by Microtech Nichion) (15,000 rpm, 1 hour), and coarsely pulverized.
  • cellulose refinement treatment was performed in the same manner as in Example 1, and an additive mainly composed of decaglycerin monolaurate (Poem [registered trademark] J-0021 manufactured by Riken Vitamin Co., Ltd.) was added.
  • decaglycerin monolaurate Pumic acid
  • FIG. 3 shows a polarization micrograph of the dispersion state of the refined cellulose fibers in the obtained fibrous resin reinforcing agent.
  • FIG. 3 shows the dispersion state of the refined cellulose fibers in the resin composition containing the fibrous resin reinforcement agent.
  • FIG. 8 shows polarization micrographs obtained by observing.
  • Example 4 Production of fibrous resin reinforcing agent and resin composition and molded body from bacterial cellulose] 2,000 parts by mass of bacterial cellulose (PT.NIRAMAS manufactured by UTAMA) was cut with scissors and chopped with a home-use mixer. The aqueous dispersion (about pH 3) obtained by shredding was filtered and then washed with 500 parts by mass of water. This operation was repeated until the pH of the dispersion reached 7. The aqueous dispersion thus obtained was subjected to a homogenizer treatment (Hiscotron manufactured by Microtech Nithion) (15,000 rpm, 1 hour) to obtain a coarsely pulverized aqueous dispersion of bacterial cellulose.
  • a homogenizer treatment Hiscotron manufactured by Microtech Nithion
  • FIG. 4 shows a polarization micrograph obtained by observing the dispersion state of the refined cellulose fibers in the obtained fibrous resin reinforcing agent.
  • FIG. 4 shows the dispersion state of the refined cellulose fibers in the resin composition containing the fibrous resin reinforcing agent.
  • FIG. 9 shows polarization micrographs obtained by observing.
  • Comparative Example 1 Production of fibrous resin reinforcing agent and resin composition and molded article from commercially available cellulose powder (3)
  • a fibrous resin reinforcing agent, a resin composition, and a molded article were produced in the same manner as in Example 1.
  • FIG. 5 shows a polarization micrograph of the dispersion state of the refined cellulose fiber in the obtained fibrous resin reinforcing agent.
  • FIG. 5 shows the dispersion state of the refined cellulose fiber in the resin composition containing the fibrous resin reinforcement agent.
  • FIG. 10 shows polarization micrographs obtained by observing.
  • FIG. 11 shows a polarizing microscope photograph observing the dispersion state of the commercially available cellulose powder in the obtained resin composition.
  • a molded body was produced in the same manner as in Example 1.
  • FIG. 12 shows a polarizing microscope photograph observing the dispersion state of the coarsely pulverized pulp in the resin composition containing the obtained fibrous resin reinforcing agent.
  • Example 4 Production of fibrous resin reinforcing agent and resin composition containing coarsely pulverized bacterial cellulose, and molded article
  • an additive containing decaglycerin monolaurate as a main component (Poem [manufactured by Riken Vitamin Co., Ltd.) was added to the aqueous dispersion of coarsely pulverized bacterial cellulose obtained in the same manner as in Example 4.
  • (Registered trademark) J-0021) was added to remove water to obtain a fibrous resin reinforcing agent containing coarsely pulverized bacterial cellulose, and then a resin composition and a molded body were produced.
  • FIG. 13 shows a polarizing microscope photograph of the dispersion state of the coarsely pulverized bacterial cellulose in the resin composition containing the obtained fibrous resin reinforcing agent.
  • Table 1 shows the weight average molecular weight of the obtained resin composition and the Izod impact strength of the molded product evaluated by an Izod impact test according to JIS K 7110.
  • the resin composition or molded product containing the fibrous resin reinforcing agent obtained by the present invention can be melt-kneaded at the same melting temperature as that of conventional polylactic acid (double-screw extruder, barrel temperature 190 ° C.). In the injection molding to be performed, it was possible to melt at a cylinder temperature (200 ° C.) similar to that of conventional polylactic acid and to inject it into a 30 ° C. mold.
  • Examples 1 and 2 are resin compositions (molded bodies) using a commercial cellulose powder subjected to the same refinement treatment, but using a fibrous resin reinforcing agent using an additive having different HLB values.
  • Comparative Example 1 was compared with Comparative Example 1 in which the HLB value of the additive was 9.4, no improvement in impact strength was observed as compared with the resin composition of Comparative Example 5 in which the additive and cellulose fiber were not added.
  • Example 1 and Example 2 in which the HLB value was 10 or more the result that the impact strength was remarkably improved was obtained.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

Cette invention a pour objet de pourvoir à un procédé de production d'un agent de renforcement de résine fibreux permettant de former plus facilement des composites fibre cellulosique et acide polylactique, la fibre cellulosique dans la composition de résine obtenue ayant une dispersibilité uniforme élevée, et la résistance au choc d'un corps moulé étant considérablement améliorée. Pour ce faire, l'agent de renforcement de résine fibreux selon l'invention est préparé par dissolution d'un additif hydrophile dans une dispersion aqueuse de fibres cellulosiques affinées pour obtenir une suspension et lesdites fibres cellulosiques affinées obtenues par élimination de l'humidité à partir de la suspension sont uniformément dispersées. La résistance au choc peut être considérablement améliorée par ajout dudit agent de renforcement à l'acide polylactique.
PCT/JP2012/051809 2011-02-15 2012-01-27 Agent de renforcement de résine fibreux et son procédé de production, et composition de résine l'utilisant WO2012111408A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2012557869A JP5975222B2 (ja) 2011-02-15 2012-01-27 繊維状樹脂補強剤の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011-029910 2011-02-15
JP2011029910 2011-02-15

Publications (1)

Publication Number Publication Date
WO2012111408A1 true WO2012111408A1 (fr) 2012-08-23

Family

ID=46672345

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/051809 WO2012111408A1 (fr) 2011-02-15 2012-01-27 Agent de renforcement de résine fibreux et son procédé de production, et composition de résine l'utilisant

Country Status (3)

Country Link
JP (1) JP5975222B2 (fr)
TW (1) TW201245293A (fr)
WO (1) WO2012111408A1 (fr)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013122171A1 (fr) * 2012-02-14 2013-08-22 京都市 Liquide de dispersion contenant des nanofibres de cellulose et une résine, et composition de résine
JP2015086388A (ja) * 2013-10-31 2015-05-07 ハンコック タイヤ カンパニー リミテッド タイヤ用ゴム組成物及びそれを用いて製造したタイヤ
JP2015117340A (ja) * 2013-12-19 2015-06-25 サンノプコ株式会社 セルロースナノファイバー水性分散体の製造方法及び高濃度化助剤
JP2016065116A (ja) * 2014-09-24 2016-04-28 第一工業製薬株式会社 セルロースナノファイバー水分散体組成物、それを用いた食品および化粧料。
JP2016162841A (ja) * 2015-02-27 2016-09-05 ニチコン株式会社 電解コンデンサ用の固定材およびそれを用いた電解コンデンサ
JP2017513977A (ja) * 2014-04-09 2017-06-01 ティコナ・エルエルシー 静電防止ポリマー組成物
JP2017099364A (ja) * 2015-12-04 2017-06-08 国立大学法人愛媛大学 極小セルロースの製造方法
EP3127954A4 (fr) * 2014-03-31 2018-01-03 Dainichiseika Color & Chemicals Mfg. Co., Ltd. Agent dispersant polymère pour cellulose, agent de traitement de dispersion aqueux comprenant cet agent dispersant polymère, composition de cellulose facilement dispersable, composition de résine à dispersion de cellulose, et composition de résine comprenant un agent dispersant pour dispersion de cellulose
EP3127955A4 (fr) * 2014-03-31 2018-01-03 Dainichiseika Color & Chemicals Mfg. Co., Ltd. Composition de cellulose facilement dispersable ainsi que procédé de fabrication de celle-ci, composition de résine à dispersion de cellulose, et procédé de fabrication d'agent de traitement de dispersion aqueux pour cellulose
WO2018012629A1 (fr) * 2016-07-14 2018-01-18 東洋製罐グループホールディングス株式会社 Fibres de cellulose comprenant des nanofibres de cellulose, et procédé de fabrication de celles-ci
JP2018080262A (ja) * 2016-11-16 2018-05-24 住友ゴム工業株式会社 タイヤ用ゴム組成物及びタイヤ
KR20180077000A (ko) 2016-12-28 2018-07-06 아사히 가세이 가부시키가이샤 셀룰로오스 제제
JP6419276B1 (ja) * 2016-12-28 2018-11-07 旭化成株式会社 セルロース含有樹脂組成物
WO2019045076A1 (fr) * 2017-09-04 2019-03-07 株式会社日本製鋼所 Dispersion liquide de nanofibres de cellulose, résine composite à base de nanofibres de cellulose, et procédés de production de la dispersion et de la résine
JP2019203108A (ja) * 2018-05-25 2019-11-28 旭化成株式会社 微細セルロース含有樹脂組成物
US10640648B2 (en) 2014-04-09 2020-05-05 Ticona Llc Camera module
JP2020094098A (ja) * 2018-12-11 2020-06-18 コニカミノルタ株式会社 繊維強化樹脂組成物、これを含む樹脂成形品、電子写真形成装置および電子写真形成装置用外装部品
US10829634B2 (en) 2017-12-05 2020-11-10 Ticona Llc Aromatic polymer composition for use in a camera module
WO2021193193A1 (fr) * 2020-03-25 2021-09-30 国立大学法人群馬大学 Morceaux de nanocellulose, procédé de fabrication de morceaux de nanocellulose, matériau composite polymère et procédé de fabrication de matériau composite polymère

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109608786A (zh) * 2018-12-07 2019-04-12 成都玉龙化工有限公司 一种高抗冲耐压pvc复合材料及其制备方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002059524A (ja) * 2000-08-18 2002-02-26 Mitsui Chemicals Inc 分解性ラミネート積層体
JP2004339454A (ja) * 2003-03-18 2004-12-02 Toray Ind Inc 樹脂組成物およびそれからなる成形品
JP2005023260A (ja) * 2003-07-04 2005-01-27 Toray Ind Inc 電気・電子部品
JP2005133039A (ja) * 2003-10-31 2005-05-26 Toray Ind Inc 脂肪族ポリエステル樹脂組成物成形体
JP2007526072A (ja) * 2004-03-03 2007-09-13 ロスタム・リミテッド 改善されたｐＨ降下用組成物
JP2009212378A (ja) * 2008-03-05 2009-09-17 Hitachi Chem Co Ltd Ｃｍｐ研磨液、基板の研磨方法及び電子部品
JP2010201414A (ja) * 2009-02-06 2010-09-16 Kao Corp 膜状成形体の製造方法
JP2010270290A (ja) * 2008-08-08 2010-12-02 Kao Corp 生分解性樹脂組成物
JP2011027898A (ja) * 2009-07-23 2011-02-10 Konica Minolta Holdings Inc 光学フィルムの製造方法、光学フィルム、及びそれを用いた偏光板、液晶表示装置

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5928676B2 (ja) * 1981-07-13 1984-07-14 日本油脂株式会社 製紙用ピツチ付着防止剤
JP3423334B2 (ja) * 1992-08-20 2003-07-07 旭化成株式会社 微粒化セルロース系素材含水組成物
JP2000178377A (ja) * 1998-12-16 2000-06-27 Asahi Chem Ind Co Ltd セルロース複合体粉末
JP2007238812A (ja) * 2006-03-09 2007-09-20 Hiroshima Pref Gov ポリ乳酸−ミクロフィブリル化セルロース複合材料およびその製造方法
JP2008274064A (ja) * 2007-04-27 2008-11-13 Mitsuboshi Belting Ltd パルプの分散方法およびパルプ配合ゴム組成物
JP5944098B2 (ja) * 2009-12-11 2016-07-05 花王株式会社 微細セルロース繊維複合体、微細セルロース繊維分散液及び複合材料

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002059524A (ja) * 2000-08-18 2002-02-26 Mitsui Chemicals Inc 分解性ラミネート積層体
JP2004339454A (ja) * 2003-03-18 2004-12-02 Toray Ind Inc 樹脂組成物およびそれからなる成形品
JP2005023260A (ja) * 2003-07-04 2005-01-27 Toray Ind Inc 電気・電子部品
JP2005133039A (ja) * 2003-10-31 2005-05-26 Toray Ind Inc 脂肪族ポリエステル樹脂組成物成形体
JP2007526072A (ja) * 2004-03-03 2007-09-13 ロスタム・リミテッド 改善されたｐＨ降下用組成物
JP2009212378A (ja) * 2008-03-05 2009-09-17 Hitachi Chem Co Ltd Ｃｍｐ研磨液、基板の研磨方法及び電子部品
JP2010270290A (ja) * 2008-08-08 2010-12-02 Kao Corp 生分解性樹脂組成物
JP2010201414A (ja) * 2009-02-06 2010-09-16 Kao Corp 膜状成形体の製造方法
JP2011027898A (ja) * 2009-07-23 2011-02-10 Konica Minolta Holdings Inc 光学フィルムの製造方法、光学フィルム、及びそれを用いた偏光板、液晶表示装置

Cited By (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013166818A (ja) * 2012-02-14 2013-08-29 Kyoto City セルロースナノファイバー及び樹脂を含む分散液、並びに樹脂組成物
WO2013122171A1 (fr) * 2012-02-14 2013-08-22 京都市 Liquide de dispersion contenant des nanofibres de cellulose et une résine, et composition de résine
JP2015086388A (ja) * 2013-10-31 2015-05-07 ハンコック タイヤ カンパニー リミテッド タイヤ用ゴム組成物及びそれを用いて製造したタイヤ
US9321909B2 (en) 2013-10-31 2016-04-26 Hankook Tire Co., Ltd. Rubber composition for tire tread and tire manufactured by using the same
JP2015117340A (ja) * 2013-12-19 2015-06-25 サンノプコ株式会社 セルロースナノファイバー水性分散体の製造方法及び高濃度化助剤
EP3127954A4 (fr) * 2014-03-31 2018-01-03 Dainichiseika Color & Chemicals Mfg. Co., Ltd. Agent dispersant polymère pour cellulose, agent de traitement de dispersion aqueux comprenant cet agent dispersant polymère, composition de cellulose facilement dispersable, composition de résine à dispersion de cellulose, et composition de résine comprenant un agent dispersant pour dispersion de cellulose
US10077357B2 (en) 2014-03-31 2018-09-18 Dainichiseika Color & Chemicals Mfg. Co., Ltd. Production method for readily dispersible cellulose composition, readily dispersible cellulose composition, cellulose dispersion resin composition, and production method for water-based dispersant for cellulose
EP3127955A4 (fr) * 2014-03-31 2018-01-03 Dainichiseika Color & Chemicals Mfg. Co., Ltd. Composition de cellulose facilement dispersable ainsi que procédé de fabrication de celle-ci, composition de résine à dispersion de cellulose, et procédé de fabrication d'agent de traitement de dispersion aqueux pour cellulose
US10081001B2 (en) 2014-03-31 2018-09-25 Dainichiseika Color & Chemicals Mfg. Co., Ltd. Polymer dispersant for cellulose, aqueous dispersion treatment agent containing same, readily dispersible cellulose composition, cellulose dispersion resin composition, and dispersant-containing resin composition for cellulose dispersion
US10287421B2 (en) 2014-04-09 2019-05-14 Ticona Llc Antistatic polymer composition
JP2017513977A (ja) * 2014-04-09 2017-06-01 ティコナ・エルエルシー 静電防止ポリマー組成物
US10640648B2 (en) 2014-04-09 2020-05-05 Ticona Llc Camera module
US11208556B2 (en) 2014-04-09 2021-12-28 Ticona Llc Camera module
JP2021176972A (ja) * 2014-04-09 2021-11-11 ティコナ・エルエルシー 静電防止ポリマー組成物
JP2016065116A (ja) * 2014-09-24 2016-04-28 第一工業製薬株式会社 セルロースナノファイバー水分散体組成物、それを用いた食品および化粧料。
JP2016162841A (ja) * 2015-02-27 2016-09-05 ニチコン株式会社 電解コンデンサ用の固定材およびそれを用いた電解コンデンサ
JP2017099364A (ja) * 2015-12-04 2017-06-08 国立大学法人愛媛大学 極小セルロースの製造方法
WO2018012629A1 (fr) * 2016-07-14 2018-01-18 東洋製罐グループホールディングス株式会社 Fibres de cellulose comprenant des nanofibres de cellulose, et procédé de fabrication de celles-ci
JP2018080262A (ja) * 2016-11-16 2018-05-24 住友ゴム工業株式会社 タイヤ用ゴム組成物及びタイヤ
JP2019014864A (ja) * 2016-12-28 2019-01-31 旭化成株式会社 セルロースを含む樹脂組成物
JP6419276B1 (ja) * 2016-12-28 2018-11-07 旭化成株式会社 セルロース含有樹脂組成物
US11390728B2 (en) 2016-12-28 2022-07-19 Asahi Kasei Kabushiki Kaisha Cellulose-containing resin composition and cellulosic ingredient
JP2019014865A (ja) * 2016-12-28 2019-01-31 旭化成株式会社 セルロース含有樹脂組成物
KR20180077000A (ko) 2016-12-28 2018-07-06 아사히 가세이 가부시키가이샤 셀룰로오스 제제
JP2018109138A (ja) * 2016-12-28 2018-07-12 旭化成株式会社 セルロース製剤
CN111094424B (zh) * 2017-09-04 2022-07-08 株式会社日本制钢所 纤维素纳米纤维分散液、纤维素纳米纤维复合树脂及它们的制造方法
CN111094424A (zh) * 2017-09-04 2020-05-01 株式会社日本制钢所 纤维素纳米纤维分散液、纤维素纳米纤维复合树脂及它们的制造方法
WO2019045076A1 (fr) * 2017-09-04 2019-03-07 株式会社日本製鋼所 Dispersion liquide de nanofibres de cellulose, résine composite à base de nanofibres de cellulose, et procédés de production de la dispersion et de la résine
JP2019044087A (ja) * 2017-09-04 2019-03-22 株式会社日本製鋼所 セルロースナノファイバー分散液、及び、セルロースナノファイバー複合樹脂
US10829634B2 (en) 2017-12-05 2020-11-10 Ticona Llc Aromatic polymer composition for use in a camera module
US11725106B2 (en) 2017-12-05 2023-08-15 Ticona Llc Aromatic polymer composition for use in a camera module
JP2019203108A (ja) * 2018-05-25 2019-11-28 旭化成株式会社 微細セルロース含有樹脂組成物
JP2020094098A (ja) * 2018-12-11 2020-06-18 コニカミノルタ株式会社 繊維強化樹脂組成物、これを含む樹脂成形品、電子写真形成装置および電子写真形成装置用外装部品
WO2021193193A1 (fr) * 2020-03-25 2021-09-30 国立大学法人群馬大学 Morceaux de nanocellulose, procédé de fabrication de morceaux de nanocellulose, matériau composite polymère et procédé de fabrication de matériau composite polymère
JPWO2021193193A1 (fr) * 2020-03-25 2021-09-30
JP7407405B2 (ja) 2020-03-25 2024-01-04 国立大学法人群馬大学 ナノセルロース片、ナノセルロース片の製造方法、高分子複合材料及び高分子複合材料の製造方法

Also Published As

Publication number Publication date
TW201245293A (en) 2012-11-16
JPWO2012111408A1 (ja) 2014-07-03
JP5975222B2 (ja) 2016-08-23

Similar Documents

Publication Publication Date Title
JP5975222B2 (ja) 繊維状樹脂補強剤の製造方法
JP5030667B2 (ja) ミクロフィブリル化セルロース複合樹脂及びその製造方法
Tian et al. Fabrication, properties and applications of soy-protein-based materials: A review
Scaffaro et al. Polysaccharide nanocrystals as fillers for PLA based nanocomposites
JP5660333B2 (ja) セルロース及びポリ乳酸を含有する組成物の製造方法
JP5150792B2 (ja) 変性セルロースナノファイバー、その製造方法及びこれを用いた樹脂組成物
Wei et al. Performance of high lignin content cellulose nanocrystals in poly (lactic acid)
CA2812868C (fr) Procede de pulverisation de cellulose, nanofibres de cellulose, melange-maitre et composition de resine
Paul et al. Effect of green plasticizer on the performance of microcrystalline cellulose/polylactic acid biocomposites
Lee et al. Cellulose nanofiber-reinforced polycaprolactone/polypropylene hybrid nanocomposite
EP2799491B1 (fr) Composition de résine polyester
US20100240806A1 (en) Materials containing polyactic acid and cellulose fibers
Chihaoui et al. Lignin-containing cellulose fibrils as reinforcement of plasticized PLA biocomposites produced by melt processing using PEG as a carrier
JP5673931B2 (ja) 混合物及びセルロースファイバー分散組成物並びにそれらの製造方法
Zhu et al. Modification of lignin with silane coupling agent to improve the interface of poly (L-lactic) acid/lignin composites
JP6075521B2 (ja) 樹脂組成物の製造方法
JP2019043977A (ja) セルロースで強化された樹脂組成物の製造方法
JP2021172671A (ja) 粉末状微細セルロース繊維、樹脂組成物、成形体およびその製造方法
Suchaiya et al. Effect of microcrystalline cellulose from banana stem fiber on mechanical properties and crystallinity of PLA composite films
Norrrahim et al. Performance evaluation of cellulose nanofiber with residual hemicellulose as a nanofiller in polypropylene-based nanocomposite. Polymers 2021; 13: 1064
JP2022026594A (ja) 樹脂組成物
Kong et al. Effect of Surface Modifying Agents Towards Enhancing Performance of Waste Gypsum Based PBAT Composite
JP2020045374A (ja) 樹脂組成物の製造方法
Banvillet et al. Advances in the Production of Cellulose Nanomaterials and Their Use in Engineering (Bio) Plastics
JP2014047234A (ja) ポリ乳酸樹脂組成物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12747542

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2012557869

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12747542

Country of ref document: EP

Kind code of ref document: A1