WO2004058883A1 - Composition polymere, fibres composites, leur procede de production et textile tisse - Google Patents

Composition polymere, fibres composites, leur procede de production et textile tisse Download PDF

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Publication number
WO2004058883A1
WO2004058883A1 PCT/JP2003/016750 JP0316750W WO2004058883A1 WO 2004058883 A1 WO2004058883 A1 WO 2004058883A1 JP 0316750 W JP0316750 W JP 0316750W WO 2004058883 A1 WO2004058883 A1 WO 2004058883A1
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WIPO (PCT)
Prior art keywords
acrylonitrile
weight
cellulose
polymer
cellulose acetate
Prior art date
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PCT/JP2003/016750
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English (en)
Japanese (ja)
Inventor
Shinichiro Tsutsumi
Ryo Ochi
Yasuyuki Fujii
Hiroko Matsumura
Nobuhisa Takayama
Original Assignee
Mitsubishi Rayon Co., Ltd.
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Application filed by Mitsubishi Rayon Co., Ltd. filed Critical Mitsubishi Rayon Co., Ltd.
Priority to JP2004544180A priority Critical patent/JP5016786B2/ja
Publication of WO2004058883A1 publication Critical patent/WO2004058883A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04B—KNITTING
    • D04B1/00—Weft knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
    • D04B1/14—Other fabrics or articles characterised primarily by the use of particular thread materials
    • D04B1/16—Other fabrics or articles characterised primarily by the use of particular thread materials synthetic threads
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/08—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C08L33/20—Homopolymers or copolymers of acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/02—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to polysaccharides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/18—Homopolymers or copolymers of nitriles
    • C09J133/20—Homopolymers or copolymers of acrylonitrile
    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/08—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyacrylonitrile as constituent
    • 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
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C08L1/12—Cellulose acetate
    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof

Definitions

  • the present invention relates to a composite functional fiber of cellulose acetate and an acrylonitrile-based polymer, which is suitable for a cloth material for use in clothing and sleeping, and an S3 ⁇ 4i method thereof.
  • acrylonitrile-based fiber PLUS is excellent in color development, bulkiness, heat retention, and soft texture, and is a material widely used in the field of clothing, bedding, interior, materials, and the like. It is mainly used in the form of a stable, but in recent years there has been a growing demand for the provision of a new wind ⁇ functional surface, especially for the development of new materials with deodorant function, moisture absorption and retention function and]! ⁇ performance.
  • Acrylo nitrile-based textiles which provide awakening performance to the quince, especially to improve the wet resistance, have been variously designed to solve this problem from » but have not been solved to the extent that they can be put to practical use.
  • the acrylonitrile-based polymer and cellulose acetate are dissolved in a common solvent such as dimethylacetamide, dimethylformamide, dimethylsulfoxide, etc., and a mixed solution of acrylonitrile-based polymer and cellulose acetate (for example, 20% by weight of polymer is dissolved in It is relatively stable and maintains a stable state without phase separation for a long time.By taking advantage of this point, a mixed solution of acrylonitrile-based polymer and cellulose acetate dissolved in a common solvent is used as a stock solution for spinning to give fibers.
  • the shaped fibers obtained are known to have excellent properties such as coolness and P wettability.
  • Such low compatibility between the acrylonitrile-based polymer and cellulose acetate has a significant effect on the physical properties of the fiber, such as fiber ⁇ 1 ⁇ and elongation. Shelving is likely to occur due to shelf resistance, for example, rubbing, resulting in poor abrasion resistance. In the woven or knitted fabric made of this fine pine, the fibrillated portion tends to have a whitish appearance, which is a fatal defect in product use and makes it very difficult to commercialize it.
  • Patent «2 Japanese Patent Application Laid-Open No. 9-2 9 14 16
  • Patent Document 4 Japanese Patent Application Laid-Open No. 55-629253 Disclosure of the Invention
  • An object of the present invention is to provide a functional polymer pirates that can be used for complexing cellulose acetate with an acrylonitrile-based polymer.
  • the present invention also provides a composite functional textile comprising cell acetate and an acrylonitrile-based polymer, which is suppressed in fibrillation, has excellent abrasion resistance, and has excellent hygroscopicity, deodorant properties, and excellent flammability.
  • the purpose is to do.
  • the present invention is to provide a fabric having excellent deodorant f production performance and excellent wear resistance. With the goal.
  • the present invention relates to the following matters.
  • Acetone-insoluble complex composed of cellulose acetate component of 10 to 70% by weight and acrylonitrile-based polymer component of 90 to 30% by weight of 20 to 100% by weight.
  • a polymer curd containing A polymer curd containing.
  • the polymer according to the above-mentioned 1 which is obtained by polymerizing a mixture of cellulose acetate and a bier monomer mainly composed of acrylonitrile.
  • polymerization initiator is a polymerization initiator selected from the group consisting of an organic peroxide, an azobis compound and potassium permanganate.
  • a fiber rip composed of cellulose acetate and / or cellulose and an acrylonitrile-based polymer, wherein the cell acetate and / or cellulose are dispersed as islands in the sea of the acrylonitrile-based polymer in the cross section of the fiber. And a size of the dispersed phase of cellulose acetate and / or cellulose is 200 nm or less.
  • a mixture of cellulose acetate and a vinyl monomer mainly composed of atarilonitrile having a weight ratio of 0.5 to 10 with respect to the cellulose acetate is added to an aqueous suspension using a polymerization initiator soluble in the vinyl monomer.
  • a polymer material obtained by turbid polymerization and an acrylonitrile-based polymer, wherein the ratio of the cellulose acetate component to the whole is 10 to 50% by weight, and the acrylonitrile-based polymer component contained in the polymer composition is ⁇ Mix the acrylonitrile-based polymer so that the total amount is 90 to 50% by weight, and use the undiluted solution in the common solvent of occluded cellulose and acrylonitrile-based polymer. M to the complex shop sales s3 ⁇ 4i method.
  • the fabric according to any one of the above items 12 to 14, comprising a fiber pulp containing a hidden cellulose and / or a cellulose component and an acrylonitrile-based polymer component. Since the polymer of the present invention has excellent compatibility with acrylonitrile-based polymers,
  • cellulose acetate can be complexed to a form not found in acrylonitrile-based polymers.
  • this polymer is mixed with an acrylonitrile-based polymer to produce fibers, fibrillation is suppressed, and fibers having excellent mechanical properties, for example, excellent abrasion resistance to friction and excellent metaphysics are obtained.
  • This fiber has practical properties, such as coolness, hygroscopicity, deodorant performance, and color development based on acrylonitrile polymer, based on cellulose acetate, and has excellent wear resistance as a force fiber. Therefore, this composite fiber is not a acrylonitrile-based material that has a new function, It is something new.
  • an acetate-insoluble complex of cellulose acetate and an acrylonitrile-based polymer and cellulose acetate that is separable from the complex are in a mixed state.
  • this polymer is obtained by suspension polymerization of a mixture of cellulose acetate and a vinyl monomer mainly composed of acrylonitrile, the cellulose acetate used in the suspension polymerization is difficult to dissolve in a solvent and has good physical properties.
  • the cellulose acetate is cellulose acetate having a degree of acetylation of 48 to 63%, particularly cellulose diacetate having a degree of acetylation of 48 to 56% and cellulose having a degree of acetylation of 56 to 63%.
  • it is rooster cellulose selected from triacetate.
  • the acrylonitrile-based vinyl monomer is a vinyl monomer containing acrylonitrile usually at least 50% by weight, preferably at least 60% by weight, more preferably at least 85% by weight.
  • the acrylonitrile-based polymer component in the polymer product of the present invention is a polymer of a vinyl-based monomer mainly composed of acrylonitrile, and the main component is an acrylonitrile unit, usually 50% by weight or more, preferably 60% by weight. It is a homopolymer or copolymer of acrylonitrile containing 85% by weight or more, more preferably 85% by weight or more.
  • Vinyl monomers that can be used together with acrylonitrile include acrylic acid, methyl methacrylate, their alkyl esters, vinyl acetate, acrylamide, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, glycidyl methacrylate, and glycidyl.
  • Examples thereof include diacrylate, sodium arylsulfonate, and sodium styrenesulfonate. These may be used alone or in combination of two or more.
  • biel acetate and methyl acrylate are preferably used in terms of quality and cost.
  • the polymer composition according to the present invention comprises 20 to 100% by weight of an acetone-insoluble complex containing a cellulose acetate component and an acrylonitrile-based polymer component and 80 to 0% by weight of cellulose acetate, preferably Acetone-insoluble complex 25-90% by weight, cellulose citrate 75-: Consists of a mixture of 0% by weight of L. It is necessary that the cellulose acetate accounts for 10 to 70% by weight and the acrylonitrile-based polymer accounts for 90 to 30% by weight in the composite.
  • the acetone-insoluble complex is formed during the polymerization of acrylonitrile-based vinyl-based monomer by the action of the monomer cell and the acid cell port.
  • a polymer is formed in a state of being dissolved in the cellulose, and the cellulose is insoluble in acetonitrile by having a structure in which cellulose and the etalilonitrile-based polymer are intertwined. Is insoluble in acetone, but is soluble in acrylonitrile-based polymer solvents, and the polymer composition of the present invention is well soluble in acrylonitrile-based polymers and cellulose acetate common solvents.
  • the acetone-insoluble complex in the polymer composition is less than 20% by weight or the cellulose acetate occupies less than 10% by weight or more than 70% by weight in the composite, cellulose acetate and acrylonitrile in the spinning dope are used.
  • the compatibility with the base polymer tends to decrease, and it is difficult to suppress the fibrillation of the resulting fiber punish due to scratching or the like, and furthermore it is difficult to obtain the flammability.
  • the polymer waste of the present invention comprises a mixture of cellulose acetate and a vinyl-based monomer mainly composed of acrylonitrile in a weight ratio of 0.5 to: L 0, preferably 1 to 5 with respect to cellulose acetate.
  • the amount can be reduced by aqueous suspension polymerization using a polymerization initiator soluble in a vinyl monomer mainly composed of acrylonitrile.
  • an organic initiator such as tert-butylhydroxy-2-ethylhexanoate, tert-butyl hydropoxide, or the like is used.
  • Peroxides, azobis compounds such as azobisisobutylinitrile, potassium permanganate, etc., especially organic peroxides and azobis compounds in that impurities such as metal ions do not remain in the product. Is preferably used.
  • the amount of the polymerization initiator used depends on the type of polymerization, polymerization conditions, etc., but is preferably 0.01 to 30 parts by weight, more preferably 100 parts by weight, based on 100 parts by weight of the HI-based monomer. Is from 0.01 to 10 parts by weight.
  • acrylonitrile to which a polymerization initiator! ⁇ is added in a drinking liquid obtained by dispersing cellulose acid in water such as deionized water is mainly used.
  • a vinyl monomer is added, and the monomer is polymerized by heating to an appropriate sculpture under a predetermined time.
  • the polymerization product is repeatedly washed with MJ and dehydrated to repeat the unreacted monomer and iron, thereby forming only the acetone-insoluble complex, or acetic acid not involved in the formation of the acetone-insoluble complex and this complex.
  • a polymer ⁇ g consisting of a cell opening is obtained.
  • Polymerization conditions vary depending on the type of polymerization and the type of liquor used.
  • examples of conditions of a polymerization initiator preferably used are as follows. Show.
  • the polymerization temperature is preferably 30 to 150 ° C, more preferably 50 to 80 ° C.
  • the polymerization time is preferably 0.5 to 12 hours, more preferably 3 to 9 hours.
  • tert-butyl hydroperoxide for example, 100 parts by weight of deionized water, 25 parts by weight of cellulose acetate having an acetylation degree of 55%, and acrylonitrile: Toryu
  • the polymerization is preferably 30 to 150. C, more preferably 50 to 80 ° C, and the polymerization time is preferably 0.5 to 4 hours.
  • the charging ratio is 1700 parts by weight of deionized water, 40 parts by weight of sulfuric acid, 55% of vinegar, 20 parts by weight of cellulose, and 15 parts by weight of cellulose.
  • Acrylonitrile: vinyl removal 93: 7
  • the polymerization is preferably at 20 to 60 ° C, and the polymerization time is preferably 0. 5 to 30 hours.
  • ⁇ IJ can initiate the reaction at a lower level than the boiling point of acrylonitrile (77.3).
  • a polymerization initiator such as ferrous sulfate may be used in combination.
  • the polymerization reaction is soluble in a vinyl monomer mainly containing acrylonitrile, so that a vinyl monomer mainly containing acrylonitrile is contained in cellulose acetate. It is presumed that the polymerization of the vinyl monomer during the polymer impregnation is selectively performed in the cellulose acid while the polymer is impregnated with the thigh, and as a result, an acetone-insoluble complex is formed.
  • the polymer compound of the present invention has an acetone-insoluble complex power of its constitution while significantly improving the compatibility between cellulose acid and an acrylonitrile-based polymer.
  • cellulose acid a common solvent of the base polymer
  • the fiber pu obtained by using the polymer composition of the present invention and mixing with an acrylonitrile-based polymer containing acrylonitrile as a main component has excellent abrasion performance of generating fibrillation by vigorous resistance, for example, rubbing, etc. It is possible to obtain a fine fiber with excellent flammability.
  • the polymer composition of the present invention may further include a weathering stabilizer, an antibacterial agent, a pigment, a dye, an antistatic agent, a conductive agent, an antifouling agent, and the like.
  • a composite function based on the variability of the acrylonitrile polymer can be imparted to the fiber.
  • the following novel multifunctional fiber pu can be provided by shaping the fiber of the present invention into a fiber pulp in combination with an acrylonitrile-based polymer.
  • the fiber composite pine of the present invention is a fiber python substantially composed of cellulose cellulose and / or an acrylonitrile-based polymer containing cellulose and acrylonitrile as main components. And / or cellulose is dispersed as islands in the acrylonitrile-based polymer sea.
  • the size of the broiler cellulose and / or the cellulose fraction is less than 200 nm in circle average 3 ⁇ 4 ⁇ . The smaller the size, the better, but it is usually 20 nm or more.
  • the composite functional fiber of the present invention is characterized in that cellulose acetate and / or cell mouth are 10 to 50% by weight and acrylonitrile-based polymer is 90 to 50% by weight. It is assumed that. When cellulose acetate and / or cellulose is less than 10% by weight, that is, when the acrylonitrile-based polymer exceeds 90% by weight, it is not possible to obtain hygroscopicity, deodorizing property, etc. based on cell acetate mouth. When the cellulose acetate content exceeds 50% by weight, the spinnability during spinning during fiber drawing and the occurrence of stretching breakage occur frequently, resulting in poor spinnability. As well as the fiber properties, the fiber properties deteriorate and the spinning process passability becomes poor.
  • the tflt self-composite fiber pine of the present invention has a peak of infertile contact (tan ⁇ 5) at least at a low temperature side of 120 ° C. or more in the measurement of dynamic viscosity. This is achieved by the fact that the acetate acetate is dispersed in the acrylonitrile-based polymer at the nm level. It is a characteristic. Since the polymer exfoliated product of the present invention described above greatly enhances the compatibility of cellulose acetate with the acrylonitrile-based polymer, when the polymer product of the present invention is dissolved in a common solvent together with the acrylonitrile-based polymer, Cellulose acetate is compatible in the polymer at the liver level. For this reason, when molded into fibers, the motility of the acrylonitrile-based polymer can be restricted, and the composite fibers have improved heat resistance.
  • the physical properties of 3 ⁇ 4 ⁇ which represents the flammability of flame, can be determined by the loss tangent (tan) by measuring dynamic viscoelasticity.
  • tan loss tangent
  • t an 6 is an index representing good motility, and is defined as the ratio between the storage elasticity E ′ and the loss elasticity E ′′ when the dynamic viscoelastic properties are measured.
  • the peak of ta ⁇ ⁇ of acrylonitrile-based cafe ⁇ is gathered at around 100 to 110, and the peak of tan ⁇ of Sas cellulose cellulose fiber is around 200 to 210 ° C. Is done.
  • acrylonitrile-based polymer and cellulose acetate are simply mixed to form a composite fiber, two peaks of ta ⁇ ⁇ due to the phase-separated phases are heard.
  • the peak position changes only by changing the peaks of each peak according to the exact ratio. do not do.
  • the position of the peak shifts closer to the other component.
  • the peak of tan (5 due to the acrylonitrile-based polymer is shifted to the high temperature side, and the peak of ta ⁇ ⁇ due to cellulose acetate is shifted to the low temperature side. That is, acrylonitrile
  • the motility of the acrylonitrile-based polymer liver is restricted, and a large amount of heat energy is required for the liver to move, thereby improving the fiber toughness of the fiber.
  • the tan (5 peaks are united at the Jt position determined by the exact ratio.
  • the compatibility between the acrylonitrile-based polymer and the cellulose acetate can be remarkably enhanced, so that ta ⁇ ⁇ caused by the acrylonitrile-based polymer is
  • the peak S can be shifted to 120 ° C. or higher, and the composite fiber of the present invention has a tan 6 peak at least on the low temperature side in the measurement of dynamic viscoelasticity at 120 ° C. or higher. There is a certain fiber.
  • At least the peak temperature of ta ⁇ ⁇ on the low temperature side means that there are two peaks of ta ⁇ ⁇ .
  • the peak of tan ⁇ is united into one, it refers to the united peak temperature.
  • the composite functional fiber pent of the present invention is repeatedly subjected to a method of complying with JISP 8121 in a disk lifter unit with a disk clearance of 0.05 mm and a disk rotation of 3 ⁇ 4500 rpm repeatedly 5 times.
  • the difference in freeness between the freeness R1 after the beating treatment and the freeness R0 before the beating treatment is 200 or less. It is difficult to split and its fibrillation is suppressed. It is. This is a characteristic obtained by dispersing cellulose acetate at a very small level in the acrylonitrile-based polymer.
  • the composite cafe of the present invention can perform S3 ⁇ 4i as follows, for example. That is, the above-described polymer pirates of the present invention and an acrylonitrile-based polymer containing acrylonitrile as a main component (hereinafter referred to as an acrylonitrile-based polymer used in combination) are composed of 10 to 40% by weight of occult cellulose, acrylonitrile, The polymer-based component (total of the component derived from the polymer material and the acrylonitrile-based polymer used in combination) is 90 to 60% by weight, and dissolves in a common manner between the cellulose and the acrylonitrile-based polymer.
  • a spinning dope is prepared by using the spinning dope to spin the spinning dope to obtain the composite fiber pine of the present invention.
  • cellulose cellulose may be further added to the extent that the ratio is equal to the sum of the kamachi ratio.
  • the acrylonitrile-based polymer used in combination is a polymer of a biel-based monomer mainly composed of acrylonitrile, and contains acrylonitrile units as a main component, usually at least 50% by weight, preferably at least 60% by weight. More preferably, it is a homopolymer or copolymer of acrylonitrile containing 85% by weight or more.
  • the vinyl monomer that can be used together with acrylonitrile include the same ones as described with respect to the “Polymerized polymer of the present invention”.
  • the common solvent used in preparing the spinning solution is not particularly limited, and may be any of an inorganic solvent and an organic solvent.However, in consideration of a recovery process and the like, dimethylformamide, dimethylacetamide, dimethylsulfoxide, etc. It is preferable to use an organic solvent. There is no particular limitation on the amount of the spinning dope, but it is preferable that the polymer content in the spinning dope is 10 to 40% by weight in consideration of productivity and spinning stability.
  • the spinning method may be the same as that used for I ⁇ of the acrylonitrile-based pine fiber, i.e., the wet yarn method, the dry-wet yarn method, or the dry-wet yarn method.
  • the coagulated yarn is stretched 2 to 8 times, and the solvent is removed in hot water at 80 to 100 ° C, an oil agent is applied, and
  • the spinning solution is first discharged into the air from a coagulation bath and a nozzle concealed for a certain period, and then coagulated from a solvent and water. After coagulation in a bath, solvent removal, stretching, application of an oil agent, and the like are repeated to obtain the multifunctional fiber of the present invention.
  • the composite fiber is made of cellulose acetate and / or cellulose acetate.
  • a composite fiber composed of cellulose and an acryl-based polymer is obtained.
  • the ratio of cellulose conversion can be appropriately set between 0 and 100% depending on the degree of alkali treatment.
  • the morphology is changed by the alkali treatment.
  • the cellulose which was initially an island when viewed from the cross section of the fiber, is partially or completely cellulized, but remains in the sea area of the acrylonitrile-based polymer. It is dispersed as an island.
  • the form of the composite restaurant of the present invention is not particularly limited, and may be any form such as a stable, a filament, and a shot-cut fiber.
  • the cross-sectional shape may be any of a circle, a bean, an oval, a dockbone, and a flat tie.
  • the fiber reinforced of the present invention is excellent in heat resistance in addition to the properties derived from the main acrylonitrile-based polymer and excellent in abrasion resistance. It has a function.
  • the fabric of the present invention contains cellulose acetate and / or a cell mouth component and an acrylonitrile-based polymer component, and has a deodorization rate of 90% or more for acetic acid and a deodorization rate of 90% or more for nonenal, In addition, the fabric has a weight loss rate of 1% or less when subjected to 500,000 times of friction by the Martindale method.
  • This fabric can be used as a knit, woven or non-woven fabric for various items such as clothing, underwear, socks, etc., blankets, riichi pets, mats and other bedding. If the deodorizing rate for acetic acid or nonenal is less than 90%, the class cannot be completely eliminated and its adsorption capacity is insufficient.
  • the weight loss rate of the fabric exceeds 500% when subjected to 500 000 frictions by the Machindale method, and the appearance of the fabric changes significantly due to friction, and pilling is likely to occur. And the quality of textile products is insufficient.
  • the fabric of the present invention contains at least 5% by weight, preferably at least 10% by weight, of the body cellulose and / or the cellulose component.
  • the content is 10% by weight or more, it has excellent deodorizing performance against acid components.
  • the cellulose acetate component is preferably 50% by weight or less of the whole fabric.
  • the fabric of the present invention specifically contains cellulose acetate and / or a textile containing a cellulose component and an acrylonitrile-based polymer component, and more specifically, the composite fabric of the present invention described above. Can be obtained by incorporating in a fabric. Therefore, it is preferable that the acetate component in the cell mouth is only derived from the composite fiber of the present invention.
  • the amount of the conjugate fiber of the present invention may be an appropriate amount depending on the use of the fabric. However, from the viewpoint of deodorizing performance and abrasion, the amount of the conjugate fiber should be the above-mentioned cellulose content. It is preferable to include it in the fabric.
  • the acrylonitrile-based polymer component in the fabric is the sum of the one derived from the composite fiber of the present invention and the one derived from the usual acrylic used together with the composite H-Pure.
  • the content of the acrylonitrile-based polymer component is 10 to 90% by weight of the whole fabric.
  • the “acrylonitrile-based polymer component” is synonymous with the “acrylonitrile-based polymer component” described in connection with poison.
  • the fabric of the present invention may contain natural fibers such as cotton, wool, etc.
  • Other fibers such as polyester fiber reinforced, such as polyester fiber reinforced, rayon fiber reinforced, etc. can be included.
  • the content can be determined according to the purpose of the fabric, for example, by increasing the content of the acrylonitrile-based polymer component and by adding the amount of moisture absorption.
  • the exfoliated polymer obtained by the suspension polymerization was stirred and dissolved in frozen powder and acetone to a concentration of 1% by weight. This solution is separated by centrifugation into an object and supernatant » The amount of the complex insoluble in setone was determined. The amount of rooster cellulose not involved in the formation of a complex other than the complex in the polymer can be obtained by exposing the amount of the complex.
  • the acetone-insoluble complex was dissolved in deuterated dimethylilesulfoxide at a concentration of 4% by weight, and the ratio of cellulose acetate to the acrylonitrile-based polymer was calculated from 1 H-NMR measurement.
  • the polymer material and the acrylonitrile polymer were stirred and dissolved in a solvent so as to be 8% by weight. A small amount of this solution was sandwiched between glass plates, and the compatibility was confirmed with a phase contrast microscope. The knee data was destroyed with image processing software (Image Pro Plus), and the phase separation size ⁇ m) was calculated.
  • the gas iU in the flask was measured with a (Kitakawa-style gas container). As a target, the same measurement was performed for £ W, which is the dimension of, and the gas concentration in the flask after standing for 1 hour was determined. The deodorization rate was calculated from the ratio of the gas contained in the sample to the target gas.
  • the gland After leaving the grate for 5 g in an environment of 40 and 90% RH for 24 hours, the gland was sampled, its mass and its mass were measured, and the moisture absorption A a (%) was calculated by the following equation. Similarly, the moisture absorption rate A b (), which is the same as the basket method at 20% and 65% RH, was also calculated by the following equation.
  • the freeness was determined after the beating treatment with a disc refineer shown below.
  • the freeness evaluation was carried out by forming the obtained tu 4 »uru into a 3 mm long floc and then fixing the force floc.
  • This solution was dispersed in water so as to have a solid content of 6% by weight, and this liquid was discarded using a disc refiner (KRK high-dissociation disc refiner NO2500—I type, manufactured by Kumagaya Riki Kogyo Co., Ltd.). Process with a clearance of 0.05 mm and a disk rotation speed of 500 rpm. This process was repeated several times, and the filtrate of the treated solution was measured according to the Canadian standard freeness test method of JISP 8121.
  • the freeness before beating treatment by this disc refiner was R 0, and the 3 ⁇ 4
  • 7 ⁇ degree after repeated beating treatments was R 1, and the i7K difference ( R 0 — R 1) was determined. . It can be determined that the lower the value of ⁇ R, the more difficult the so-called fiber is to split, and the greater the effect of suppressing fibrillation.
  • the obtained composite machine Yoshika Akishima was cut by a Miku mouth tome in a direction perpendicular to the axis of the fiber optic to obtain a section, which was stained with ruthenium tetroxide vapor at room temperature for 10 minutes, and the stained section was subjected to TEM injection.
  • the size (nm) of the dispersed phase of cellulose was measured.
  • Image processing software Image Pro Plus was used to measure the size of the dispersed phase, and for at least 100 dispersed phases, the diameter equivalent to a circle was determined from the area of each dispersed phase, and the average value was calculated.
  • the obtained compound machine »Pure (approximately 200 dtex) was sampled and aligned without slack, using a DMS 200 manufactured by Seiko Co., Ltd., test length 20 mm, frequency 10 H
  • the dynamic viscoelasticity in the range from room temperature to 250 ° C was measured at z and ffi3 ⁇ 42 ° CZ, and the peak of ta ⁇ located at least on the low temperature side due to the polyacrylonitrile-based polymer was determined. .
  • Wa Weight of fabric before treatment
  • Wb Weight of fabric after Martindale 500,000 times treatment
  • Fabric weight loss R (%) (Wa-Wb) / Wa X 1 0 0
  • a wear test was carried out by five people from the country, and the appearance change after wearing for 12 hours was so-called. The judgment was made in two stages according to the following.
  • Cellulose acetate (degree of decay 55%) Cellulose diacetate M-flake manufactured by Daicel Corporation 100 parts by weight was dispersed in 550 parts by weight of deionized water, and 1N-sulfuric acid 20 parts 100 parts by weight and 100 parts by weight of a 0.3% by weight aqueous solution of potassium permanganate in the polymerization j were added to obtain a pH of 5, and the pH was adjusted to 50.
  • Cellulose acetate degree of acetylation: 55%) (Cellulose diacetate Ml flake, manufactured by Daicel Co., Ltd.) 60 weight%! 5, 200 parts by weight of deionized water, tert- Butyl hydroperoxide 2.9 parts by weight mixed in a 3 L separable flask and stirred at 30 ° C for 1 hour After that, the temperature was raised to 70 ° C, and then 1 part by weight of ⁇ -K) and 1 part by weight of Rongalite were added as auxiliaries, and after holding for 30 minutes, 140 parts by weight of AN monomer was added. Added over 1 hour.
  • the obtained polymer curd and AN 93% by weight and VA 7% by weight of an AN polymer were mixed with each other to make the mixture 100% by weight so that the cellulose acetate in the mixture was 30% by weight.
  • the AN polymer was mixed at a ratio of 18.4.3 parts by weight, and further dissolved in dimethylacetamide to a concentration of 18% by weight to prepare a spinning dope, and the compatibility of the spinning dope was confirmed. Then, the spinning stock solution is subjected to a wet-weft process using a pore diameter of 60 ⁇ ,?
  • the nozzle was discharged into a coagulation bath of a 40% aqueous solution of dimethylacetamide at a bath temperature of 40 ⁇ , and the coagulated yarn was stretched 5 times under moist heat, The solvent was removed, the oil was applied, and the mixture was densified. The mixture was further treated in a calo-pressure steam of 135 to obtain a single-fiber 4 dtex tow-like restaurant.
  • the obtained fiber was formed into a floc having a length of 3 mm. Then, according to the method of fibrillation by measuring the freeness by a disc refiner, the 3 ⁇ 4 ⁇ ⁇ degree (R 0) before lipolysis was repeated 5 times. The freeness after the round beating treatment (Rl) and the difference in freeness were determined. In addition, the dispersed phase size and paintability of cellulose acetate on the fiber cross section were measured, and the results are shown in Table 3. Example 4 to lock Table 3 also shows the results for 7. Table 3
  • the spinning dope has a small phase separation size and good compatibility.
  • the fiber pine obtained by spinning using this spinning stock solution has an extremely small value of ⁇ R in a disc refiner and has an improved durability. It can be seen that cellulose acetate is dispersed as fine islands in the cross section of the fiber. According to the metaphysical dragon, the obtained fiber pu had a high tan 6 peak temperature as measured by dynamic viscoelasticity, and had improved heat resistance. The above-mentioned dragon can be said about ⁇ key in Examples 4-8. Compare!
  • the AN polymer (AN 93% by weight, VA 7% by weight), cellulose acetate (degree of acetylation 55%) (cellulose diacetate Ml flake manufactured by Daicel Co., Ltd.) and block are shown in Table 4.
  • a mixture of the copolymer was dissolved in dimethylileacetamide to a concentration of 22% by weight to prepare an undiluted spinning solution. Thereafter, wet spinning was performed under the same conditions as in Example 3 to obtain a tow having a single fiber density of 4 dte X. I got a fiber rape.
  • the block copolymer had a segment having an affinity for an acrylonitrile-based polymer and a segment having an affinity for cellulose acetate, and was prepared by the following method. Table 4
  • the ⁇ ⁇ obtained in Comparative Examples 1 to 5 was used to determine the drainage wisteria ⁇ R, and the results are shown in Table 5 together with the results of Difficult Example 3.
  • do the fiber pulps obtained by comparisons 1 to 5 deodorize acetic acid and absorb moisture? 13 ⁇ 4 was performed, and the results are shown in Table 5.
  • the fiber reinforced according to Comparative Examples 1 to 5 has a large phase separation size of the spinning raw material and is easy to fibrillate, so that it is inferior in abrasion resistance as compared with the occlusion according to Example 3, and the flammability is also high.
  • the properties were not improved at all, and the deodorizing properties and the hygroscopicity were also poor.
  • the fibers were not fibers having a composite function. Table 5
  • the obtained product was washed with water and dehydrated, and then leaked at 70 ° C. to obtain a polymer pirate comprising an acetate-insoluble complex and cellulose acetate shown in Table 2.
  • the obtained polymer II ⁇ and AN 93% by weight and VA 7% by weight of an AN polymer were added to 100 parts by weight of the polymer yarn so that the cellulose acetate in the mixture was 30% by weight.
  • the AN polymer was mixed at a ratio of 1 34.2 parts by weight, and further dissolved in dimethylacetamide so that the concentration became 1 8% by weight.
  • a spinning stock solution was prepared, and its compatibility was determined based on the phase separation size in the spinning stock solution. Did. Thereafter, wet yarn was formed under the same conditions as in Example 3 to obtain a tow-shaped fiber nit of single dtex. Table 3 shows the results of the obtained fibers.
  • Example 3 an aqueous suspension polymerization was carried out in the same manner as in Example 3 except that cumene hydroperoxide was used as a polymerization initiator, and a polymer of cellulose acetate and an acetate-insoluble complex shown in Table 2 was obtained.
  • AN93 and 7% by weight of VA An AN polymer is mixed with a polymer thread at a ratio of 17.9.2 parts by weight of AN polymer to 100 parts by weight of the polymer yarn so that the rooster cellulose in the mixture becomes 30% by weight.
  • a stock solution for spinning was prepared by dissolving the solution in dimethylacetamide to a concentration of 18% by weight, and the compatibility in the stock solution for spinning was evaluated. Thereafter, wet yarn was produced under the same conditions as in Example 3 to obtain a toe-shaped fiber rip having a single fiber density of 4 dte X. Table 3 shows the results of the consultation of the obtained fines.
  • Example 4 azobisisobutyronitrile was used as the polymerization initiator, but a polymer suspension comprising an acetate-insoluble complex and cellulose acetate shown in Table 2 by aqueous suspension polymerization as in Example 4 was used. I got something. The obtained polymer yarn! And 100% by weight of the polymer pirates were combined with 93% by weight of AN and 7% by weight of an AN polymer so that the cellulose content in the mixture was 30% by weight. On the other hand, the AN polymer was mixed at a ratio of 17.8 parts by weight, and further dissolved in dimethylacetamide to a concentration of 8% by weight to prepare a spinning stock solution, and the compatibility of the spinning stock solution was evaluated. Thereafter, wet spinning was performed under the same conditions as in Example 3 to obtain a tow-shaped fiber having a single fiber density of 4 dtex. Table 3 shows the I ⁇ results of the obtained fine pu.
  • the polymer exfoliated product obtained in the same manner as in Example 7 and AN 93% by weight and VA 7% by weight of an AN-based polymer were mixed with each other so that the cellulose acetate in the mixture was 30% by weight.
  • An AN polymer was mixed at a ratio of 107.5 parts by weight to 100 parts by weight, and further dissolved in dimethylacetamide so as to have a concentration of 18% by weight to prepare a spinning stock solution.
  • the hiding between the nozzle and the coagulation liquid orchid was set to 12 mm, and the spinning solution was used with a hole diameter of 120 m.
  • the resulting solution stream was immediately extruded from a nozzle of 60H into the air, and was immediately introduced into a coagulation bath of a 70% by weight aqueous solution of dimethylacetamide at a bath temperature of 40 ° C. to form a fine pulp. After that, it was washed with water, stretched 3.5 times in boiling water, further dried and stretched 1.2 times, and then 270. A 10% relaxation was performed on a hot plate of C to obtain a composite fiber filament with 8 dtex single fiber and 170 d tex total separation. Table 3 shows the pain results of the obtained fibers.
  • the pine fiber obtained in Example 3 was treated at 60 ° C for 30 minutes under the conditions of 12 wt% of Na ⁇ ⁇ H added to the fiber pu under the conditions of 12 wt%.
  • the moisture-absorbing performance of Senpuru was improved.
  • AN polymer (AN 93% by weight, VA 7% by weight) and rooster cell mouth (degree of acetylation 55%) (cellulose diacetate manufactured by Daicel Corporation)
  • a mixture of Ml flakes) and a block copolymer is dissolved in dimethylacetamide so as to have a wisteria content of 22% by weight to prepare a spinning stock solution. Thereafter, spinning is performed in the same manner as in Example 8, and spinning is performed.
  • ⁇ 2.8 dtex a composite fiber filament of Tole I3 ⁇ 4l70 dtex was obtained.
  • the AN polymer (AN 93% by weight, VA 7% by weight) and cellulose acetate (acetylation degree 55%) (Cellulose diacetate Ml manufactured by Daicel Corporation) Flake) and a block copolymer are dissolved in dimethylacetamide so as to obtain 22% by weight to prepare a stock solution for spinning. Thereafter, spinning is performed in the same manner as in Example 8, and the single fiber is prepared. 2.8dtex, toe! ⁇ A filament of 170 dtex composite fiber was obtained.
  • Example 9 since the cell opening of cellulose acetate progressed due to the treatment with alcohol, it can be seen that as a result, the performance of absorbing moisture and the dampness were improved. Table 6
  • Example 7 The multi-functional device obtained in Example 7 was cut into 51 mm and cut into a 1.7-dtex commercially available acrylic fiber (Mitsubishi Rayon (fine 815)) so that its weight ratio was 50% by weight. A 1/52 drunk spun yarn was prepared and dyed, and three dyed spun fibers were applied to the yarn, and FTY (40/75)
  • FTY is a twisted yarn of polyurethane long fiber 75 decitex and polyamide long fiber 40 decitex.
  • the composite functional fiber obtained in Example 7 was pressed to a height of 51 mm to obtain a single fiber
  • the spun yarns of 1Z52 group were prepared by heating to 0% by weight and dyed.
  • the yarn is made of two dyed spun yarns and 1/30 ⁇ cotton spun noble yarn, and the back yarn is made of FTY (40/75), and the back yarn is 4 inches in diameter and has 1 36 needles.
  • a sock knitting machine was used to knit socks by 2 ⁇ 2 rib knitting.
  • Example 9 Spinning obtained in Example 9! After dyeing ⁇ , the fabric is knitted by smooth knitting of 22G, 33 inches, 60 lots, and each knit from the knitted fabric! Underwear of size ⁇ was made.
  • socks were prepared in the same manner as in Example 10.
  • the underwear was prepared in the same manner as in Example 11 using the composite fiber penta obtained in Example 9:
  • the composite machine obtained in Comparative Example 2 was weighed to 51 mm, and the weight ratio of a single fiber 1.7 1.7 dtex commercially available acrylic fiber ⁇ (Mitsubishi Rayon (Fine 815)) to 50% by weight A 1/52 group of spun yarn was prepared in this manner, and three dyed spun yarns were put on the yarn, and one FTY (40/75) was put on the shelves. Knitted socks with 2 x 2 ribs.
  • the fabric was knitted by smooth knitting of 22G, 33 inches, 60 lots, and underwear was produced from the knitted fabric to the size of each fiber. .
  • Examples 9 to ⁇ 2 have excellent deodorizing performance against rooster and nonenal, and also have a base cloth obtained by performing a Martindale friction tester 500 times as compared with Comparative Examples 8 to 10. It can be seen that the fabric has a very small weight loss rate and has almost no change in appearance due to the fitting test 1 ⁇ ⁇ >.
  • acrylonitrile-based fibers especially in the form of woven fabric, such as knits and jerseys.
  • a fiber material or fabric suitable for the field of knitted fabrics especially garments such as woven fabrics requiring steam ironing, curtains, nipples, pores, blankets, mats, mattresses, etc. Can be used.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Artificial Filaments (AREA)
  • Woven Fabrics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)
  • Multicomponent Fibers (AREA)

Abstract

L'invention concerne des fibres composites obtenues par une solution à filer contenant, sous forme dissoute, un polymère acrylonitrile et une composition polymère qui contient (a) 20 à 100 % en poids d'acétone, une matière composite insoluble contenant 10 à 70 % en poids d'ingrédient d'acétate de cellulose et 90 à 30 % en poids d'ingrédient polymère d'acrylonitrile et (b) 80 à 0 % en poids d'acétate de cellulose. Les fibres sont des fibres composites fonctionnelles qui sont protégées de toute fibrillation, ont une excellente résistance à l'usure, procurent une excellente sensation de fraîcheur et ont une excellente capacité hygrométrique, désodorisante et thermorésistance.
PCT/JP2003/016750 2002-12-26 2003-12-25 Composition polymere, fibres composites, leur procede de production et textile tisse WO2004058883A1 (fr)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009155626A (ja) * 2007-12-06 2009-07-16 Mitsubishi Rayon Co Ltd 耐熱性向上剤、熱可塑性樹脂組成物及び成形品
JP2011051127A (ja) * 2009-08-31 2011-03-17 Mitsubishi Rayon Co Ltd 樹脂成形体の製造方法
JP2012102454A (ja) * 2011-11-28 2012-05-31 Mitsubishi Rayon Co Ltd アクリロニトリル系重合体とセルロース系重合体が均一に混合された繊維を含有する不織布。
JP2013199718A (ja) * 2012-03-26 2013-10-03 Mitsubishi Rayon Co Ltd アクリル系消臭繊維並びにそれを含む紡績糸および織編物。
JP2015030925A (ja) * 2013-08-01 2015-02-16 三菱レイヨン株式会社 抗菌防臭性、消臭性を有するアクリル系複合繊維並びにそれを含む紡績糸および織編物
JP2016187549A (ja) * 2015-03-27 2016-11-04 株式会社リブドゥコーポレーション 消臭材およびそれを備えた吸収性物品
WO2018098072A1 (fr) * 2016-11-22 2018-05-31 E. I. Du Pont De Nemours And Company Procédé de fabrication de fibres de polyacrylonitrile

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JPS56148915A (en) * 1980-04-07 1981-11-18 Asahi Chem Ind Co Ltd Novel composite fiber
JPS6454014A (en) * 1987-08-25 1989-03-01 Nippon Oils & Fats Co Ltd Production of graft copolymer resin
JPH10158928A (ja) * 1996-11-19 1998-06-16 Kanebo Ltd 分割性アクリル系合成繊維及びその製造方法

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DE69936C (de) * B. MÜNSBERG in Berlin O., Mühlenstrafse 8 Mikrophon, bei welchem der Stromschlufstheil durch verkohlte Faser gebildet wird
JPH01158928A (ja) * 1987-09-17 1989-06-22 Sanyo Electric Co Ltd 飲食用器具脱水機

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Publication number Priority date Publication date Assignee Title
JPS56148915A (en) * 1980-04-07 1981-11-18 Asahi Chem Ind Co Ltd Novel composite fiber
JPS6454014A (en) * 1987-08-25 1989-03-01 Nippon Oils & Fats Co Ltd Production of graft copolymer resin
JPH10158928A (ja) * 1996-11-19 1998-06-16 Kanebo Ltd 分割性アクリル系合成繊維及びその製造方法

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009155626A (ja) * 2007-12-06 2009-07-16 Mitsubishi Rayon Co Ltd 耐熱性向上剤、熱可塑性樹脂組成物及び成形品
JP2011051127A (ja) * 2009-08-31 2011-03-17 Mitsubishi Rayon Co Ltd 樹脂成形体の製造方法
JP2012102454A (ja) * 2011-11-28 2012-05-31 Mitsubishi Rayon Co Ltd アクリロニトリル系重合体とセルロース系重合体が均一に混合された繊維を含有する不織布。
JP2013199718A (ja) * 2012-03-26 2013-10-03 Mitsubishi Rayon Co Ltd アクリル系消臭繊維並びにそれを含む紡績糸および織編物。
JP2015030925A (ja) * 2013-08-01 2015-02-16 三菱レイヨン株式会社 抗菌防臭性、消臭性を有するアクリル系複合繊維並びにそれを含む紡績糸および織編物
JP2016187549A (ja) * 2015-03-27 2016-11-04 株式会社リブドゥコーポレーション 消臭材およびそれを備えた吸収性物品
WO2018098072A1 (fr) * 2016-11-22 2018-05-31 E. I. Du Pont De Nemours And Company Procédé de fabrication de fibres de polyacrylonitrile
US11248314B2 (en) 2016-11-22 2022-02-15 Nutrition & Biosciences USA 4, Inc. Process for making polyacrylonitrile fibers

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