WO2012008401A1 - Procédé pour la production de fibres de cellulose purifiée - Google Patents

Procédé pour la production de fibres de cellulose purifiée Download PDF

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Publication number
WO2012008401A1
WO2012008401A1 PCT/JP2011/065777 JP2011065777W WO2012008401A1 WO 2012008401 A1 WO2012008401 A1 WO 2012008401A1 JP 2011065777 W JP2011065777 W JP 2011065777W WO 2012008401 A1 WO2012008401 A1 WO 2012008401A1
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ionic liquid
group
cellulose fiber
cellulose
raw material
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PCT/JP2011/065777
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English (en)
Japanese (ja)
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暁 奥村
アショカ クマル カルモカル
健一 杉本
光治 小出
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株式会社ブリヂストン
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B16/00—Regeneration of cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
    • C08B1/003—Preparation of cellulose solutions, i.e. dopes, with different possible solvents, e.g. ionic liquids
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/02—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from solutions of cellulose in acids, bases or salts

Definitions

  • the present invention relates to a method for producing purified cellulose fibers from cellulose raw materials.
  • Cellulose is a natural polymer classified as a polysaccharide, and cellulose fibers artificially produced from cellulose are widely used in a large amount in various applications.
  • regenerated cellulose fibers such as rayon produced by the viscose method have been mainstream as cellulose fibers.
  • the viscose method has a problem that harmful carbon disulfide is generated in the production process.
  • NMMO N-methylmorpholine-N-oxide
  • the refined cellulose fiber produced by the production method has a problem that the strength and fatigue resistance are inferior compared to regenerated cellulose fiber such as rayon produced by the viscose method.
  • Patent Document 1 describes a method of dissolving cellulose, which includes a step of mixing cellulose with a molten ionic liquid not containing a nitrogen-containing base to form a mixture.
  • nitrogen-containing aromatic cations such as imidazolium cation, or one or more carbon atoms forming a ring of a cyclic alkane is substituted with a nitrogen atom, and the nitrogen atom is substituted with an alkyl group or an alkoxy group.
  • a cation moiety having an alkyl group attached thereto is disclosed.
  • halogen ions, perchlorate ions, and pseudohalogen ions are disclosed as the anion portion of the molten ionic liquid.
  • the ionic liquid When producing purified cellulose fibers by spinning or the like using an ionic liquid as described above, the ionic liquid has heat resistance that is stable against heat in order to facilitate the recovery and reuse of the ionic liquid. It will be necessary.
  • the ionic liquid using a cation as described in Patent Document 1 has been said to be stable against heat until now, but the present inventors have insufficient thermal stability. I found a new problem. Further, the ionic liquid having a cation other than the cation described in Patent Document 1 has a problem that cellulose solubility becomes insufficient and satisfactory spinning cannot be performed.
  • the present invention has been made in view of the above circumstances, and uses purified ionic liquid with high thermal stability to produce purified cellulose fiber having the same strength as rayon without producing a high environmental impact byproduct. It is an object of the present invention to provide a method for producing purified cellulose fibers.
  • the present inventor used an ionic liquid having an anion moiety represented by the following general formula (A1) or (A2) as an anion moiety to produce a by-product with a high environmental load.
  • the present inventors have found that a purified cellulose fiber having the same strength as rayon can be produced without occurrence, and that the ionic liquid has high thermal stability, thereby completing the present invention.
  • this invention provides the manufacturing method of the refined cellulose fiber which has the following characteristics.
  • the manufacturing method of the refined cellulose fiber characterized by doing.
  • R 11 , R 12 and R 13 are each independently an alkyl group, and R 14 is a hydrogen atom or an alkyl group.
  • the ionic liquid is heated while being heated at a rate of 10 ° C./min, and an ionic liquid having a mass reduction rate of 20% by mass or less when the heating temperature reaches 250 ° C.
  • the method for producing a purified cellulose fiber according to any one of (1) to (4).
  • the purified cellulose fiber can be produced in a closed system without producing harmful substances such as carbon disulfide, the environmental load can be reduced. Moreover, the purified cellulose fiber obtained by the present invention has high utility value because it has a strength equal to or higher than that of regenerated cellulose fiber such as rayon. Furthermore, since the ionic liquid used in the present invention has high thermal stability, the degree of freedom of the process temperature when performing the production method of the present invention is high, and the ionic liquid can be easily recovered and reused.
  • FIG. 4 is a graph showing the relationship among mass increase / decrease (%), temperature (° C.), and heat flow rate (W / g) when heat is applied to 1,3-dimethylimidazolium dimethyl phosphate in Experimental Example 1. is there. The relationship between mass increase / decrease (%), temperature (° C.), and heat flow rate (W / g) when heat was applied to 1-ethyl-3-methylimidazolium diethylphosphate in Experimental Example 1 was shown.
  • Example 5 is a graph showing the relationship among mass increase / decrease (%), temperature (° C.), and heat flow rate (W / g) when heat is applied to 1-ethyl-3-methylimidazolium acetate in Experimental Example 1. is there. 1 is a photograph of purified cellulose fibers obtained in Example 1.
  • FIG. 1 is a photograph of purified cellulose fibers obtained in Example 1.
  • a cellulose solution obtained by dissolving a cellulose raw material in a liquid containing an ionic liquid having an anion moiety represented by the general formula (A1) or (A2) as an anion moiety used to spin purified cellulose fiber.
  • the cellulose raw material is not particularly limited as long as it contains cellulose, and may be a plant-derived cellulose raw material, an animal-derived cellulose raw material, or a microorganism-derived cellulose raw material. Or a regenerated cellulose raw material.
  • Plant-derived cellulose raw materials include cellulose raw materials derived from unprocessed natural plants such as wood, cotton, hemp, and other herbs, and those derived from plants that have been pre-processed, such as pulp, wood flour, and paper products. Examples include processed cellulose raw materials. Examples of animal-derived cellulose raw materials include squirt-derived cellulose raw materials.
  • cellulose raw materials derived from microorganisms include those produced by the raw materials of microorganisms belonging to the genus Aerobacter, Acetobacter, Achromobacter, Agrobacterium, Alcaligenes, Azotobacter, Pseudomonas, Rhizobium, Sarcina and the like.
  • the regenerated cellulose raw material include a cellulose raw material obtained by regenerating a cellulose raw material derived from plants, animals, or microorganisms as described above by a known method such as a viscose method.
  • dissolves especially favorably in an ionic liquid is preferable.
  • the cellulose raw material before the cellulose raw material is dissolved in the liquid containing the ionic liquid, the cellulose raw material can be pretreated for the purpose of improving the solubility in the ionic liquid.
  • the pretreatment may include a drying treatment, a physical pulverization treatment such as pulverization and attrition, and a chemical modification treatment using an acid or an alkali. Any of these can be performed by a conventional method.
  • the ionic liquid refers to a liquid that is liquid at 150 ° C. or lower and is composed of organic ions
  • the ionic liquid in the present invention is represented by the following general formula (A1) or (A2) as an anion portion. Having an anionic moiety.
  • R 11 , R 12 and R 13 are each independently an alkyl group, and R 14 is a hydrogen atom or an alkyl group.
  • R 11 and R 12 are each independently an alkyl group.
  • Alkyl groups R 11, R 12 represents a linear, branched, and may be any of circular, and is preferably linear or branched alkyl group.
  • the alkyl group of R 11 and R 12 preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms for industrial reasons. Or an alkyl group of 2 is particularly preferred.
  • R 11 and R 12 may be the same or different from each other.
  • R 13 is an alkyl group, and examples thereof include the same alkyl groups as R 11 and R 12 in formula (A1).
  • R 14 is a hydrogen atom or an alkyl group, and examples of the alkyl group include the same alkyl groups as R 11 and R 12 in the above formula (A1).
  • R 14 is an alkyl group
  • the alkyl group of R 13 and the alkyl group of R 14 may be the same or different.
  • Preferred specific examples of the cation moiety represented by the formulas (A1) and (A2) are shown as the following formulas (A3) to (A5).
  • the ionic liquid has a cation portion that is paired with the above-described anion portion.
  • the cation portion of the ionic liquid is not particularly limited, and those generally used for the cation portion of the ionic liquid can be used.
  • a phosphonium cation and a nitrogen-containing aromatic cation are mentioned.
  • the phosphonium cation is not particularly limited as long as it has “P + ”.
  • a general formula “R 4 P + (a plurality of R's independently represents A hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.) ”.
  • the hydrocarbon group having 1 to 30 carbon atoms may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
  • the aliphatic hydrocarbon group is preferably a saturated hydrocarbon group (alkyl group), and the alkyl group may be linear, branched, or cyclic.
  • the linear alkyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 16 carbon atoms.
  • the branched alkyl group has 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, and more preferably 3 to 16 carbon atoms.
  • the cyclic alkyl group has 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 3 to 16 carbon atoms, even if it is a monocyclic group, It may be a polycyclic group.
  • Specific examples include monocyclic groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group, and polycyclic groups such as norbornyl group, adamantyl group, and isobornyl group.
  • the aromatic hydrocarbon group preferably has 6 to 30 carbon atoms.
  • an aryl group such as a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a biphenyl group, a tolyl group, or a benzyl group
  • arylalkyl groups such as a phenethyl group, a naphthylmethyl group, and a naphthylethyl group.
  • the plurality of R in the general formula “R 4 P + ” may be the same or different.
  • the cation part represented by a following formula (C1) is preferable.
  • R 1 to R 4 each independently represents an alkyl group having 1 to 16 carbon atoms.
  • R 1 to R 4 each independently represents an alkyl group having 1 to 16 carbon atoms.
  • the alkyl group having 1 to 16 carbon atoms may be linear, branched, or cyclic, and is preferably linear or branched, and more preferably linear.
  • examples of the linear, branched, and cyclic alkyl groups include those described above.
  • R 1 ⁇ R 4 can be the respectively same or different, but from the ease of availability, it is preferred that three or more of R 1 ⁇ R 4 are the same.
  • the alkyl group of R 1 to R 4 is preferably a linear or branched alkyl group having 1 to 14 carbon atoms, and is a linear or branched chain group having 1 to 10 carbon atoms.
  • linear or branched alkyl groups having 1 to 8 carbon atoms are more preferable, and linear or branched alkyl groups having 1 to 4 carbon atoms are particularly preferable.
  • a preferred specific example of the cation moiety represented by the formula (C1) is shown as the following formula (C2).
  • the nitrogen-containing aromatic cation examples include a pyridinium cation, a pyridazinium cation, a pyrimidinium cation, a pyrazinium cation, an imidazolium cation, a pyrazonium cation, an oxazolium cation, and 1,2. , 3-triazolium cation, 1,2,4-triazolium cation, thiazolium cation, piperidinium cation, pyrrolidinium cation and the like.
  • an imidazolium cation is preferable and the imidazolium cation mentioned by the following general formula (C3) is more preferable.
  • R 5 to R 6 are each independently an alkyl group having 1 to 10 carbon atoms or an allyl group, and R 7 to R 9 are each independently a hydrogen atom or 1 to 10 carbon atoms. It is an alkyl group.
  • R 5 to R 6 each independently represents an alkyl group having 1 to 10 carbon atoms or an allyl group.
  • the alkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic, and is preferably linear or branched, and more preferably linear.
  • examples of the linear, branched, and cyclic alkyl groups include the same alkyl groups as those described above for R 1 to R 4 .
  • R 5 to R 6 may be the same or different from each other.
  • R 7 to R 9 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • the alkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic, and is preferably linear or branched, and more preferably linear.
  • examples of the linear, branched, and cyclic alkyl groups include the same alkyl groups as those described above for R 5 to R 6 .
  • R 7 ⁇ R 9 can be the respectively same or different.
  • the ionic liquid in the present invention is composed of a cation portion and an anion portion as described above.
  • the combination of a cation part and an anion part is not specifically limited, The thing which can melt
  • the ionic liquid in the present invention is heated at a rate of 10 ° C./min while heating the ionic liquid, and the mass reduction of the ionic liquid when the heating temperature reaches 250 ° C., preferably 300 ° C.
  • the rate is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less.
  • a lower mass reduction rate when the ionic liquid is heated means that the thermal stability of the ionic liquid is higher.
  • TGA thermogravimetric analyzer
  • the ionic liquid having the anion portion represented by the general formula (A1) or (A2) as the anion portion is more stable than the ionic liquid having the conventional imidazolium cation. Therefore, the ionic liquid can be easily recovered and reused. Moreover, the viscosity of a solution can be kept moderate by using the ionic liquid which has an anion part represented by general formula (A1) or (A2) as an anion part.
  • the use amount of the ionic liquid is not particularly limited, but is preferably 1 to 50 parts by weight, and preferably 3 to 30 parts by weight with respect to 1 part by weight of the cellulose raw material. More preferred is 5 to 25 parts by mass. By setting it as the said range, it can be set as the cellulose solution of a more moderate viscosity.
  • the liquid for dissolving the cellulose raw material contains the ionic liquid.
  • the liquid may or may not contain liquid components other than the ionic liquid.
  • Specific examples of liquid components other than the ionic liquid include organic solvents.
  • the organic solvent is not particularly limited as long as it is other than the ionic liquid, and can be appropriately selected in consideration of compatibility with the ionic liquid, viscosity, and the like.
  • the organic solvent is preferably at least one selected from the group consisting of amide solvents, sulfoxide solvents, nitrile solvents, cyclic ether solvents, and aromatic amine solvents.
  • amide solvents include N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1-vinyl-2-pyrrolidone and the like.
  • sulfoxide solvent include dimethyl sulfoxide and hexamethylene sulfoxide.
  • nitrile solvents include acetonitrile, propionitrile, benzonitrile and the like.
  • cyclic ether solvent include 1,3-dioxolane, tetrahydrofuran, tetrahydropyran, 1,3-dioxane, 1,4-dioxane, 1,3,5-trioxane and the like.
  • aromatic amine solvent include pyridine.
  • the blending mass ratio between the ionic liquid and the organic solvent is preferably 6: 1 to 0.1: 1, more preferably 5: 1 to 0.2: 1. More preferably, the ratio is 4: 1 to 0.5: 1.
  • the amount of the organic solvent used is not particularly limited, but is preferably 1 to 30 parts by weight, preferably 1 to 25 parts by weight, based on 1 part by weight of the cellulose raw material. More preferably, it is 20 parts by mass.
  • it By setting it as the said range, it can be set as the cellulose solution of moderate viscosity. Since the solubility of a cellulose raw material improves more by using the above organic solvents together with an ionic liquid, these combined use is preferable.
  • the viscosity of the liquid containing the ionic liquid at 80 ° C. is preferably 100 to 10,000,000 Pa ⁇ s, more preferably 105 to 1,000,000 Pa ⁇ s, and further preferably 110 to 100,000 Pa ⁇ s. preferable. By setting it as the said range, a refined cellulose fiber can be manufactured more suitably.
  • the viscosity of the liquid containing the ionic liquid can be measured by a conventional method. Specifically, based on JIS Z8803, it can measure using a commercially available viscometer, a viscoelasticity measuring apparatus, etc.
  • the method for dissolving the cellulose raw material in the liquid containing the ionic liquid is not particularly limited.
  • the liquid containing the ionic liquid and the cellulose raw material are brought into contact with each other and heated or stirred as necessary. By performing, a cellulose solution can be obtained.
  • the method for bringing the liquid containing the ionic liquid into contact with the cellulose raw material is not particularly limited.
  • the cellulose raw material may be added to the liquid containing the ionic liquid, or the liquid containing the ionic liquid in the cellulose raw material. May be added.
  • the heating temperature is preferably 30 to 200 ° C, more preferably 70 to 120 ° C.
  • Heating is preferably performed because the solubility of the cellulose raw material is further improved by heating.
  • the stirring method is not particularly limited, and the liquid containing the ionic liquid and the cellulose raw material may be mechanically stirred using a stirrer, a stirring blade, a stirring bar, etc., and the liquid containing the ionic liquid
  • the cellulose raw material may be sealed in a sealed container and stirred by shaking the container.
  • the stirring time is not particularly limited, and it is preferable to carry out the stirring until the cellulose raw material is suitably dissolved.
  • the organic solvent and the ionic liquid may be mixed in advance, and after mixing the ionic liquid and the cellulose raw material The organic solvent may be added and dissolved, or after mixing the organic solvent and the cellulose raw material, the ionic liquid may be added and dissolved.
  • the viscosity of the cellulose solution at 80 ° C. is preferably 100 to 10,000,000 Pa ⁇ s, more preferably 105 to 1,000,000 Pa ⁇ s, and even more preferably 110 to 100,000 Pa ⁇ s. By setting it as the said range, a refined cellulose fiber can be manufactured more suitably.
  • the viscosity of the cellulose solution can be measured in the same manner as the viscosity of the liquid containing the ionic liquid.
  • the method for spinning the purified cellulose fiber using the cellulose solution obtained as described above is not particularly limited.
  • the purified cellulose fiber is obtained by a known spinning method such as dry-wet spinning or wet spinning. Can be spun.
  • the purified cellulose fiber produced by the method for producing a purified cellulose fiber of the present invention is preferable because it has the same strength as a conventional regenerated cellulose fiber.
  • % means “% by mass” unless otherwise specified.
  • Example 1 The thermal stability of ionic liquids was investigated.
  • the ionic liquid according to the present invention include methyltributylphosphonium dimethyl phosphate, 1,3-dimethylimidazolium dimethyl phosphate, and 1-ethyl-3-methylimidazolium diethyl phosphate.
  • the thermal stability was examined using 1-ethyl-3-methylimidazolium acetate. Specifically, these ionic liquids were heated from room temperature at 10 ° C./min in a nitrogen atmosphere using a thermogravimetric measuring device (Q600, manufactured by T.A. Instruments Inc.) to change the temperature. , Mass change, and heat flow were measured.
  • Q600 thermogravimetric measuring device
  • the results for methyltributylphosphonium dimethyl phosphate are shown in FIG. 1, the results for 1,3-dimethylimidazolium dimethyl phosphate are shown in FIG. 2, and the results for 1-ethyl-3-methylimidazolium diethyl phosphate are shown in FIG. The results for 1-ethyl-3-methylimidazolium acetate are shown in FIG.
  • methyltributylphosphonium dimethyl phosphate, 1,3-dimethylimidazolium dimethyl phosphate, and 1-ethyl-3-methylimidazolium diethyl phosphate which are ionic liquids according to the present invention.
  • the mass reduction rate when the temperature reached 250 ° C. was 20% by mass or less, and had high thermal stability.
  • methyltributyl phosphonium dimethyl phosphate has a mass reduction rate of 20% by mass or less when reaching 300 ° C., and has been found to have very high thermal stability.
  • 1-ethyl-3-methylimidazolium acetate had a mass reduction rate of more than 20% by mass at around 200 ° C., and its thermal stability was insufficient.
  • Example 1 A plastic syringe (capacity) having a syringe needle (22G, 11/4) after heating 3 mL of the cellulose solution of sample 4 (viscosity 110 Pa ⁇ s at 80 ° C.) obtained in Experimental Example 2 to 80 ° C. 5 mL, manufactured by Terumo Corporation), and extruded through a syringe needle into a water bath. Spinning was performed by pulling the extruded filamentous material with tweezers to obtain purified cellulose fibers. The photograph figure which observed the obtained refined cellulose fiber using the digital camera is shown in FIG. From the photograph of FIG. 5, it was confirmed that purified cellulose fibers were obtained.
  • the method for producing purified cellulose fiber of the present invention is particularly useful in the textile industry.

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  • Engineering & Computer Science (AREA)
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Abstract

La présente invention porte sur un procédé de production de fibres de cellulose purifiée qui permet de produire des fibres de cellulose régénérée ayant le même niveau de résistance que celui de la rayonne à l'aide d'un liquide ionique ayant une stabilité thermique élevée sans produire un quelconque sous-produit ayant un impact élevé sur l'environnement. Le procédé de production de fibres de cellulose purifiée de la présente invention est caractérisé par la filature de fibres de cellulose purifiée à l'aide d'une solution de cellulose dissoute qui est produite par dissolution d'une matière première cellulosique dans une solution comprenant un liquide ionique ayant une fraction anionique représentée par la formule générale (A1) ou (A2) [dans la formule, R11, R12 et R13 représentent chacun indépendamment un groupe alkyle ; et R14 représente un atome d'hydrogène ou un groupe alkyle].
PCT/JP2011/065777 2010-07-12 2011-07-11 Procédé pour la production de fibres de cellulose purifiée WO2012008401A1 (fr)

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WO2013176113A1 (fr) * 2012-05-21 2013-11-28 株式会社ブリヂストン Câble, structure composite de câble en caoutchouc, et pneu
JP2013241709A (ja) * 2012-05-21 2013-12-05 Bridgestone Corp 精製多糖類繊維、ゴム−繊維複合体、ゴム−コード複合体、及びタイヤ
JP2013241705A (ja) * 2012-05-21 2013-12-05 Bridgestone Corp 精製多糖類繊維、コード、及びゴム−コード複合体、並びに、タイヤ及びランフラットタイヤ
JP2013241707A (ja) * 2012-05-21 2013-12-05 Bridgestone Corp ハイブリッドコード、ゴム−コード複合体、及びタイヤ
JP2013241706A (ja) * 2012-05-21 2013-12-05 Bridgestone Corp コード、ゴム−コード複合体及びタイヤ
JP2013241708A (ja) * 2012-05-21 2013-12-05 Bridgestone Corp 精製多糖類繊維、ゴム−繊維複合体、補強用コード、ゴム−コード複合体、及びタイヤ
WO2015163291A1 (fr) * 2014-04-21 2015-10-29 日東紡績株式会社 Procédé de fabrication de solution de cellulose

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WO2023171699A1 (fr) * 2022-03-08 2023-09-14 国立大学法人京都工芸繊維大学 Composition contenant un polymère, procédé de production d'une composition contenant un polymère, et procédé de production de fibres polymères

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WO2013176113A1 (fr) * 2012-05-21 2013-11-28 株式会社ブリヂストン Câble, structure composite de câble en caoutchouc, et pneu
JP2013241709A (ja) * 2012-05-21 2013-12-05 Bridgestone Corp 精製多糖類繊維、ゴム−繊維複合体、ゴム−コード複合体、及びタイヤ
JP2013241705A (ja) * 2012-05-21 2013-12-05 Bridgestone Corp 精製多糖類繊維、コード、及びゴム−コード複合体、並びに、タイヤ及びランフラットタイヤ
JP2013241707A (ja) * 2012-05-21 2013-12-05 Bridgestone Corp ハイブリッドコード、ゴム−コード複合体、及びタイヤ
JP2013241706A (ja) * 2012-05-21 2013-12-05 Bridgestone Corp コード、ゴム−コード複合体及びタイヤ
JP2013241708A (ja) * 2012-05-21 2013-12-05 Bridgestone Corp 精製多糖類繊維、ゴム−繊維複合体、補強用コード、ゴム−コード複合体、及びタイヤ
CN104508194A (zh) * 2012-05-21 2015-04-08 株式会社普利司通 帘线、橡胶-帘线复合体和轮胎
WO2015163291A1 (fr) * 2014-04-21 2015-10-29 日東紡績株式会社 Procédé de fabrication de solution de cellulose
JPWO2015163291A1 (ja) * 2014-04-21 2017-04-13 日東紡績株式会社 セルロース溶解液の製造方法

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