WO2015053226A1 - Longues fibres de cellulose ayant une résistance élevée et une élasticité élevée - Google Patents

Longues fibres de cellulose ayant une résistance élevée et une élasticité élevée Download PDF

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Publication number
WO2015053226A1
WO2015053226A1 PCT/JP2014/076713 JP2014076713W WO2015053226A1 WO 2015053226 A1 WO2015053226 A1 WO 2015053226A1 JP 2014076713 W JP2014076713 W JP 2014076713W WO 2015053226 A1 WO2015053226 A1 WO 2015053226A1
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cellulose
strength
fiber
less
gpa
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PCT/JP2014/076713
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English (en)
Japanese (ja)
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昌範 和田
彰 吉村
あかね 武永
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日東紡績株式会社
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Priority to JP2015541569A priority Critical patent/JPWO2015053226A1/ja
Publication of WO2015053226A1 publication Critical patent/WO2015053226A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • 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 regenerated cellulose long fiber having good spinnability, high strength and high elasticity, and a method for producing the same, in a regenerated cellulose fiber obtained by dissolving a cellulose raw material in an ionic liquid and reprecipitating it in a solvent by spinning.
  • fiber composite materials blended with high-strength and high-elastic fibers such as glass fibers are used in various fields such as automobile parts, sporting goods, building materials, and miscellaneous goods.
  • the glass fiber reinforced composite material that has been used as a lightweight high-strength material exhibits excellent characteristics during use.
  • glass fiber is used as the reinforcing fiber, a residue is generated at the time of disposal, which causes a problem that the load on the environment is large.
  • glass fiber is used as a base material for the printed wiring board in order to improve insulation and rigidity.
  • a residue is generated at the time of disposal, which causes a problem that the load on the environment is large.
  • cellulose having excellent properties such as high mechanical properties, dimensional stability, low thermal expansion, electrical insulation, and low specific gravity as the base material for fiber reinforced composite materials and printed wiring boards. It is being considered. Since cellulose is derived from plants and has biodegradability, no residue is produced at the time of disposal, and the environmental load during production and disposal is small (for example, Patent Document 1).
  • regenerated cellulose fibers such as rayon fiber, cupra fiber, and lyocell fiber are known.
  • any fiber uses a highly toxic solvent or a solvent having a high risk of explosion, etc., there is a risk in the production process, a highly safe method for producing cellulose fibers is required. It was.
  • Patent Document 2 describes that a nonwoven fabric is produced from cellulose dissolved in an ionic liquid, but there is no description about obtaining cellulose long fibers.
  • Patent Documents 3 and 4 describe that a cellulose raw material is dissolved in an ionic liquid to spin a fiber, but industrially stable spinning is not considered. If regenerated cellulose long fibers can be stably obtained, secondary processing such as cloth, cloth, sheet, membrane material, and cutting into lengths according to applications such as chopped strands will be easy. It can be used in a wide range of applications as electrical materials and fiber reinforced composite materials. For this reason, it has been necessary to industrially spin regenerated cellulose filaments stably using an ionic liquid.
  • the inventors of the present invention have established and already disclosed a technique that can be industrially stably produced from a cellulose raw material dissolved in an ionic liquid (Patent Document 5).
  • An object of the present invention is to obtain a regenerated cellulose long fiber with high productivity and high strength and high elasticity.
  • the present invention is a regenerated cellulose long fiber obtained by dissolving a cellulose raw material in an ionic liquid and spinning, wherein the average degree of polymerization is 500 or more and 3000 or less, and the average fiber diameter is 30 ⁇ m or less. It is a high strength and high elasticity cellulose continuous fiber.
  • the high-strength and high-elasticity cellulose continuous fiber means one having at least a tensile strength of 0.55 GPa or more and a tensile elastic modulus of 35 GPa or more.
  • the inventors of the present invention have obtained a regenerated cellulose long fiber obtained by dissolving a cellulose raw material in an ionic liquid and spinning it, and spinning it as a thin fiber having an average fiber diameter of 30 ⁇ m or less, whereby a tensile strength of 0.55 GPa or more, It has been clarified that the tensile elastic modulus is high strength and high elasticity cellulose long fiber of 35 GPa or more.
  • the high-strength and high-elasticity cellulose long fiber of the present invention is characterized in that the intramolecular hydrogen bond degree is 42% or more and 60% or less.
  • the degree of intramolecular hydrogen bonding indicates the bonding strength between adjacent glucose molecules in the cellulose molecule, and it is considered that the higher the value, the denser the structure.
  • the intramolecular hydrogen bond degree is 42% or more and 60% or less, a high strength and highly elastic cellulose continuous fiber having a tensile strength of 0.55 GPa or more and a tensile modulus of 35 GPa or more can be realized.
  • the high-strength and high-elasticity cellulose continuous fiber of the present invention is characterized in that the birefringence is 68 ⁇ ⁇ 10 ⁇ 3 or more and 90 ⁇ ⁇ 10 ⁇ 3 or less.
  • the birefringence is said to correlate with the molecular orientation in the entire structure consisting of a crystalline structure and an amorphous structure forming the fiber.
  • the birefringence is 68 ⁇ ⁇ 10 ⁇ 3 or more and 90 ⁇ ⁇ 10 ⁇ 3 or less, it is possible to realize a high-strength and highly elastic cellulose filament having a tensile strength of 0.55 GPa or more and a tensile modulus of 35 GPa or more.
  • the high-strength and high-elasticity cellulose continuous fiber of the present invention is characterized by having an intramolecular hydrogen bond degree of 45% or more and 60% or less.
  • a high-strength and highly elastic cellulose continuous fiber having a tensile strength of 0.80 GPa or more and a tensile modulus of 45 GPa or more can be obtained. If the fiber has a tensile strength of 0.80 GPa or more and a tensile elastic modulus of 45 GPa or more, it can exhibit characteristics equivalent to or higher than those of glass fibers when used as a reinforcing fiber or a substrate.
  • the high-strength and highly elastic cellulose continuous fiber of the present invention is characterized in that the birefringence is 70 ⁇ ⁇ 10 ⁇ 3 or more and 90 ⁇ ⁇ 10 ⁇ 3 or less.
  • a high-strength and highly elastic cellulose continuous fiber having a tensile strength of 0.80 GPa or more and a tensile modulus of 45 GPa or more can be obtained. If the fiber has a tensile strength of 0.80 GPa or more and a tensile elastic modulus of 45 GPa or more, it can exhibit characteristics equivalent to or higher than those of glass fibers when used as a reinforcing fiber or a substrate.
  • the cellulose raw material is dissolved in an ionic liquid so that the average degree of polymerization is 500 or more and 3000 or less so that the average fiber diameter is 30 ⁇ m or less. It is characterized by being spun into
  • the fiber-reinforced composite material of the present invention is characterized by being obtained by mixing high-strength and high-elastic cellulose long fibers and a resin.
  • a fiber-reinforced composite material having a strength equal to or higher than that of a composite material in which glass fibers are mixed as reinforcing fibers can be obtained.
  • the high-strength and high-elasticity cellulose long fiber refers to those having a tensile strength of 0.55 GPa or more and a tensile modulus of 35 GPa or more.
  • the long fiber means a fiber of 5 m or longer.
  • the high-strength and highly elastic cellulose long fiber of the present invention is characterized by having an average degree of polymerization of 500 to 3000 and an average fiber diameter of 30 ⁇ m or less.
  • the present inventors have found that there is a correlation between the average fiber diameter and the fiber strength, and when the average fiber diameter is 30 ⁇ m or less, the tensile strength is 0.55 GPa or more and the tensile elastic modulus is 35 GPa or more. It revealed that. If the tensile elastic modulus is 35 GPa or more, it has a specific elastic modulus substantially equivalent to that of glass fiber, and thus functions sufficiently as a substitute for glass fiber.
  • the average fiber diameter is preferably 22 ⁇ m or less because the tensile strength is 0.75 GPa or more and the tensile modulus is 40 GPa or more.
  • the average fiber diameter is 20 ⁇ m or less, and the tensile strength is 0.80 GPa.
  • the tensile modulus is more preferably 45 GPa or more, and the average fiber diameter is preferably 12 ⁇ m or less, more preferably 0.95 GPa or more and the tensile modulus is 50 GPa or more.
  • 1 ⁇ m can be mentioned at present from the viewpoint of manufacturing difficulty.
  • the high-strength and highly elastic cellulose filaments of the present invention have an average degree of polymerization of 500 to 3000 and an average fiber diameter of 30 ⁇ m or less. If the average degree of polymerization exceeds 3000, it is difficult to dissolve in the ionic liquid, and therefore, the influence of undissolved substances and the viscosity of the cellulose solution become too high, so that it is difficult to stably spin fine fibers. Further, if the average degree of polymerization is 500 or less, fibers having high tensile strength and high tensile modulus cannot be spun.
  • the high-strength and highly elastic cellulose continuous fiber of the present invention preferably has an average degree of polymerization of 500 or more and 2000 or less from the viewpoint of spinnability, and an average degree of polymerization of 600 or more and 1800 or less is excellent spinnability. Further, it is more preferable because a fiber having tensile strength and tensile elastic modulus can be obtained. In order to obtain a finer yarn, the smaller the average degree of polymerization, the easier it is to spin. However, in order to obtain a high strength and highly elastic cellulose filament, a certain degree of average degree of polymerization is required. When the average degree of polymerization is within the above range, it is possible to obtain cellulose continuous fibers having good spinnability and high strength and high elasticity.
  • the high-strength and highly elastic cellulose long fiber of the present invention has a tensile strength of 0.55 GPa or more and a tensile modulus of 35 GPa or more.
  • the tensile strength is preferably 0.70 GPa or more and the tensile modulus is 40 GPa or more, and the intramolecular hydrogen bond degree is 45% or more and 60% or less. More preferably, the tensile strength is 0.80 GPa or more and the tensile modulus is 45 GPa or more.
  • the high-strength and highly elastic cellulose continuous fiber of the present invention has a tensile strength of 0.55 GPa or more and a tensile elastic modulus of 35 GPa or more if the birefringence is 68 ⁇ ⁇ 10 ⁇ 3 or more and 90 ⁇ ⁇ 10 ⁇ 3 or less. Further, the birefringence is preferably 69 ⁇ ⁇ 10 ⁇ 3 or more and 90 ⁇ ⁇ 10 ⁇ 3 or less because the tensile strength is 0.75 GPa or more and the tensile elastic modulus is 40 GPa or more, and the birefringence is 70 ⁇ ⁇ 10.
  • the tensile strength is 0.80 GPa or more and the tensile modulus is 45 GPa or more, and the birefringence is 71 ⁇ ⁇ 10 ⁇ 3 or more and 90 ⁇ ⁇ 10 ⁇ 3.
  • a tensile strength above 1.00GPa tensile more preferably from becoming a more 50GPa modulus, degree birefringence 74 ⁇ ⁇ 10 -3 or more 90 ⁇ ⁇ 10 -3 der less It tensile strength above 1.05GPa, particularly preferred since the tensile modulus is equal to or greater than 53GPa, that the degree of birefringence is less than 80 ⁇ ⁇ 10 -3 or more 90 ⁇ ⁇ 10 -3, the tensile strength is 1.
  • the most preferable is 50 GPa or more and the tensile elastic modulus is 60 GPa or more.
  • the high-strength and highly elastic cellulose long fiber of the present invention has an average degree of polymerization of 700 to 2000, an average fiber diameter of 6 ⁇ m or less, an intramolecular hydrogen bond degree of 49% to 60%, and a birefringence of 74 ⁇ .
  • the tensile strength is 1.10 GPa or more and the tensile elastic modulus is 55 GPa or more
  • the average degree of polymerization is 700 to 2000 and the average fiber diameter is ⁇ 10 ⁇ 3 or more and 90 ⁇ ⁇ 10 ⁇ 3 or less.
  • it is 4 ⁇ m or less
  • the degree of intramolecular hydrogen bonding is 50% or more and 60% or less
  • the birefringence is 80 ⁇ ⁇ 10 ⁇ 3 or more and 90 ⁇ ⁇ 10 ⁇ 3 or less.
  • the high-strength and highly elastic cellulose long fiber of the present invention is obtained by dissolving a cellulose raw material in an ionic liquid composed of an imidazolium compound to obtain a cellulose solution. Next, the cellulose solution is extruded into a coagulating liquid in which the imidazolium compound is soluble and insoluble in cellulose, and the cellulose contained in the cellulose solution is coagulated to produce.
  • the cellulose raw material may be basically any material, for example, natural cellulose raw materials such as wood pulp, cotton, cotton linter, hemp, bamboo, abaca, regenerated cellulose fibers such as rayon, cupra, lyocell, and the like.
  • the resulting paper or clothing may be reused as a cellulose raw material.
  • natural cellulose raw materials are preferable, and among them, dissolving pulp, cotton linter and bamboo are preferable because of high cellulose purity and average cellulose polymerization degree.
  • the cellulose purity of the cellulose raw material is high, there are few impurities such as fats and oils, lignin and hemicellulose contained in the cellulose raw material, and the homogeneity of the cellulose solution, the spinnability during spinning, and the stretchability are not hindered.
  • the average degree of polymerization of cellulose is preferably at least 500 or more, and preferably 3000 or less in view of solubility, considering the physical properties of the obtained fiber.
  • Examples of the ionic liquid comprising an imidazolium compound include 1-ethyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium diethyl phosphate, 1-butyl-3. -Methylimidazolium acetate, 1,3-dimethylimidazolium acetate, 1-ethyl-3-methylimidazolium propionate, 1-allyl-3-methylimidazolium chloride and the like.
  • Preferred examples include 1-ethyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium chloride, and 1-ethyl-3-methylimidazolium diethyl phosphate.
  • cellulose having a relatively large average degree of polymerization having an average degree of polymerization of 800 or more can be easily dissolved.
  • the dissolution time and dissolution temperature may be adjusted according to the average degree of polymerization of cellulose and the type of ionic liquid, and the cellulose raw material may be dissolved until it becomes a homogeneous solution.
  • the heating means is arbitrary, but general heating means such as heating with an oven, heating with a water bath or oil bath, heating with a microwave, etc. may be used.
  • Stirring means are also optional, and among the known stirring methods represented by mechanical stirring with a stirrer or stirring blade, stirring by shaking the container, stirring by ultrasonic irradiation, etc., an appropriate means according to the scale etc. Adopt it.
  • the cellulose solution obtained by dissolving the cellulose raw material in the ionic liquid may be used as it is in the subsequent step, but if undissolved or insoluble matter remains in the solution, after filtering these It may be used.
  • the obtained cellulose solution may be used immediately, but may be used after being stored for a predetermined time as long as various properties such as moldability and physical properties of the molded product can be maintained.
  • the product is stored at a temperature below room temperature while paying attention to moisture absorption, it can be stored for a long time.
  • the dissolved cellulose is extruded from a nozzle and then spun by immersing it in a coagulation liquid.
  • a coagulation liquid water having a temperature in the range of 0 ° C. or higher and 100 ° C. or lower, or a lower alcohol, a polar solvent, a nonpolar solvent, or the like having a temperature in the range of ⁇ 40 ° C. or higher and 100 ° C. or lower can be used. In view of economy and work environment, it is preferable to use water.
  • the lower alcohol means an alcohol having 1 to 5 carbon atoms.
  • the spun regenerated cellulose long fiber is washed with water, but the remaining amount of the ionic liquid after washing is 10000 ppm or less when converted from the nitrogen amount detected by elemental analysis of the regenerated cellulose long fiber to the ionic liquid amount.
  • the cellulose solution may be extruded from nozzles having different diameters while controlling the extrusion flow rate, and spinning may be performed while controlling the winding speed and stretching conditions. For example, for a cellulose fiber having a fiber diameter of 20 ⁇ m, a winding speed is gradually increased until the fiber diameter reaches 20 ⁇ m while fixing an extrusion flow rate in a range of 0.01 to 1 mL / min using a nozzle having a diameter of 0.15 mm. It can be obtained by spinning while increasing the draw ratio.
  • thermoplastic resin in the fiber reinforced composite material examples include polyamide (nylon), polyacetal, polycarbonate, polyvinyl chloride, ABS, polysulfone, polyethylene, polypropylene, polystyrene, (meth) acrylic resin, fluororesin, and melamine resin.
  • curable resin examples include unsaturated polyester resins, epoxy resins, melamine resins, and phenol resins.
  • the fiber reinforced composite material includes a thermosetting resin
  • the fiber reinforced composite material includes a prepreg in which the thermosetting resin is semi-cured in addition to the fiber reinforced composite material in which the thermosetting resin is completely cured. Is also included.
  • the fiber reinforced composite material contains additives such as a low shrinkage agent, a flame retardant, a flame retardant aid, a plasticizer, an antioxidant, an ultraviolet absorber, a colorant, a pigment, and a filler as necessary. It may be.
  • Average fiber diameter The average fiber diameter was measured with a scanning electron microscope (manufactured by Hitachi, Ltd., SN-3400N). Ten fiber diameters were measured from the regenerated cellulose long fiber slice (fiber length 20 mm), and the average value was defined as the average fiber diameter.
  • Test piece (Tensile strength, tensile modulus, elongation) Tensile strength, tensile modulus, and elongation were tested using a tensile tester (Orientec, TENSILON RTC-1150A) under the conditions of test piece length: 50 mm, tensile test speed: 5 mm / min, load cell load: 2N. . The test piece was subjected to an absolute drying treatment at 110 ° C. for 1 hour, and was evaluated after cooling to room temperature in a desiccator.
  • the birefringence was measured by a compensator method using an incident light of 546 nm with a polarizing microscope (Olympus, BH-2), and obtained from the following calculation formula.
  • the birefringence is defined as a value measured by this method.
  • ⁇ n ⁇ n ⁇ + a ⁇ (x ⁇ 1605) ⁇ / d n: number of fringes found in the fiber cross section, ⁇ : wavelength of incident light (546 nm), d: fiber thickness (nm), a ⁇ : constant determined by light source and compensator (0.97), x: reading value (average polymerization) Every time)
  • the average degree of polymerization of cellulose was calculated by measuring the average molecular weight by the TAPPI T230 standard method (viscosity method) and dividing the measured average molecular weight by the molecular weight of glucose, which is a constituent unit of cellulose. In the present invention, the average degree of polymerization is defined as a value calculated by this method.
  • Crystal orientation The crystal orientation was measured according to JIS K0131. Specifically, the measurement was performed by the transmission method using a ROTA-Flex RTP-300 manufactured by Rigaku Corporation which is an X-ray diffractometer. The regenerated cellulose long fiber set on the fiber sample stage was irradiated with X-rays for 30 minutes, detected with an imaging plate detector, and the detected value was determined by analyzing with a reading device (R-AXIS DS3C, manufactured by Rigaku Corporation). In the present invention, the degree of crystal orientation is defined as a value measured by this method.
  • Crystallinity The crystallinity was measured by a reflection method using a Multi Flex manufactured by Rigaku Corporation which is an X-ray diffractometer. While the regenerated cellulose long fiber was placed on the sample stage, the sample stage was rotated at 120 rpm, X-rays were irradiated, and detection was performed using a scintillation counter at a measurement speed of 1 ° / min in a measurement range of 5 ° to 40 °. Based on the obtained spectrum data, the crystallinity was calculated using a peak separation method (area method) (Non-patent Document 1). In the present invention, crystallinity is defined as a value measured by this method.
  • the intramolecular hydrogen bond degree was measured by CPMAS method using AVANCE300 manufactured by Bruker, which is a solid-state NMR measurement apparatus.
  • the detection nucleus was 13 C (resonance frequency 75.4 MHz), the MAS condition was 3 kHz, and the contact time was 2 milliseconds.
  • the degree of intramolecular hydrogen bonding is defined as a value measured by this method.
  • Examples 1 to 8 and Comparative Examples 1 and 2 were spun by dissolving a cellulose raw material in an ionic liquid and then extruding it from a nozzle. At that time, fibers having different diameters were obtained by changing the nozzle diameter, winding speed, stretching conditions, and the like, and the physical properties were measured.
  • Comparative Example 1 the average degree of polymerization is 880, which is within the range of the present invention, but the average fiber diameter is as large as 41.0 ⁇ m, and in Comparative Example 2, the average degree of polymerization is smaller than the range of the present invention. It is the result of having measured the physical property of the obtained fiber. Comparative Examples 3 to 5 show the results of measuring physical properties of conventional regenerated cellulose long fibers within the fiber diameter range of the present invention. Comparative Example 3 is a cupra, Comparative Example 4 is a rayon, and Comparative Example 5 is a lyocell.
  • the regenerated cellulose long fibers obtained by dissolving a cellulose raw material in an ionic liquid and spinning the finer the average fiber diameter the higher the tensile strength and the tensile elastic modulus.
  • a thin regenerated cellulose long fiber having an average fiber diameter of 3.1 ⁇ m has a tensile strength of 1.54 GPa, a tensile elastic modulus of 62.5 GPa, and physical properties equivalent to or higher than those of glass fiber produced from E glass. It has.
  • Comparative Examples 3 to 5 show evaluations such as the tensile strength and tensile modulus of cupra, rayon, and lyocell having an average fiber diameter of about 10 ⁇ m.
  • other regenerated cellulose long fibers such as cupra, it is also possible that, as with the long fibers obtained by dissolving the cellulose raw material of the present invention in an ionic liquid and spinning, the strength and elasticity become higher as the fiber diameter becomes smaller. .
  • the regenerated cellulose long fiber of the present invention having an average fiber diameter of 27.9 ⁇ m shown in Example 8 has a high tensile strength and tensile strength even though the fiber diameter is about 3 times that of the cupra of Comparative Example 3. Elastic modulus is obtained. Therefore, even if another regenerated cellulose long fiber having a thin fiber diameter of about 3 ⁇ m, such as cupra, is obtained, it is considered that the regenerated cellulose long fiber of the present invention has a higher strength and higher elasticity. Absent.
  • Regenerated cellulose filaments such as rayon are high because of differences in crystallinity of cellulose due to various spinning conditions (stretching, drying, etc.), and low polymerization degree due to treatment with strong acid or strong alkali. It is considered that regenerated cellulose long fibers having physical properties are difficult to obtain.
  • the degree of intramolecular hydrogen bonding is an index indicating that hydrogen and oxygen are bonded more closely between cellulose molecular chains.
  • cellulose long fibers dissolved and spun in an ionic liquid, It was also shown that the degree of crystallinity, the degree of crystal orientation, the tensile strength, and the tensile modulus are highly correlated.
  • Comparative Examples 3 to 5 in the case of cellulose fibers produced by other methods, there is not always a strong correlation between the degree of intramolecular hydrogen bonding, tensile strength, and tensile modulus.
  • the cellulose raw material is dissolved in an ionic liquid, and the regenerated cellulose long fibers are spun to an average degree of polymerization of 500 to 3000 and an average fiber diameter of 30 ⁇ m or less. It has become possible to spin high-strength and high-elasticity cellulose long fibers that can replace glass fibers as a base material for reinforcing fibers and printed wiring boards.
  • Example 4 the regenerated cellulose filaments of Example 4 were actually aligned in one direction, impregnated with epoxy resin, drawn into the mold, heated and cured in the mold, and then removed from the mold.
  • a fiber reinforced composite material was prepared and evaluated for physical properties such as flexural modulus, flexural strength, and thermal expansion coefficient (developed product).
  • cupra and E glass fibers which are general regenerated cellulose long fibers and have relatively high physical properties, were mixed with a resin at the same fiber content to prepare a composite material. The results are shown in Table 2.
  • the flexural modulus and thermal expansion coefficient of the developed product were almost the same as when E glass fiber was used.
  • the regenerated cellulose long fiber of the present invention was obtained for the first time using the regenerated cellulose long fiber, and the same bending elastic modulus as that of the glass fiber, and the substrate of the printed wiring board required to have high elastic modulus and low thermal expansion A wide range of applications are expected as reinforcing fibers for fiber-reinforced composite materials.
  • the high-strength and high-elasticity cellulose long fiber of the present invention exhibits a much higher tensile strength and tensile modulus than conventional cellulose fibers, and the specific modulus obtained by dividing the tensile modulus by specific gravity. Is equal to or better than glass fiber. Further, when mixed with resin as a reinforcing fiber or a base material, a fiber-reinforced composite material having an excellent bending elastic modulus and a thermal expansion coefficient similar to that when E glass is used can be obtained.

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Abstract

La présente invention a pour objet de mettre en œuvre de longues fibres de cellulose régénérée ayant une résistance élevée et une élasticité élevée. Les longues fibres de cellulose obtenues en dissolvant un matériau cellulosique dans un liquide ionique et en filant la solution sont préparées sous la forme de longues fibres de cellulose ayant un degré moyen de polymérisation compris entre 500 et 3000 inclus et un diamètre moyen de fibre de 30 µm ou moins. Ainsi, il est possible de mettre en œuvre des fibres ayant une résistance élevée et une élasticité élevée.
PCT/JP2014/076713 2013-10-07 2014-10-06 Longues fibres de cellulose ayant une résistance élevée et une élasticité élevée WO2015053226A1 (fr)

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WO2017170745A1 (fr) * 2016-03-31 2017-10-05 古河電気工業株式会社 Composition de résine thermoplastique, procédé de production d'une composition de résine thermoplastique, produit moulé en résine renforcée par de la cellulose et procédé de fabrication d'un produit moulé en résine renforcée par de la cellulose
KR101856501B1 (ko) 2017-07-07 2018-05-11 광성기업 주식회사 미소셀룰로오스 장섬유 및 이의 제조방법
WO2019066070A1 (fr) * 2017-09-29 2019-04-04 古河電気工業株式会社 Article moulé
KR20200106047A (ko) * 2018-01-15 2020-09-10 렌징 악티엔게젤샤프트 리오셀 공정을 위한 리오셀 셀룰로오스의 재사용
WO2020218280A1 (fr) 2019-04-23 2020-10-29 三菱瓦斯化学株式会社 Composition et procédé de production de fibres de cellulose
US11466140B2 (en) 2016-03-31 2022-10-11 Furukawa Electric Co., Ltd. Thermoplastic resin composition, method of producing thermoplastic resin composition, molded article of cellulose-reinforced resin, and method of producing molded article of cellulose-reinforced resin
US11578192B2 (en) 2017-09-29 2023-02-14 Furukawa Electric Co., Ltd. Molded article
US11629244B2 (en) 2016-03-31 2023-04-18 Furukawa Electric Co., Ltd. Thermoplastic resin composition, cellulose-reinforced thermoplastic resin composition, method of producing cellulose-reinforced thermoplastic resin composition, molded article of cellulose-reinforced resin, and method of producing molded article of cellulose-reinforced resin
US11746215B2 (en) 2017-09-29 2023-09-05 Furukawa Electric Co., Ltd. Molded article
US11891498B2 (en) 2017-10-31 2024-02-06 Furukawa Electric Co., Ltd. Molded article provided with a resin part
WO2024048626A1 (fr) * 2022-09-01 2024-03-07 三菱瓦斯化学株式会社 Fibres de cellulose et leur procédé de production, composition de résine et article moulé

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