Classifications

• • 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
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D01F6/40—Modacrylic fibres, i.e. containing 35 to 85% acrylonitrile
• • A—HUMAN NECESSITIES
  • A41—WEARING APPAREL
  • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
  • A41D13/00—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches
• • A—HUMAN NECESSITIES
  • A41—WEARING APPAREL
  • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
  • A41D31/00—Materials specially adapted for outerwear
• • A—HUMAN NECESSITIES
  • A41—WEARING APPAREL
  • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
  • A41D31/00—Materials specially adapted for outerwear
  • A41D31/04—Materials specially adapted for outerwear characterised by special function or use
  • A41D31/08—Heat resistant; Fire retardant
• • 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
  • D01F1/00—General methods for the manufacture of artificial filaments or the like
  • D01F1/02—Addition of substances to the spinning solution or to the melt
  • D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
• • D—TEXTILES; PAPER
  • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
  • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
  • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
  • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
  • D02G3/04—Blended or other yarns or threads containing components made from different materials
  • D02G3/045—Blended or other yarns or threads containing components made from different materials all components being made from artificial or synthetic material
• • D—TEXTILES; PAPER
  • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
  • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
  • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
  • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
  • D02G3/443—Heat-resistant, fireproof or flame-retardant yarns or threads
• • D—TEXTILES; PAPER
  • D03—WEAVING
  • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
  • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
  • D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
• • D—TEXTILES; PAPER
  • D03—WEAVING
  • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
  • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
  • D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
  • D03D15/208—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads cellulose-based
  • D03D15/225—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads cellulose-based artificial, e.g. viscose
• • D—TEXTILES; PAPER
  • D03—WEAVING
  • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
  • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
  • D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
  • D03D15/283—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads synthetic polymer-based, e.g. polyamide or polyester fibres
• • D—TEXTILES; PAPER
  • D03—WEAVING
  • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
  • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
  • D03D15/50—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads
  • D03D15/513—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads heat-resistant or fireproof
• • 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
• • 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
  • D04B1/22—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 specially adapted for knitting goods of particular configuration
  • D04B1/24—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 specially adapted for knitting goods of particular configuration wearing apparel
• • D—TEXTILES; PAPER
  • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
  • D04B—KNITTING
  • D04B21/00—Warp knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
  • D04B21/14—Fabrics characterised by the incorporation by knitting, in one or more thread, fleece, or fabric layers, of reinforcing, binding, or decorative threads; Fabrics incorporating small auxiliary elements, e.g. for decorative purposes
  • D04B21/16—Fabrics characterised by the incorporation by knitting, in one or more thread, fleece, or fabric layers, of reinforcing, binding, or decorative threads; Fabrics incorporating small auxiliary elements, e.g. for decorative purposes incorporating synthetic threads
• • D—TEXTILES; PAPER
  • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
  • D04B—KNITTING
  • D04B21/00—Warp knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
  • D04B21/20—Warp knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes specially adapted for knitting articles of particular configuration
  • D04B21/207—Wearing apparel or garment blanks
• • D—TEXTILES; PAPER
  • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
  • D10B2201/20—Cellulose-derived artificial fibres
• • D—TEXTILES; PAPER
  • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
  • D10B2201/20—Cellulose-derived artificial fibres
  • D10B2201/22—Cellulose-derived artificial fibres made from cellulose solutions
• • D—TEXTILES; PAPER
  • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D10B2321/10—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
  • D10B2321/101—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide modacrylic
• • D—TEXTILES; PAPER
  • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B2401/00—Physical properties
  • D10B2401/04—Heat-responsive characteristics
• • D—TEXTILES; PAPER
  • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B2501/00—Wearing apparel
  • D10B2501/04—Outerwear; Protective garments

Definitions

• the present invention relates to a flame-retardant acrylic fiber with improved flame retardancy while being environmentally friendly, a method for producing the same, and a flame-retardant fiber aggregate and flame-retardant work clothes containing the same.
• halogen-containing fibers such as acrylic fibers flame retardant
• Patent Document 1 an antimony compound as a flame retardant
• antimony compounds may affect the environment and the human body
• flame retardants other than antimony compounds are being considered.
• Patent Documents 2 and 3 tin-based compounds are used in addition to antimony compounds as compounds that impart flame retardancy to halogen-containing fibers.
• Patent Document 2 there was a problem that the cost was high because the halogen-containing fiber contained 20 to 50% by weight of a zinc stannate compound. Furthermore, when the acrylic fiber described in Patent Document 3 is used in combination with other fibers, such as cellulose fiber, for work clothes, etc., the flame retardance may not be sufficient.
• the present invention is environmentally friendly, reduces costs, and has improved flame retardancy, and exhibits high flame retardancy especially when used in combination with other fibers such as cellulose fibers.
• flame-retardant acrylic fibers a method for producing the same, and flame-retardant fiber aggregates and flame-retardant work clothes containing the same.
• One or more embodiments of the present invention include 100 parts by mass of an acrylic copolymer and 1 to 18 parts by mass of a zinc stannate compound, and the zinc stannate compound has an average particle diameter D50 of 0.5 ⁇ m or more. , relating to flame-retardant acrylic fibers.
• the method for producing the flame-retardant acrylic fiber includes the step of wet spinning a spinning dope containing an acrylic copolymer, a zinc stannate compound, and a solvent;
• the stock solution contains 1 to 18 parts by mass of a zinc stannate compound based on 100 parts by mass of the acrylic copolymer, and in the spinning stock solution, the average particle diameter D50 of the zinc stannate compound is 0.5 ⁇ m or more.
• the present invention relates to a method for producing polyacrylic fibers.
• One or more embodiments of the present invention provide flame-retardant acrylic fibers comprising 30-80% by weight of the flame-retardant acrylic fibers and 20-70% by weight of other fibers selected from the group consisting of natural fibers and synthetic fibers. Regarding fiber aggregates.
• One or more embodiments of the present invention relate to flame-retardant work clothes using the flame-retardant fiber aggregate.
• the present invention provides environmentally friendly, low cost, and highly flame retardant fibers that exhibit high flame retardancy, especially when used in combination with other fibers such as cellulosic fibers.
• Flame-retardant acrylic fibers, flame-retardant fiber aggregates, and flame-retardant work clothes can be provided.
• the inventors of the present invention have conducted repeated studies to improve the flame retardancy of acrylic fibers while being environmentally friendly. As a result, it has been found that the flame retardance of acrylic fibers is improved by using a zinc stannate compound having an average particle diameter D50 of 0.5 ⁇ m or more as a flame retardant.
• the flame retardancy of fiber aggregates that use the flame-retardant acrylic fibers in combination with other fibers, specifically cellulose fibers is significantly improved, and the fiber aggregates meet the flame-retardant standards for work clothes. It has been found that it exhibits excellent flame retardancy (flame retardancy) in the combustion test used for evaluation, for example, the ISO 15025:2016 combustion test method.
• the upper limit of the particle size has been adjusted from the viewpoint of spinnability. It is generally said that as the particle size of the flame retardant decreases, the surface area increases, making it easier for reactions to suppress combustion to occur.
• the particle size is smaller than a threshold value, the fire extinguishing performance of acrylic fibers deteriorates significantly, and in particular, the acrylic fibers are used in combination with cellulose fibers. It has been found that fiber aggregates made of such materials become difficult to meet flame retardant standards for work clothes.
• the average particle diameter D50 of the zinc stannate compound may be 0.5 ⁇ m or more, but from the viewpoint of further improving the flame retardance of fibers, fiber aggregates, and work clothes, it is more preferably 0.6 ⁇ m or more. It is particularly preferable that the thickness is 0.7 ⁇ m or more.
• the upper limit of the average particle diameter D50 of the zinc stannate compound is not particularly limited, but from the viewpoint of spinnability and fiber strength, it is preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less, and still more preferably 2 ⁇ m or less.
• the average particle diameter D50 of a compound such as a zinc stannate compound can be measured by a laser diffraction/scattering method or a dynamic light scattering method using a dispersion (dispersion liquid) dispersed in water or an organic solvent. I can do it.
• the zinc stannate compound may be, for example, zinc stannate (ZnSnO 3 ) or zinc hydroxystannate (ZnSn(OH) 6 ). From the viewpoint of increasing the strength, zinc hydroxystannate is preferred.
• the acrylic copolymer may contain acrylonitrile, a halogen-containing monomer, and other copolymerizable vinyl monomers. From the viewpoint of further increasing heat resistance and flame retardancy, the acrylic copolymer contains 30 to 85% by mass of acrylonitrile, 15 to 70% by mass of a halogen-containing monomer, and other copolymerizable vinyl monomers. It preferably contains 0 to 3% by mass or less of acrylonitrile, 35 to 75% by mass of acrylonitrile, 25 to 65% by mass of a halogen-containing monomer, and 0 to 3% by mass of other copolymerizable vinyl monomers.
• the halogen-containing monomer includes one or more selected from the group consisting of a halogen-containing vinyl monomer and a halogen-containing vinylidene monomer.
• the other copolymerizable vinyl monomer is not particularly limited as long as it is copolymerizable with acrylonitrile.
• halogen-containing vinyl monomer examples include vinyl chloride and vinyl bromide
• examples of the halogen-containing vinylidene monomer include vinylidene chloride and vinylidene bromide. These halogen-containing monomers may be used alone or in combination of two or more. Among these, one or more selected from the group consisting of vinyl chloride and vinylidene chloride is preferred, and vinylidene chloride is more preferred.
• the other copolymerizable vinyl monomers are not particularly limited, but include, for example, unsaturated carboxylic acids such as acrylic acid and methacrylic acid, salts thereof, and methacrylic esters such as methyl methacrylate. , esters of unsaturated carboxylic acids such as glycidyl methacrylate, vinyl esters such as vinyl acetate and vinyl butyrate, monomers containing sulfonic acid groups, and the like can be used.
• the monomer containing the sulfonic acid group is not particularly limited, but includes allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, isoprenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and sodium salts thereof. Metal salts such as, amine salts, etc. can be used. These other copolymerizable vinyl monomers may be used alone or in combination of two or more.
• a monomer containing a sulfonic acid group may be used as necessary, but if the content of the monomer containing a sulfonic acid group in the acrylic copolymer is 3% by mass or less, it may be used in the spinning process. Excellent production stability.
• the acrylic copolymer contains 35 to 75% by mass of acrylonitrile, 25 to 65% by mass of vinyl chloride and/or vinylidene chloride, and other copolymerizable vinyls, from the viewpoint of improving handleability and flame retardance. It preferably contains 0 to 3% by mass of monomers, including 40 to 70% by mass of acrylonitrile, 30 to 60% by mass of vinyl chloride and/or vinylidene chloride, and other copolymerizable vinyl monomers. More preferably, it contains 0 to 3% by mass.
• the acrylic copolymer preferably contains 35 to 75% by mass of acrylonitrile, 25 to 65% by mass of vinylidene chloride, and 0 to 3% by mass of other copolymerizable vinyl monomers. More preferably, it contains 40 to 70% by mass of vinylidene chloride, 30 to 60% by mass of vinylidene chloride, and 0 to 3% by mass of other copolymerizable vinyl monomers.
• the acrylic copolymer can be obtained by known polymerization methods such as bulk polymerization, suspension polymerization, emulsion polymerization, and solution polymerization. Among these, suspension polymerization, emulsion polymerization, and solution polymerization are preferred from an industrial viewpoint.
• the flame-retardant acrylic fiber contains 1 to 18 parts by mass of a zinc stannate compound based on 100 parts by mass of the acrylic copolymer.
• a zinc stannate compound based on 100 parts by mass of the acrylic copolymer.
• zinc stannate was added to 100 parts by mass of the acrylic copolymer.
• the content of the compound is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and even more preferably 4 parts by mass or more.
• the flame-retardant acrylic fiber is prepared by adding stannic acid to 100 parts by mass of the acrylic copolymer from the viewpoint of strength, spinnability, color prevention, dyeability, etc.
• the zinc compound is preferably contained in an amount of 16 parts by mass or less, more preferably 15 parts by mass or less, even more preferably 14 parts by mass or less, and even more preferably 13 parts by mass or less.
• the flame-retardant acrylic fiber preferably contains 1.0 to 15.3% by mass of a zinc stannate compound based on the total mass of the fiber, and preferably contains 2.0 to 15.3% by mass of a zinc stannate compound. It is more preferable to contain 13.8% by mass, even more preferably 2.5 to 13.0% by mass, even more preferably 3.0 to 12.3% by mass, and even more preferably 3.5 to 11.5% by mass. It is even more preferable to include % by mass.
• the content of "zinc stannate compound" in the flame-retardant acrylic fiber can be measured by fluorescent X-ray analysis.
• the flame-retardant acrylic fiber optionally contains an antistatic agent, a thermal coloring inhibitor, a light fastness improver, a whiteness improver, a devitrification inhibitor, and a colorant. It may also contain other additives such as.
• the flame-retardant acrylic fibers may be short fibers or long fibers, and can be appropriately selected depending on the method of use.
• the single fiber fineness is appropriately selected depending on the fiber aggregate used and the purpose of the textile product, but it may be 1 to 50 dtex, 1.5 to 30 dtex, or 1.7 to 15 dtex. It's okay.
• the fiber length is appropriately selected depending on the use of the fiber aggregate and textile product. Examples include short-cut fibers (fiber length 0.1 to 5 mm), short fibers (fiber length 15 to 176 mm, 20 to 160 mm, 25 to 138 mm, or 30 to 128 mm), and long fibers (filaments).
• the flame-retardant acrylic fiber preferably has a single fiber strength of 1.0 to 4.0 cN/dtex, and 1.5 to 3.0 cN/dtex, for example, from the viewpoint of durability. More preferably, it is 5 cN/dtex. In one or more embodiments of the present invention, the flame-retardant acrylic fiber preferably has an elongation of 20 to 40%, and more preferably an elongation of 20 to 30%, for example from a practical standpoint. preferable. In this specification, the single fiber strength and elongation of the flame-retardant acrylic fiber can be measured according to JIS L 1013:2021 or JIS L 1015:2021.
• the flame-retardant acrylic fiber can be produced by spinning a composition preferably including, but not limited to, an acrylic copolymer and a zinc stannate compound. Specifically, known methods such as a wet spinning method, a dry spinning method, and a semi-dry semi-wet method can be used.
• the flame-retardant acrylic fiber is preferably produced by wet spinning a spinning solution containing an acrylic copolymer, a zinc stannate compound, and a solvent.
• the spinning stock solution contains 1 to 18 parts by mass of a zinc stannate compound based on 100 parts by mass of the acrylic copolymer, and in the spinning stock solution, the average particle diameter D50 of the zinc stannate compound is 0.5 ⁇ m or more. good.
• the spinning stock solution may be prepared by dissolving the acrylic copolymer in a solvent and then adding a zinc stannate compound thereto. It may be prepared by adding the acrylic copolymer to a solution of the acrylic copolymer dissolved in a solvent.
• the spinning dope is coagulated by extruding it into a coagulation bath through a nozzle, followed by stretching, washing, and drying in the same manner as in general wet spinning of acrylic fibers.
• This makes it possible to produce flame-retardant acrylic fibers.
• stretching and heat treatment thermal relaxation treatment
• the fibers may be crimped and cut into a predetermined fiber length.
• the solvent include organic solvents such as dimethylformamide, dimethylacetamide, acetone, and dimethyl sulfoxide, and inorganic solvents such as a rhodan salt aqueous solution and a nitric acid aqueous solution.
• the average particle diameter D50 of the zinc stannate compound in the flame-retardant acrylic fiber obtained by wet spinning is almost the same as the average particle diameter D50 of the compound in the spinning stock solution, and The average particle diameter D50 of the zinc stannate compound in the system fiber can be expressed by the average particle diameter of the compound in the spinning dope.
• the average particle diameter D50 of the zinc stannate compound in the flame-retardant acrylic fiber is determined by dissolving the flame-retardant acrylic fiber in a solvent and using the obtained dispersion of the insoluble matter. The distribution may be confirmed by measuring and calculating the distribution using a laser diffraction/scattering method or a dynamic light scattering method.
• the solvent the organic solvent used for preparing the above-mentioned spinning dope can be used as appropriate.
• flame-retardant acrylic fibers may be used alone or in combination with other fibers, such as natural fibers, recycled fibers, or other synthetic fibers other than flame-retardant acrylic fibers. It is also possible to use them in combination.
• the flame-retardant fiber composite of one or more embodiments of the present invention contains the flame-retardant acrylic fibers.
• the flame retardant fiber composite may be a flame retardant fiber mixture.
• the flame-retardant fiber composite is formed by combining the flame-retardant acrylic fiber and other fibers.
• the other fibers may be short fibers or long fibers, and can be appropriately selected depending on the method of use.
• the single fiber fineness is appropriately selected depending on the fiber aggregate used and the purpose of the textile product, but it may be 1 to 50 dtex, 1.5 to 30 dtex, or 1.7 to 15 dtex. It's okay.
• the fiber length is appropriately selected depending on the use of the fiber aggregate and textile product. Examples include short-cut fibers (fiber length 0.1 to 5 mm), short fibers (fiber length 15 to 176 mm, 20 to 160 mm, 25 to 138 mm, or 30 to 128 mm), and long fibers (filaments).
• the flame-retardant fiber aggregate preferably contains 30-80% by mass of the flame-retardant acrylic fiber and 20-70% by mass of other fibers selected from the group consisting of natural fibers and chemical fibers. This makes it possible to maintain good flame retardancy of the flame-retardant fiber aggregate while imparting the characteristics of other fibers.
• the flame-retardant fiber aggregate more preferably contains 35-75% by mass of the flame-retardant acrylic fibers and 25-65% by mass of one or more other fibers selected from the group consisting of natural fibers and chemical fibers. %, more preferably 40 to 75% by mass of the flame-retardant acrylic fibers, and 25 to 60% by mass of one or more other fibers selected from the group consisting of natural fibers and chemical fibers.
• the natural fibers include natural cellulose fibers such as cotton fiber, kapok fiber, flax fiber, hemp fiber, ramie fiber, jute fiber, Manila hemp fiber, and kenaf fiber; wool fiber, mohair fiber, cashmere fiber, camel fiber, alpaca fiber, Examples include natural animal fibers such as angora fiber and silk fiber.
• regenerated fibers examples include regenerated cellulose fibers such as rayon, polynosic, cupro, and lyocell, regenerated collagen fibers, regenerated protein fibers, cellulose acetate fibers, and promix fibers.
• the synthetic fibers include polyester fibers, polyamide fibers, polylactic acid fibers, acrylic fibers, polyolefin fibers (polyethylene fibers, polypropylene fibers, etc.), polyvinyl alcohol fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, polyclar fibers, polyurethane fibers, Examples include polyoxymethylene fibers, polytetrafluoroethylene fibers, aramid fibers, benzoate fibers, polyphenylene sulfide fibers, polyetheretherketone fibers, polybenzazole fibers, polyimide fibers, polyamideimide fibers, and the like.
• flame-retardant polyester polyethylene naphthalate fiber, melamine fiber, acrylate fiber, polybenzoxide fiber, etc. may be used as the synthetic fiber.
• Other examples include acrylic oxide fiber, carbon fiber, glass fiber, and activated carbon fiber.
• the other fibers include natural fibers, regenerated cellulose fibers, polyester fibers, aramid fibers, and melamine fibers.
• the other fibers mentioned above may be used alone or in combination of two or more.
• Examples of the composite form of the flame-retardant fiber aggregate include blended cotton, blended spinning, mixed fibers, aligned yarns, doubled yarns, composite yarns such as core-sheath yarns, mixed weaving, mixed knitting, and lamination.
• Specific examples of the flame-retardant fiber aggregate include cotton such as stuffing, spun yarn, nonwoven fabric, woven fabric, knitted fabric, and braided fabric.
• Examples of cotton for stuffing include spread cotton, cotton balls, webs, shaped cotton, and the like.
• spun yarn examples include ring spun yarn, air spun yarn, air jet spun yarn, and the like.
• nonwoven fabrics include wet paper-formed nonwoven fabrics, carded nonwoven fabrics, air laid nonwoven fabrics, thermal bonded nonwoven fabrics, chemically bonded nonwoven fabrics, needle punched nonwoven fabrics, hydroentangled nonwoven fabrics, stitch bonded nonwoven fabrics, and the like. Thermal bond nonwoven fabrics and needle punched nonwoven fabrics are industrially inexpensive. Further, the nonwoven fabric may have any of a uniform structure, a clear laminated structure, and an indefinite laminated structure in the thickness, width, and length directions.
• Fabrics include plain weave, oblique weave, satin weave, variable plain weave, variable oblique weave, variable satin weave, variable weave, patterned weave, single layer weave, double weave, multiple weave, warp pile weave, weft pile weave, and Examples include twine weave. Plain weave, satin weave, and patterned weave have excellent texture and strength as products.
• Knitted fabrics include circular knitting, weft knitting, warp knitting, pile knitting, etc., flat knitting, jersey knitting, rib knitting, smooth knitting (double-sided knitting), rubber knitting, pearl knitting, denby knitting, cord knitting, atlas knitting, Examples include chain tissue and intercalated tissue. Tenjiku knitting and ribbed knitting have excellent texture as products.
• the above-mentioned flame-retardant acrylic fibers and flame-retardant fiber aggregates can be used for various textile products (applications).
• textile products include the following. (1) Clothing and daily necessities Clothing (including jackets, underwear, sweaters, vests, pants, etc.), gloves, socks, mufflers, hats, bedding, pillows, cushions, stuffed animals, etc. (2) Special clothing Protective clothing and firefighting clothing (3) Interior materials: Upholstery, curtains, wallpaper, carpets, etc. (4) Industrial materials: Filters, flame-resistant padding, lining materials, etc.
• the flame-retardant fiber aggregate preferably has an afterflame time of 10 seconds or less, more preferably 5 seconds or less in the ISO15025:2016 combustion test, More preferably it is 3 seconds or less, particularly preferably 2.0 seconds or less.
• the flame-retardant work clothes for work involving fire such as protective clothing and firefighting clothing.
• Flame-retardant fabrics such as woven and/or knitted fabrics having the following fiber compositions can be suitably used as fabrics for flame-retardant work clothes for work involving fire, such as protective clothing and firefighting clothing.
• cellulose fibers in combination, hygroscopicity and comfort can be imparted to fabrics and work clothes. If the content of cellulose fibers is less than 20% by mass, comfort may not be maintained.
• flame-retardant fabrics such as woven and/or knitted fabrics with the following fiber compositions are recommended as flame-retardant fabrics for work that handles fire, such as protective clothing and firefighting clothing. It can be suitably used.
• Lyocell and flame-retardant acrylic fibers containing zinc stannate compounds significantly improved flame retardancy, especially in the ISO 15025:2016 flame test method. show. (1) Contains 30 to 80% by mass of the flame-retardant acrylic fiber and 20 to 70% by mass of Lyocell. (2) Contains 35-75% by mass of the flame-retardant acrylic fiber and 25-65% by mass of Lyocell. (3) Contains 40 to 70% by mass of the flame-retardant acrylic fiber and 30 to 60% by mass of Lyocell.
• the flame retardant fabric is not particularly limited, but from the viewpoint of texture, it is preferable that the fabric weight is 150 to 400 g/m 2 , more preferably 200 to 380 g/m 2 , and still more preferably 220 to 350 g/m 2 . m2 .
• Average particle diameter D50 The particle size distribution of the target compound in the dispersion of the target compound was measured by the laser diffraction/scattering method using a laser diffraction/scattering type particle size distribution measuring device (manufactured by Horiba, Ltd., particle size distribution measuring device LA-950V2). , the average particle diameter D50 was determined.
• the combustion test method based on ISO 15025:2016 is a method in which a flame of 25 ⁇ 2 mm is ignited for 10 seconds from a position 17 ⁇ 1 mm away at right angles to an evaluation sample set in a specified holder.
• Example 1 ⁇ Preparation of acrylic fiber> An acrylic copolymer consisting of 51% by mass of acrylonitrile, 48% by mass of vinylidene chloride, and 1% by mass of sodium p-styrene sulfonate was dissolved in dimethyl sulfoxide so that the concentration of the acrylic copolymer was 30% by mass. A dispersion of zinc hydroxystannate was added to the obtained solution of the acrylic copolymer so that the amount of zinc hydroxystannate was 4 parts by mass per 100 parts by mass of the acrylic copolymer, and the mixture was mixed with the spinning stock solution. did.
• the dispersion of zinc hydroxystannate is prepared by adding zinc hydroxystannate (ZnSn(OH) 6 , manufactured by SCL Italia. Spa, product name "Zinflam (registered trademark) ZHS”) to dimethyl sulfoxide to a concentration of 30% by mass. Then, using a bead mill dispersion machine Dyno Mill RESEARCH LAB type manufactured by Shinmaru Enterprises Co., Ltd., using beads with a bead diameter of 1.5 ⁇ m, the mixture was uniformly dispersed by passing it three times. In the dispersion, the average particle diameter D50 of zinc hydroxystannate was 1.0 ⁇ m.
• the obtained spinning stock solution was extruded into a 50% by mass dimethyl sulfoxide aqueous solution to solidify it, then washed with water and dried at 120°C, and after drying, it was tripled in size. After the stretching, an acrylic fiber was obtained by further performing a heat treatment at 145° C. for 5 minutes.
• the obtained acrylic fiber of Example 1 had a single fiber fineness of 1.7 dtex and a cut length of 38 mm.
• a roving yarn was produced using a high-speed roving frame FL200 manufactured by Toyota Industries Corporation, and a spun yarn with a count of 20/1 was produced using a high-speed spinning frame UA37 manufactured by Howa Kogyo Co., Ltd.
• a single knit fabric having a basis weight shown in Table 1 below was produced using a computerized flat knitting machine SSG series 122FC manufactured by Shima Seiki Co., Ltd.
• Example 2 ⁇ Preparation of acrylic fiber> Except for using beads with a bead diameter of 0.5 ⁇ m, a dispersion of zinc hydroxystannate having an average particle diameter D50 of 0.7 ⁇ m, which was prepared in the same manner as in Example 1, was used. Acrylic fibers were produced in the same manner as in Example 1. The obtained acrylic fiber of Example 2 had a single fiber fineness of 1.8 dtex and a cut length of 38 mm. ⁇ Preparation of flame-retardant fiber aggregate> Spun yarn and single knit fabric were produced in the same manner as in Example 1 except that the obtained acrylic fibers were used.
• (Comparative example 1) ⁇ Preparation of acrylic fiber> Except for using beads with a bead diameter of 0.1 ⁇ m, a dispersion of zinc hydroxystannate having an average particle diameter D50 of 0.4 ⁇ m, which was prepared in the same manner as in Example 1, was used. Acrylic fibers were produced in the same manner as in Example 1. The obtained acrylic fiber of Comparative Example 1 had a single fiber fineness of 1.8 dtex and a cut length of 38 mm. ⁇ Preparation of flame-retardant fiber aggregate> Spun yarn and single knit fabric were produced in the same manner as in Example 1 except that the obtained acrylic fibers were used.
• (Comparative example 2) ⁇ Preparation of acrylic fiber> Zinc hydroxystannate having an average particle diameter D50 of 0.2 ⁇ m was prepared in the same manner as in Example 1 except that beads with a bead diameter of 0.1 ⁇ m were used and the number of passes was 6 times. Acrylic fibers were produced in the same manner as in Example 1 except that a dispersion was used. The obtained acrylic fiber of Comparative Example 2 had a single fiber fineness of 1.7 dtex and a cut length of 38 mm. ⁇ Preparation of flame-retardant fiber aggregate> Spun yarn and single knit fabric were produced in the same manner as in Example 1 except that the obtained acrylic fibers were used.
• Acrylic fibers were produced in the same manner as in Example 1, except that a molybdenum trioxide dispersion was used instead of the zinc hydroxystannate dispersion.
• a dispersion of molybdenum trioxide was prepared by adding molybdenum trioxide (manufactured by Japan Inorganic Chemical Industry Co., Ltd.) to dimethyl sulfoxide to a concentration of 30% by mass, and using a bead mill dispersion machine Dyno Mill RESEARCH manufactured by Shinmaru Enterprises Co., Ltd.
• Using the LAB type beads with a bead diameter of 1.25 mm were used and uniformly dispersed and adjusted by making one pass.
• the average particle diameter D50 of molybdenum trioxide was 1.4 ⁇ m.
• the obtained acrylic fiber of Reference Example 1 had a single fiber fineness of 1.8 dtex and a cut length of 38 mm.
• ⁇ Preparation of flame-retardant fiber aggregate> Spun yarn and single knit fabric were produced in the same manner as in Example 1 except that the obtained acrylic fibers were used.
• Acrylic fibers were produced in the same manner as in Example 1, except that a tin dioxide dispersion was used instead of the zinc hydroxystannate dispersion.
• the tin dioxide dispersion was prepared by adding tin dioxide (manufactured by Showa Kako Co., Ltd.) to dimethyl sulfoxide to a concentration of 30% by mass, and using a bead mill dispersion machine Dyno Mill RESEARCH LAB model manufactured by Shinmaru Enterprises Co., Ltd. Using beads with a bead diameter of 1.25 mm, the particles were uniformly dispersed in one pass. In this dispersion, the average particle diameter D50 of tin dioxide was 2.0 ⁇ m.
• the obtained acrylic fiber of Reference Example 3 had a single fiber fineness of 1.9 dtex and a cut length of 38 mm.
• ⁇ Preparation of flame-retardant fiber aggregate> Spun yarn and single knit fabric were produced in the same manner as in Example 1 except that the obtained acrylic fibers were used.
• Reference Examples 1 and 2 use molybdenum trioxide as a flame retardant, but Reference Example 2, which uses molybdenum trioxide with an average particle diameter D50 of less than 0.5 ⁇ m, has an average particle diameter D50 of 0.5 ⁇ m. The flame retardance was higher than that of Reference Example 1 using molybdenum trioxide exceeding . Further, Reference Examples 3 and 4 use tin dioxide as a flame retardant, but Reference Example 4, which uses tin dioxide with an average particle diameter D50 of less than 0.5 ⁇ m, has an average particle diameter D50 of 0.5 ⁇ m. The flame retardance was higher than that of Reference Example 3, which used tin dioxide exceeding 30%.
• [1] Contains 100 parts by mass of an acrylic copolymer and 1 to 18 parts by mass of a zinc stannate compound, A flame-retardant acrylic fiber, wherein the zinc stannate compound has an average particle diameter of 0.5 ⁇ m or more.
• [2] The flame-retardant acrylic fiber according to [1], wherein the zinc stannate compound is zinc hydroxystannate.
• the acrylic copolymer contains 30 to 85% by mass of acrylonitrile and 15 to 70% by mass of one or more halogen-containing monomers selected from the group consisting of halogen-containing vinyl monomers and halogen-containing vinylidene monomers.
• [4] The method for producing a flame-retardant acrylic fiber according to any one of [1] to [3], Including a step of wet spinning a spinning stock solution containing an acrylic copolymer, a zinc stannate compound and a solvent,
• the spinning stock solution contains 1 to 18 parts by mass of a zinc stannate compound based on 100 parts by mass of the acrylic copolymer,
• [5] 30 to 80% by mass of the flame-retardant acrylic fiber according to any one of [1] to [3], and 20 to 70% by mass of other fibers selected from the group consisting of natural fibers and chemical fibers. Including flame retardant fiber aggregate.
• [8] The flame-retardant fiber aggregate according to [7], wherein the cellulosic fibers include Lyocell.

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