Classifications

• • 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
  • 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
  • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
• • 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
  • D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
• • 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
• • 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
  • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
  • D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
  • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
  • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
  • D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic Table; Zincates; Cadmates
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
  • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
  • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
  • D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
• • 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
  • D10B2201/01—Natural vegetable 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
  • D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D10B2321/04—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of halogenated hydrocarbons
  • D10B2321/041—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of halogenated hydrocarbons polyvinyl chloride or polyvinylidene chloride
• • 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

Definitions

• the present invention relates to modacrylic fibers, flame-retardant fiber assemblies containing the same, and methods for producing the same.
• Patent Document 1 proposes incorporating a zinc stannate compound as a compound that imparts flame retardancy to halogen-containing fibers, and using the halogen-containing fibers in combination with cellulosic fibers.
• Patent Document 3 also describes a halogen-containing polymer, a flame-retardant synthetic fiber that contains a halogen-containing substance and a zinc compound.
• the present invention provides a modacrylic fiber with enhanced flame retardancy while being environmentally friendly, a flame-retardant fiber assembly containing the same, and a method for producing the same.
• One or more embodiments of the present invention relate to a modacrylic fiber that includes a modacrylic polymer, a halogen-containing compound other than a modacrylic polymer, and a compound containing tin and zinc, the halogen-containing compound containing 50% or more by mass, a halogen content of 40% or more by mass relative to a total of 100% by mass of the modacrylic polymer and the halogen-containing compound, and a molar ratio (halogen/tin) of the halogen element derived from the modacrylic polymer and the halogen-containing compound to the tin element derived from the compound containing tin and zinc is 32 or more.
• One or more embodiments of the present invention relate to a flame-retardant fiber assembly that includes the modacrylic fiber.
• One or more embodiments of the present invention relate to a method for producing modacrylic fibers, the method including a step of wet spinning a spinning solution containing a modacrylic polymer, a halogen-containing compound other than a modacrylic polymer, a compound containing tin and zinc, and a solvent.
• the present invention provides modacrylic fibers with enhanced flame retardancy while being environmentally friendly, flame-retardant fiber assemblies containing the same, and methods for producing the same.
• the inventors of the present invention have conducted extensive research to improve the flame retardancy of modacrylic fibers using modacrylic polymers while taking into consideration the environment. As a result, they have found that flame retardancy can be improved by using a modacrylic polymer in combination with a halogen-containing compound other than the modacrylic polymer (hereinafter referred to as the other halogen-containing compound) and a compound containing tin and zinc, and by setting the molar ratio (halogen/tin) of the halogen derived from the modacrylic polymer and the other halogen-containing compound to the tin derived from the compound containing tin and zinc to a predetermined value or more.
• a modacrylic polymer in combination with a halogen-containing compound other than the modacrylic polymer hereinafter referred to as the other halogen-containing compound
• the other halogen-containing compound a compound containing tin and zinc
• the inventors of the present invention have discovered that in modacrylic fibers using a compound containing tin and zinc as a flame retardant, when the modacrylic fibers are burned, halogens such as chlorine react with tin to produce second tin halides such as tin tetrachloride ( SnCl4 ) and first tin halides such as tin dichloride ( SnCl2 ), and that second tin halides such as tin tetrachloride ( SnCl4 ) exhibit gas-phase flame retardancy while first tin halides such as tin dichloride ( SnCl2 ) exhibit solid-phase flame retardancy; however, when the production rate of second tin halides such as tin tetrachloride ( SnCl4 ) is low, the gas-phase flame retardant effect is inferior to when an antimony-containing compound is used as the flame retardant, and that this is the reason why the flame retardancy is inferior when
• the modacrylic fibers contain modacrylic polymers, other halogen-containing compounds, and compounds containing tin and zinc.
• the modacrylic polymer contains acrylonitrile and a halogen-containing monomer, and the acrylonitrile content is not particularly limited as long as it is less than 85% by mass. From the viewpoint of flame retardancy and heat resistance, however, it preferably contains 30 to 70% by mass of acrylonitrile and 30 to 70% by mass of the halogen-containing monomer, more preferably contains 35 to 65% by mass of acrylonitrile and 35 to 65% by mass of the halogen-containing monomer, and even more preferably contains 40 to 60% by mass of acrylonitrile and 40 to 60% by mass of the halogen-containing monomer.
• halogen-containing monomer examples include halogen-containing vinyl monomers and halogen-containing vinylidene monomers.
• examples of the halogen-containing vinyl monomers include vinyl chloride and vinyl bromide.
• examples of the halogen-containing vinylidene monomers include vinylidene chloride and vinylidene bromide.
• the halogen-containing monomers may be used alone or in combination of two or more. Among them, one or more selected from the group consisting of vinyl chloride and vinylidene chloride are preferred, and vinylidene chloride is more preferred due to its synergistic flame retardant effect with compounds containing tin and zinc.
• the modacrylic polymer may contain, in addition to acrylonitrile and halogen-containing monomers, 0 to 3% by weight of other copolymerizable monomers.
• the other copolymerizable monomer is not particularly limited as long as it is copolymerizable with acrylonitrile, and examples of the monomer that can be used include unsaturated carboxylic acid compounds and their salts, such as acrylic acid and methacrylic acid, methacrylic acid esters, such as methyl methacrylate, ester compounds of unsaturated carboxylic acids, such as glycidyl methacrylate, vinyl ester compounds, such as vinyl acetate and vinyl butyrate, and sulfonic acid group-containing monomers.
• unsaturated carboxylic acid compounds and their salts such as acrylic acid and methacrylic acid, methacrylic acid esters, such as methyl methacrylate, ester compounds of unsaturated carboxylic acids, such as glycidyl methacrylate, vinyl ester compounds, such as vinyl acetate and vinyl butyrate, and sulfonic acid group-containing monomers.
• the sulfonic acid group-containing monomer is not particularly limited, and examples of the monomer that can be used include allyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, isoprene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and metal salts and amine salts thereof, such as sodium salts.
• One of these other copolymerizable vinyl monomers may be used alone, or two or more may be used in combination.
• sulfonic acid group-containing monomers may be used from the viewpoint of improving dyeability.
• the other halogen-containing compound is not particularly limited as long as it contains 50% or more by mass of halogen, and for example, a halogen-containing polymer containing 50% or more by mass of halogen can be used.
• the halogen-containing polymer may contain 50 to 73% by mass, 50 to 68% by mass, or 50 to 61% by mass of halogen.
• the halogen-containing polymer may be a homopolymer or copolymer of a halogen-containing monomer such as a halogen-containing vinyl monomer such as vinyl chloride and vinyl bromide, or a halogen-containing vinylidene monomer such as vinylidene chloride and vinylidene bromide.
• the halogen-containing polymer may be a copolymer of a halogen-containing monomer and another copolymerizable monomer.
• the other copolymerizable monomer is not particularly limited, and examples thereof include ethylene, propylene, vinyl acetate, allyl chloride, allyl glycidyl ether, acrylic ester, and vinyl ether. More specifically, examples thereof include polyvinyl chloride and chlorinated polyvinyl chloride.
• Polyvinyl chloride may contain 50% or more by mass of halogen, and may be a homopolymer of vinyl chloride or a copolymer of vinyl chloride and one or more monomers selected from the group consisting of other halogen-containing monomers and other copolymerizable monomers.
• the halogen content relative to the total 100% by mass of the modacrylic polymer and the halogen-containing compound is 40% by mass or more, preferably 41% by mass or more, and more preferably 42% by mass or more.
• the upper limit of the halogen content relative to the total 100% by mass of the modacrylic polymer and the halogen-containing compound is not particularly limited, but is desirably 60% by mass or less, or 50% by mass or less from the viewpoint of heat resistance. More specifically, in the modacrylic fiber, the halogen content relative to the total 100% by mass of the modacrylic polymer and the halogen-containing compound may be 40 to 60% by mass, 41 to 60% by mass, or 41 to 50% by mass.
• the modacrylic polymer is preferably 50 to 75% by mass and the halogen-containing compound is 25 to 50% by mass, and more preferably 55 to 75% by mass and 25 to 45% by mass of the modacrylic polymer and the halogen-containing compound, based on a total of 100% by mass of the modacrylic polymer and the halogen-containing compound.
• modacrylic fiber can be obtained with good spinnability by wet spinning.
• the compound containing tin and zinc is not particularly limited, but from the viewpoint of versatility, for example, a zinc stannate compound can be used.
• the zinc stannate compound may be, for example, either zinc tin trioxide ( ZnSnO3 ) or zinc tin hexahydroxide (ZnSn(OH) 6 ), but it is preferable to include zinc tin hexahydroxide, for example, from the viewpoint of further increasing the flame retardancy of the modacrylic fiber.
• the modacrylic fiber preferably contains 1 to 20% by mass of the tin- and zinc-containing compound. From the viewpoint of further improving flame retardancy, the modacrylic fiber more preferably contains 2% by mass or more of the tin- and zinc-containing compound, even more preferably contains 4% by mass or more, even more preferably contains 6% by mass or more, and particularly preferably contains 8% by mass or more. Also, from the viewpoints of fiber strength and fabric strength, the modacrylic fiber more preferably contains 18% by mass or less of the tin- and zinc-containing compound, even more preferably contains 16% by mass or less, and particularly preferably contains 14% by mass or less. In this specification, the content of the "tin- and zinc-containing compound" in the modacrylic fiber can be measured by fluorescent X-ray analysis.
• the molar ratio (halogen/tin) of the halogen elements derived from the modacrylic polymer and the halogen-containing compound to the tin elements derived from the tin and zinc-containing compound is 32 or more. This can improve flame retardancy, particularly gas-phase flame retardancy.
• the halogen/tin molar ratio is more preferably 33 or more, even more preferably 34 or more, and even more preferably 35 or more.
• the upper limit of the halogen/tin molar ratio is not particularly limited, but may be, for example, 59 or less, 55 or less, 49 or less, 46 or less, or 44 or less. More specifically, the halogen/tin molar ratio may be 32 to 59, 32 to 55, 33 to 49, 33 to 46, or 33 to 44.
• the modacrylic fiber is substantially free of antimony compounds. This reduces environmental concerns and also reduces costs.
• substantially free of antimony compounds means that antimony compounds are not intentionally added as flame retardants to the fiber or flame-retardant fiber assembly, and “substantially free of antimony compounds” means that antimony compounds are not intentionally added as flame retardants to the fiber or flame-retardant fiber assembly.
• the modacrylic fiber may contain other additives such as antistatic agents, thermal coloring inhibitors, light resistance improvers, whiteness improvers, devitrification inhibitors, and colorants, as necessary.
• the amount of other additives may be, for example, 10% by mass or less, 5% by mass or less, 3% by mass or less, or 1% by mass or less.
• the modacrylic fiber preferably contains 80 to 99% by mass of the modacrylic polymer and the halogen-containing compound in total, 1 to 20% by mass of the tin- and zinc-containing compound, and 0 to 10% by mass of other additives, more preferably 82 to 98% by mass of the modacrylic polymer and the halogen-containing compound in total, 2 to 18% by mass of the tin- and zinc-containing compound, and 0 to 5% by mass of other additives, even more preferably 84 to 96% by mass of the modacrylic polymer and the halogen-containing compound in total, 4 to 16% by mass of the tin- and zinc-containing compound, and 0 to 3% by mass of other additives, and even more preferably 86 to 92% by mass of the modacrylic polymer and the halogen-containing compound in total, 8 to 14% by mass of the tin- and zinc-containing compound, and 0 to 1% by mass of other additives.
• the modacrylic fiber preferably has a single fiber strength of 1.0 to 4.0 cN/dtex, more preferably 1.5 to 3.5 cN/dtex, from the viewpoint of durability, for example.
• the acrylic fiber preferably has an elongation of 15 to 40%, more preferably 20 to 30%, from the viewpoint of practicality, for example.
• the single fiber strength and elongation of the fiber can be measured in accordance with JIS L 1013:2010 or JIS L 1015:2010.
• the modacrylic fiber preferably has a production rate of tin second halide of 55 mass% or more and a production rate of tin first halide of 45 mass% or less when burned at 350°C for 30 minutes. From the viewpoint of achieving both gas phase flame retardancy and heat resistance, it is more preferable that the production rate of tin second halide is 55 to 80 mass% and the production rate of tin first halide is 20 to 45 mass% when burned at 350°C for 30 minutes.
• the modacrylic fiber preferably has a limiting oxygen index (LOI value) of more than 45, more preferably 45.5 or more, even more preferably 46.0 or more, even more preferably 46.5 or more, even more preferably 47.0 or more, and particularly preferably 47.5 or more, in a twist measurement (E-1) based on the E method of JIS L 1091.
• LOI value can be measured specifically as described in the examples.
• the spinning solution is extruded through a nozzle into a coagulation bath to be coagulated, and then stretched, washed with water, dried, and stretched and heat-relaxed as necessary, in the same manner as in the case of general modacrylic fibers. In addition, if necessary, it may be crimped and cut to a predetermined fiber length.
• the spinning solution may be produced by adding a dispersion of a compound containing tin and zinc dispersed in a solvent to a solution in which a modacrylic polymer and other halogen-containing compounds are dissolved in a solvent.
• the flame-retardant fiber assembly of one or more embodiments of the present invention contains the modacrylic fiber. This results in a flame-retardant fiber assembly that exhibits excellent flame retardancy, particularly excellent gas-phase flame retardancy, during combustion.
• the flame-retardant fiber assembly (composite) may be a flame-retardant fiber composite (mixture).
• the flame-retardant fiber assembly preferably contains 25 to 75 mass% of the modacrylic fibers and 25 to 75 mass% of the cellulosic fibers, more preferably contains 30 to 70 mass% of the modacrylic fibers and 30 to 70 mass% of the cellulosic fibers, and even more preferably contains 35 to 65 mass% of the modacrylic fibers and 35 to 65 mass% of the cellulosic fibers.
• the cellulose-based fiber may be one or more selected from the group consisting of natural cellulose-based fibers and regenerated cellulose-based fibers.
• Examples of the natural cellulosic fibers include cotton fiber, kapok fiber, flax fiber, hemp fiber, ramie fiber, jute fiber, Manila hemp fiber, and kenaf fiber.
• the regenerated cellulose fibers include, for example, rayon fibers, flame-retardant rayon fibers, lyocell fibers, and flame-retardant lyocell fibers.
• the rayon fibers are obtained by dissolving cellulose xanthate, which is a cellulose raw material reacted with an alkali and carbon disulfide, in caustic soda and wet spinning.
• the lyocell fibers are obtained without a process of denaturing the cellulose raw material, by dissolving it in N-methylmontforin N-oxide and dry-wet spinning.
• the cellulose-based fibers may be either short or long fibers, and can be appropriately selected depending on the method of use.
• the single fiber fineness of the cellulose-based fibers is appropriately selected depending on the use of the fabric, etc., and is preferably 1 to 50 dtex, more preferably 1.5 to 30 dtex, and even more preferably 1.7 to 15 dtex.
• the fiber length of the cellulose-based fibers is appropriately selected depending on the use of the fabric, etc. Examples include short-cut fibers (e.g., fiber length 0.1 to 5 mm), short fibers (e.g., fiber length 15 to 176 mm, 20 to 160 mm, 25 to 138 mm, or 30 to 128 mm), and long fibers (filaments) that are not cut at all.
• the flame-retardant fiber assembly may contain other fibers in addition to the modacrylic fibers and cellulosic fibers.
• the other fibers may be any of natural fibers, regenerated fibers, and synthetic fibers.
• the other fibers are preferably one or more types selected from the group consisting of polyester fibers, aramid fibers, melamine fibers, and the like.
• the flame-retardant fiber assembly may contain 20% by mass or less of other fibers, 10% by mass or less, or 1% by mass or less.
• the other fibers may be short or long fibers, and can be selected appropriately depending on the method of use.
• the single fiber fineness of the other fibers is selected appropriately depending on the use of the fiber assembly, and may be 1 to 50 dtex, 1.5 to 30 dtex, or 1.7 to 15 dtex.
• the fiber length of the other fibers is selected appropriately depending on the use of the fiber assembly. Examples include short cut fibers (e.g., fiber length 0.1 to 5 mm), short fibers (e.g., fiber length 15 to 176 mm, 20 to 160 mm, 25 to 138 mm, or 30 to 128 mm), and long fibers (filaments).
• composite forms of the flame-retardant fiber aggregate include blended cotton, blended spinning, blended fibers, paralleled yarns, doubled yarns, composite yarns such as core-sheath, interwoven, interknitted, and laminated.
• Specific examples of the flame-retardant fiber aggregate include cotton such as stuffing, spun yarn, nonwoven fabric, fabrics such as woven fabrics and knitted fabrics, and braids.
• Examples of cotton for stuffing include spread cotton, balls of cotton, webs, and molded cotton.
• spun yarns examples include ring spun yarns, air spun yarns, and air jet spun yarns.
• nonwoven fabrics include wet-laid nonwoven fabrics, carded nonwoven fabrics, air-laid nonwoven fabrics, thermally bonded nonwoven fabrics, chemically bonded nonwoven fabrics, needle-punched nonwoven fabrics, hydroentangled nonwoven fabrics, and stitch-bonded nonwoven fabrics.
• Thermally bonded nonwoven fabrics and needle-punched nonwoven fabrics are industrially inexpensive.
• Nonwoven fabrics may have a uniform structure in the thickness, width, and length directions, a clear layered structure, or an unclear layered structure.
• woven fabrics include plain weave, twill weave, satin weave, variegated plain weave, variegated twill weave, variegated satin weave, variegated weave, patterned weave, single-layer weave, double weave, multi-layer weave, warp pile weave, weft pile weave, and twill weave.
• Plain weave, satin weave, and patterned weave are excellent in terms of texture and strength as products.
• the knitted fabrics include, for example, circular knitting, weft knitting, warp knitting, and pile knitting, and more specifically, plain knitting, jersey knitting, rib knitting, smooth knitting (double-sided knitting), elastic knitting, pearl knitting, Denbigh weave, cord weave, atlas weave, chain weave, and insertion weave. Jersey knitting and/or rib knitting provide excellent texture as a product.
• the modacrylic fiber and the flame-retardant fiber assembly can be used in various textile applications.
• textile applications include the following: (1) Clothing and daily necessities materials: clothing (including jackets, underwear, sweaters, vests, trousers, etc.), gloves, socks, scarves, hats, bedding, pillows, cushions, stuffed toys, etc. (2) Special clothing: protective clothing, firefighting clothing, and other work clothing worn by workers who handle fire, cold weather clothing, etc. (3) Interior materials: upholstery, curtains, wallpaper, carpets, etc. (4) Industrial materials: filters, flame-resistant padding, lining materials, etc.
• the flame-retardant fiber aggregate preferably contains 1.4 mass% or more of tin derived from the modacrylic fiber. Also, from the viewpoint of gas-phase flame retardancy and fabric strength, the flame-retardant fiber aggregate preferably contains 1.4 to 6.2 mass% of tin derived from the modacrylic fiber, more preferably 1.4 to 6.0 mass%, even more preferably 1.4 to 5.8 mass%, and even more preferably 1.4 to 5.5 mass%.
• the flame-retardant fiber aggregate has excellent flame retardancy, and in the Koyori measurement (E-1) based on the E method of JIS L 1091, the limiting oxygen index (LOI value) is preferably 30.5 or more, more preferably 31.0 or more, and even more preferably 31.4 or more.
• the LOI value can be measured specifically as described in the examples.
• the basis weight is preferably 150 to 400 g/ m2 , more preferably 200 to 380 g/ m2 , and even more preferably 220 to 350 g/ m2 , although there are no particular limitations thereon, from the viewpoint of texture.
• the combustion residue was placed in a TFM decomposition vessel and precisely weighed, and then sulfuric acid, nitric acid, and hydrochloric acid were added thereto, and pressure acid decomposition was performed using a microwave decomposition device (Milestone General "ETHOS One"), and the decomposition liquid was adjusted to 50 mL and subjected to ICP-AES measurement.
• ETHOS One Microwave decomposition device
• Modacrylic polymer A modacrylic polymer consisting of 51.5% by mass of acrylonitrile, 47.0% by mass of vinylidene chloride, and 1.5% by mass of sodium p-styrenesulfonate obtained by emulsion polymerization of acrylonitrile, vinylidene chloride, and sodium p-styrenesulfonate.
• Halogen-containing compound Polyvinyl chloride (homopolymer of vinyl chloride monomer, chlorine content 57% by mass).
• Antimony compound Compound containing tin and zinc: zinc tin hexahydroxide (manufactured by SCL Italia S.P.A., product name "ZHS”)
• Antimony compound Antimony trioxide (manufactured by Nihon Seiko Co., Ltd., product name "Antimony Trioxide”)
• Examples 1-2, Comparative Examples 1-2 The modacrylic polymer was dissolved in dimethyl sulfoxide so that the content of the modacrylic polymer was 28% by mass.
• a halogen-containing compound and zinc hexahydroxide in the amount shown in Table 1 below per 100 parts by mass of the modacrylic polymer and polyvinyl chloride were added so that the blending ratio of the modacrylic polymer and polyvinyl chloride was as shown in Table 1 below, and the mixture was uniformly mixed to prepare a spinning solution.
• the obtained spinning solution was extruded into a 57% by mass aqueous solution of dimethyl sulfoxide at 25°C using a nozzle with a hole diameter of 0.07 mm and 115,000 holes, washed with water, dried at 130 to 140°C for 20 minutes, stretched 2.6 times at 135°C, and then heat-treated at 155°C for 15 minutes to obtain a modacrylic fiber having a single fiber fineness of 1.7 dtex.
• the modacrylic polymer was dissolved in dimethyl sulfoxide so that the content of the modacrylic polymer was 28% by mass.
• Antimony trioxide was added to the obtained modacrylic polymer solution in an amount of 10 parts by mass per 100 parts by mass of the modacrylic polymer, and the mixture was uniformly mixed to prepare a spinning solution.
• the obtained spinning solution was extruded into a 57% by mass dimethyl sulfoxide aqueous solution at 25°C using a nozzle with a hole diameter of 0.07 mm and 115,000 holes, washed with water, dried at 130 to 140°C for 20 minutes, stretched 2.6 times at 135°C, and then heat-treated at 155°C for 15 minutes to obtain a modacrylic fiber having a single fiber fineness of 1.7 dtex.
• the production ratio of the second tin halide (gas), specifically tin tetrachloride, and the production ratio of the first tin halide, specifically tin dichloride, during combustion of the modacrylic fibers of Examples 1-2 and Comparative Examples 1-2 were measured and calculated as described above.
• the LOI values of the modacrylic fibers of Examples 1-2, Comparative Examples 1-2, and Reference Example 1 were also measured as described above. The results are shown in Table 1 below.
• Table 1 below also shows the halogen content relative to 100% by mass of the total of the modacrylic polymer and the halogen-containing compound (hereinafter referred to as the halogen content in the resin) and the molar ratio of chlorine/tin.
• the modacrylic fibers of the examples which contain a modacrylic polymer, a halogen-containing compound other than a modacrylic polymer containing 50% or more by mass of halogen, and a compound containing tin and zinc, have a halogen content of 40% or more by mass relative to the total of 100% by mass of the modacrylic polymer and the halogen-containing compound, and have a molar ratio (halogen/tin) of the halogen element derived from the modacrylic polymer and the halogen-containing compound to the tin element derived from the compound containing tin and zinc of 32 or more, have a higher LOI and better gas-phase flame retardancy than the modacrylic fibers of the comparative examples.
• the modacrylic fibers of the comparative examples generate a lower rate of tin tetrachloride (gas) than the rate of tin dichloride upon combustion, whereas the modacrylic fibers of the examples generate a higher rate of tin tetrachloride than the rate of tin dichloride upon combustion, resulting in improved gas-phase flame retardancy.
• the fiber assembly in which the modacrylic fiber of the embodiment was mixed with cotton had a higher LOI and was superior in gas-phase flame retardancy than the fiber assembly in which the modacrylic fiber of the comparative example was mixed with cotton.
• a compound including a modacrylic polymer, a halogen-containing compound other than a modacrylic polymer, and a compound containing tin and zinc contains 50% by mass or more of halogen, the halogen content is 40% by mass or more relative to 100% by mass of the total of the modacrylic polymer and the halogen-containing compound, a molar ratio (halogen/tin) of the halogen element derived from said modacrylic polymer and said halogen-containing compound to the tin element derived from said tin and zinc-containing compound is 32 or more; and [2] The modacrylic fiber according to [1], wherein the compound containing tin and zinc includes a zinc stannate compound.
• a flame-retardant fiber assembly comprising the modacrylic fiber according to any one of [1] to [8]. [10] The flame-retardant fiber assembly according to [9], comprising 25 to 75 mass% of the modacrylic fiber and 25 to 75 mass% of the cellulosic fiber. [11] The flame-retardant fiber assembly according to [9] or [10], containing 1.4 mass% or more of tin derived from the modacrylic fiber. [12] The flame-retardant fiber assembly according to any one of [9] to [11], wherein the cellulose-based fibers include natural cellulose-based fibers.

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• 2024
  • 2024-01-31 JP JP2025505125A patent/JPWO2024185346A1/ja active Pending
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  • 2025-08-20 US US19/304,870 patent/US20250389059A1/en active Pending

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