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WO2010010639A1 - Fibre synthétique ignifuge, son processus de fabrication, composites et produits textiles formés de fibres ignifuges - Google Patents

Fibre synthétique ignifuge, son processus de fabrication, composites et produits textiles formés de fibres ignifuges Download PDF

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Publication number
WO2010010639A1
WO2010010639A1 PCT/JP2008/065832 JP2008065832W WO2010010639A1 WO 2010010639 A1 WO2010010639 A1 WO 2010010639A1 JP 2008065832 W JP2008065832 W JP 2008065832W WO 2010010639 A1 WO2010010639 A1 WO 2010010639A1
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Prior art keywords
flame
fiber
mass
parts
synthetic fiber
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PCT/JP2008/065832
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English (en)
Japanese (ja)
Inventor
田中健
羽木裕康
戎敏明
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Kaneka Corp
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Kaneka Corp
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Priority to PCT/JP2009/062454 priority Critical patent/WO2010010815A1/fr
Priority to CN2009801227804A priority patent/CN102066625B/zh
Priority to JP2009549329A priority patent/JP4457182B2/ja
Priority to TW98123876A priority patent/TWI408266B/zh
Priority to US12/506,647 priority patent/US8003555B2/en
Publication of WO2010010639A1 publication Critical patent/WO2010010639A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • 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

Definitions

  • the present invention expresses an extremely high degree of carbonization, shape retention, and self-extinguishing properties at the time of combustion, so that it can be suitably used for textile products that require high flame retardancy, such as bedding and furniture.
  • the present invention relates to a flame retardant synthetic fiber having flame retardancy, a method for producing the same, and a flame retardant fiber composite.
  • flammable materials such as cotton, polyester and urethane foam are often used for the interior and surface for comfort and design at the time of use.
  • flammable materials such as cotton, polyester and urethane foam
  • the flame-retardant material needs to maintain the comfort and design of products such as bedding and furniture.
  • polyester fiber which is an inexpensive material, melts when burned, when it is made only with polyester fiber, a hole is formed and the structure cannot be maintained, and it is used for the bedding and furniture described above. Cotton and urethane foam flared, and the performance was insufficient. Although there are flame retardant polyester fibers containing phosphorus atoms and the like, the behavior at the time of combustion was finally melted as described above, and the performance was insufficient.
  • the method of obtaining highly flame-retardant modacrylic fiber by adding antimony trioxide, antimony pentoxide, magnesium oxide, etc. to the spinning dope can provide flame retardancy, but has a shielding property against flame and heat.
  • One of these performances that is, flame retardancy and satisfying flame and heat barrier properties, is a crosslinked highly flame retardant acrylic fiber to which a polymer containing glycidyl methacrylate is added (patent) Document 1) When exposed to a strong flame such as a burner flame, the fiber itself may decompose and eventually pass through the flame.
  • Patent Document 2 a highly flame-retardant modacrylic fiber added with a solid phase flame retardant represented by water glass or zinc oxide (Patent Document 2), these fibers are excellent in fire extinguishing performance and flame blocking performance.
  • the carbonized film formed during combustion is hard, and depending on the type of furniture and bedding and the shape of the burning part, the shrinkage of the fiber is large, so stress is applied to the carbonized film during combustion, cracking occurs in the carbonized film, and a little In some cases, the carbonized film was perforated by a load of.
  • a modacrylic fiber has been proposed in which zinc oxide and a condensed phosphate compound are added and the carbonization rate at the time of shrinkage is controlled so that cracks are hardly generated (Patent Document 3).
  • Patent Document 3 a modacrylic fiber has been proposed in which zinc oxide and a condensed phosphate compound are added and the carbonization rate at the time of shrinkage is controlled so that cracks are hardly generated.
  • Patent Document 4 a manufacturing method for obtaining acrylic synthetic fibers having good heat shrinkage resistance by performing wet heat tension heat treatment has been proposed (Patent Document 4).
  • the residual shrinkage stress cannot be removed sufficiently to apply heat treatment in a tension state, and the shrinkage can be suppressed at a relatively low temperature of 160 ° C., but it shrinks significantly at a high temperature of 200 ° C. or more like a flame.
  • a flame retardance was inferior.
  • it is not considered at all to be mixed with other fibers necessary as a practical fiber product it cannot be used as a practical flame retardant material.
  • a flame retardant fiber composite comprising a highly flame retardant halogen-containing fiber and a non-flame retardant fiber to which a large amount of a flame retardant is added (Patent Document 5), and an essentially flame-retardant fiber and a halogen-containing fiber
  • Patent Document 6 A flame-retardant nonwoven fabric having a bulky structure composed of, for example, has been proposed.
  • the form before combustion such as a fabric or a woven fabric cannot be maintained at the time of combustion, and a desired flame retardancy, in particular, a flame shielding property cannot be ensured, and a plurality of limited types of fibers are further limited.
  • the fiber content is not high, high flame retardancy cannot be obtained, which may hinder the product design and manufacturing process.
  • heat-resistant fibers and inherently flame-retardant fibers have the desired flame retardancy. Easy, but the fibers themselves are often hard and brittle, and handling is extremely difficult and costly.
  • high flame retardancy cannot be obtained unless the fiber mixing ratio is limited, and in terms of product design and manufacturing. There is a problem in the process.
  • the present invention provides a flame retardant synthetic fiber that satisfies high flame retardancy and high flame shielding properties, a method for producing the same, a flame retardant fiber composite, and a fiber product.
  • the flame-retardant synthetic fiber of the present invention comprises 30 to 70 parts by mass of acrylonitrile, 70 to 30 parts by mass of a halogen-containing vinylidene monomer and / or a halogen-containing vinyl monomer, and a copolymer thereof with 100 parts by mass of the polymer.
  • the method for producing a flame-retardant synthetic fiber according to the present invention comprises 30 to 70 parts by mass of acrylonitrile, 70 to 30 parts by mass of a halogen-containing vinylidene monomer and / or a halogen-containing vinyl monomer, and 100 parts by mass of a polymer.
  • the shrinkage variation when the temperature was raised from 50 ° C. to 300 ° C. under a load of 0.0054 mN / dtex was 45% or less. It is characterized by obtaining a certain flame-retardant synthetic fiber.
  • the flame-retardant fiber composite of the present invention is 10% by mass or more of the above-mentioned flame-retardant synthetic fiber and 90% by mass of at least one kind of fiber selected from natural fibers, recycled fibers, and synthetic fibers other than the above-mentioned flame-retardant synthetic fibers. It includes the following.
  • the fiber product of the present invention is characterized by containing the above-mentioned flame-retardant synthetic fiber.
  • FIG. 1 is an overall view showing the structure of a flame retardant evaluation specimen in one embodiment of the present invention.
  • FIG. 2 is a side sectional view showing the structure of the flame retardant evaluation specimen of FIG.
  • FIG. 3 is an overall view showing the structure of a flame retardant evaluation specimen in another example of the present invention.
  • FIG. 4 is a side sectional view showing the structure of the flame retardant evaluation specimen of FIG.
  • FIG. 5 is a graph showing the shrinkage behavior when the halogen-containing fiber obtained in Production Example 10 which is an example product of the present invention and the fiber of the comparative example product are heated.
  • FIG. 6 is a graph showing a shrinkage pattern of the flame-retardant synthetic fiber in one example of the present invention.
  • FIG. 7 is a graph showing the shrinkage pattern of the flame retardant synthetic fiber of the comparative example.
  • FIG. 8 is a graph showing the shrinkage pattern of the flame retardant synthetic fiber of the comparative example.
  • FIG. 9 is a graph showing a shrinkage pattern of a flame-retardant synthetic fiber in another example of the present invention.
  • FIG. 10 is a graph showing a shrinkage pattern of a flame-retardant synthetic fiber in still another example of the present invention.
  • FIG. 11 is a graph showing a shrinkage pattern of a flame-retardant synthetic fiber in still another example of the present invention.
  • FIG. 12 is a graph showing the shrinkage pattern of the flame retardant synthetic fiber of the comparative example.
  • the present inventors have promoted dehalogenation reaction and carbonization reaction on synthetic fibers containing acrylonitrile and halogen-containing vinylidene and / or halogen-containing vinyl monomer.
  • the present inventors have found that this can be done and have completed the present invention.
  • the polymer (1) of the present invention comprises 30 to 70 parts by mass of acrylonitrile, 70 to 30 parts by mass of a halogen-containing vinylidene monomer and / or halogen-containing vinyl monomer, and a copolymer thereof with 100 parts by mass of the polymer. Contains 0-10 parts by weight of possible vinylic monomers.
  • containing 0 to 10 parts by mass of a vinyl monomer copolymerizable with means that 30 to 70% by mass of acrylonitrile, halogen-containing vinylidene monomer and / or halogen with respect to the total mass of the polymer (1). This means that it contains 70 to 30% by mass of the contained vinyl monomer and 0 to 10% by mass of the vinyl monomer copolymerizable therewith.
  • the acrylonitrile content is 30 to 70 parts by mass, heat resistance necessary for fiberization can be obtained and flame retardancy can be achieved.
  • the acrylonitrile content is preferably 40 to 60 parts by mass, more preferably 40 to 46 parts by mass. When the acrylonitrile content is in the range of 40 to 60 parts by mass, the fiber is less colored.
  • polymer (1) containing 0 to 10 parts by mass include a copolymer of acrylonitrile and one or more halogen-containing vinylidene monomers such as acrylonitrile-vinylidene chloride and acrylonitrile-vinylidene chloride-vinylidene fluoride.
  • a copolymer of at least one halogen-containing vinylidene monomer such as vinylidene chloride, vinylidene bromide, and vinylidene fluoride with acrylonitrile and a vinyl monomer copolymerizable therewith. It is not limited to. Further, one or more of the above copolymers may be appropriately mixed and used.
  • vinyl monomers copolymerizable therewith examples include acrylic acid and esters thereof, methacrylic acid and esters thereof, acrylamide, methacrylamide, vinyl acetate, vinyl sulfonic acid and salts thereof, methallyl sulfonic acid and salts thereof.
  • Styrene sulfonic acid and its salt, 2-acrylamido-2-methyl sulfonic acid and its salt, and one or more of them are used.
  • it is preferable that at least one of them is a sulfonic acid group-containing vinyl monomer because dyeability is improved.
  • polymer (1) containing 30 to 70 parts by mass of the acrylonitrile, 70 to 30 parts by mass of the halogen-containing vinylidene monomer, and 0 to 10 parts by mass of a vinyl monomer copolymerizable therewith
  • the following polymers may be mentioned.
  • Copolymer containing 51 parts by weight of acrylonitrile, 48 parts by weight of vinylidene chloride and 1 part by weight of sodium styrenesulfonate (2) 43 parts by weight of acrylonitrile, 56.1 parts by weight of vinylidene chloride, 2-acrylamido-2-methyl Copolymer containing 0.9 part by weight of sodium propanesulfonate (3) 57 parts by weight of acrylonitrile, 41 parts by weight of vinylidene chloride, copolymer containing 2 parts by weight of sodium allyl sulfonate (4) 60 parts by weight of acrylonitrile, A copolymer containing 30 parts by weight of vinylidene chloride, 10 parts by weight of sodium 2-acrylamido-2-methylpropanesulfonate (5) 55 parts by weight of acrylonitrile, 43 parts by weight of vinylidene chloride, 2 parts by weight of sodium methallylsulfonate Copolymer (6) 69 parts by weight of acrylonitrile,
  • the copolymer can be obtained by a known polymerization method.
  • the polymerization method includes bulk polymerization, suspension polymerization, emulsion polymerization, solution polymerization, and the like, and the polymerization form includes, but is not limited to, continuous, batch, and semi-batch.
  • emulsion polymerization and solution polymerization are preferable as polymerization methods, and continuous and semi-batch methods are preferable as polymerization forms.
  • the at least one metal compound (2) that promotes the dehalogenation reaction during combustion and the carbonization reaction during combustion of the polymer (1) of the present invention includes zinc oxide that promotes both the dehalogenation reaction and the carbonization reaction. , Zinc carbonate, zinc sulfide, zinc borate, zinc phosphate, zinc stannate, metastannic acid, tungsten oxide, zirconium oxide, tin oxide, copper oxide, copper phosphate, indium trioxide and barium titanate (2 -1) or an antimony compound that promotes a dehalogenation reaction with the metal compound (2-1), iron oxide, iron phosphate, iron oxalate, iron sulfide, metastannic acid, molybdenum oxide, bismuth trioxide, bismuth oxychloride
  • a metal compound (2-2) selected from copper iodide can be used in combination.
  • the metal compound (2-1) promotes the dehalogenation reaction at the time of combustion of the polymer (1), promotes the production of a polyene that is a precursor of the carbonization reaction at the time of combustion, and further, a metal halogen produced by dehalogenation. It is believed that the chemical compound catalyzes the polyene structure to promote carbonization.
  • a compound that causes a dehalogenation reaction at 200 ° C. or lower is preferable from the viewpoint of the subsequent promotion of carbonization.
  • at least one selected from zinc oxide, zinc stannate, zinc carbonate, and tin oxide is preferable.
  • the metal compound (2-1) may be used alone or in combination of one or more. Further, a polymer (1) selected from a metal compound (2-1) and an antimony compound, iron oxide, iron phosphate, iron oxalate, iron sulfide, molybdenum oxide, bismuth trioxide, bismuth oxychloride, and copper iodide.
  • a metal compound (2-2) that promotes the dehalogenation reaction during combustion can also be used in combination.
  • the metal compound (2-2) that promotes the dehalogenation reaction of the polymer (1) promotes the formation of a polyene that is a precursor of the carbonization reaction by promoting the dehalogenation reaction of the polymer (1).
  • the single use of the metal compound (2-2) is not effective in the present invention because it does not have the ability to promote carbonization from the generated polyene structure.
  • an antimony compound is particularly preferable.
  • the antimony compound not only promotes the dehalogenation reaction during combustion of the polymer (1), but the antimony halide produced by dehalogenation becomes a gas in a wide temperature range during combustion, and this gas traps radicals. Works to suppress combustion, that is, exhibits fire extinguishing performance.
  • antimony compounds include, but are not limited to, antimony oxide compounds such as antimony trioxide, antimony tetraoxide, and antimony pentoxide, inorganic antimony compounds such as antimonic acid and salts thereof, and antimony oxychloride. is not. These may be used in combination. Among these, antimony trioxide and antimony pentoxide are preferable from the viewpoints of performance and industrial availability.
  • the addition amount of the metal compound (2) is 30 to 70 parts by mass of acrylonitrile, 70 to 30 parts by mass of a halogen-containing vinylidene monomer and / or a halogen-containing vinyl monomer, and a vinyl monomer copolymerizable therewith.
  • 0.05 to 50 parts by mass is preferable with respect to 100 parts by mass of the polymer (1) containing 0 to 10 parts by mass.
  • about a lower limit, 0.1 mass part is more preferable, and 1 mass part is still more preferable.
  • about an upper limit, 40 mass parts is more preferable, and 30 mass parts is still more preferable.
  • the amount of the metal compound (2) used is 0.05 to 50 parts by mass, there is an effect of carbonizing the polymer at the time of combustion (carbonization effect), and the carbonization necessary for obtaining the desired high flame retardance performance. An effect can be obtained and a desired shrinkage rate can be obtained. In the preferred range, the above-mentioned effects are further increased.
  • the amount of the metal compound (2-1) added is 30 to 70 parts by mass of acrylonitrile, 70 to 30 parts by mass of a halogen-containing vinylidene monomer and / or a halogen-containing vinyl monomer, and a vinyl-based monomer copolymerizable therewith.
  • 0.05 to 50 parts by mass is preferable with respect to 100 parts by mass of the polymer (1) containing 0 to 10 parts by mass of the monomer.
  • About a lower limit, 0.1 mass part is more preferable, and 1 mass part is still more preferable.
  • about an upper limit, 40 mass parts is more preferable, and 30 mass parts is still more preferable.
  • the amount of the metal compound (2-1) used is 0.05 to 50 parts by mass, there is an effect of carbonizing the polymer at the time of combustion (carbonization effect), and the necessary carbonization to obtain the desired high flame resistance performance. An effect can be obtained and a desired shrinkage rate can be obtained. In the preferred range, the above-mentioned effects are further increased.
  • the addition amount of the metal compound (2-2) is 30 to 70 parts by mass of acrylonitrile, 70 to 30 parts by mass of a halogen-containing vinylidene monomer and / or a halogen-containing vinyl monomer, and a vinyl-based monomer copolymerizable therewith. 0 to 50 parts by weight, preferably 3 to 40 parts by weight, and more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the polymer (1) containing 0 to 10 parts by weight of the monomer. Even if it is 0 parts by mass, the desired flame retardant performance may be achieved, but since the self-extinguishing effect is small, it is 3 parts by mass or more when used for applications that require a higher level of self-extinguishing effect. It is preferable to add 40 parts by mass or less.
  • the average particle size of the metal compound (2) is preferably 3 ⁇ m or less, and more preferably 2 ⁇ m or less.
  • the average particle size of the metal compound (2) is 3 ⁇ m or less, troubles such as nozzle clogging in the production process of the fiber obtained by adding the metal compound component to the halogen-containing polymer, improvement of the fiber strength, From the viewpoint of dispersion of the metal compound component particles.
  • the minimum in the average particle diameter of a metal compound (2) is not specifically limited, 0.01 micrometer or more is preferable from the point of handling property, and 0.05 micrometer or more is more preferable.
  • the metal compound (2) may be subjected to chemical modification on the particle surface in order to improve blocking properties, or may be used in a state dispersed in water or an organic solvent.
  • the average particle diameter means a median diameter. As a method for measuring the median diameter, a light scattering method can be used.
  • the flame-retardant synthetic fiber of the present invention preferably further contains 0.1 to 20 parts by mass of an epoxy group-containing compound with respect to 100 parts by mass of the polymer (1).
  • an epoxy group-containing compound By including an epoxy group-containing compound, it is crosslinked by drying or heat treatment in the fiber production process, a polymer crosslinked structure is formed in the fiber, and fiber shrinkage can be further suppressed.
  • the epoxy group-containing compound may be a glycidyl ether type, a glycidyl amine type, a glycidyl ester type, a cyclic aliphatic type, or a copolymer containing these.
  • a glycidyl ether type a glycidyl amine type, a glycidyl ester type, a cyclic aliphatic type, or a copolymer containing these.
  • polyglycidyl methacrylate weight average molecular weight 3000 to 100,000
  • the heat treatment of the present invention includes relaxation heat treatment and tension heat treatment.
  • the relaxation heat treatment referred to in the present invention means that, for example, assuming that the heat treatment is applied when the yarn (fiber bundle) moves between the two rollers, the two rollers are identical under the temperature condition in which the fibers do not contract. This refers to heat treatment in the state of the yarn when moving between rollers when the rotation speed is set (constant length state), or in the state where the moving yarn is more slack (relaxed state). Even when the fiber contracts between the two rollers by heat treatment, if the tension applied to the fiber is at the same level as the above state, relaxation heat treatment is performed.
  • the tension heat treatment referred to in the present invention is a state other than the state of the yarn in the relaxation heat treatment, for example, when the two rollers are moved at the same rotational speed under temperature conditions where the fibers do not contract.
  • the heat treatment is in a tension state equivalent to the yarn state in the relaxation heat treatment, the heat treatment is a relaxation heat treatment, and if the heat treatment is in the tension state equivalent to the yarn state in the tension heat treatment, the tension is It becomes heat treatment.
  • any of a general heat treatment method, a dry heat treatment method and a wet heat treatment method is possible.
  • examples of the wet heat treatment method include, but are not limited to, a heat steam treatment method and a wet heat pressure steam treatment method.
  • the fiber state during the heat treatment may be either relaxed or tensioned.
  • the relaxed state includes a constant length state.
  • a relaxation heat treatment method, a heated steam relaxation heat treatment method, and a wet heat pressurized steam relaxation heat treatment method are preferred, and a dry heat relaxation heat treatment method and a wet heat pressurized steam relaxation heat treatment method are more preferred. Further, a heat treatment step may be formed by combining a plurality of these methods and fiber states.
  • the heat treatment of the flame-retardant synthetic fiber can reduce the spinning residual shrinkage stress as the treatment temperature is higher.
  • the heat necessary for heat transfer to the inside of the fiber even at a temperature lower than the softening temperature or decomposition temperature of the flame-retardant synthetic fiber enables sufficient heat treatment without coloring or strength reduction.
  • the said heat processing can be performed by a continuous type or batch type process.
  • a heated steam treatment method and a wet heat pressurized steam treatment method are preferable, and when using a copolymer having acrylonitrile of 50 parts by mass or less, a dry heat treatment method, The wet heat pressurized steam treatment method is preferred.
  • the heat treatment temperature is 120 to 200 ° C., preferably 140 to 180 ° C., more preferably 150 to 170 ° C. for the dry heat treatment method, and 80 to 160 ° C. for the wet heat pressurized steam treatment method.
  • the temperature is preferably 90 to 150 ° C., more preferably 100 to 140 ° C., and 140 to 230 ° C., preferably 150 to 210 ° C., more preferably 160 to 190 ° C. in the case of the heat steam treatment method.
  • the dry heat treatment method is 180 to 260 ° C, preferably 180 to 240 ° C
  • the wet heat pressure steam treatment method is 150 to 230 ° C, preferably 160 to 210 ° C.
  • the temperature is 160 to 250 ° C, preferably 170 to 220 ° C.
  • the upper limit of the heat treatment temperature is not particularly limited, but is 300 ° C., preferably 250 ° C., more preferably 220 ° C. from the viewpoint of coloring of the flame-retardant synthetic fiber and an industrial viewpoint.
  • the heat treatment is preferably a relaxation heat treatment, a dry heat tension heat treatment at 180 ° C. or higher, or a wet heat tension heat treatment at 150 ° C. or higher.
  • a flame-retardant synthetic fiber having a shrinkage variation of 45% or less when the temperature is raised from 50 ° C. to 300 ° C. under a load of 0.0054 mN / dtex is easily obtained.
  • a relaxation heat treatment is more preferable.
  • the heat treatment referred to in the present invention refers to reducing or removing the spinning shrinkage stress by shrinking the fiber under heating.
  • the flame retardant synthetic fiber after the spinning and before the heat treatment, has a shrinkage variation of 45% or less when the temperature is increased from 50 ° C. to 300 ° C. under a load of 0.0054 mN / dtex. Stretching may be performed.
  • shrinkage fluctuation shrinkage rate at point b ⁇ shrinkage rate at point b ′. 3.
  • contraction fluctuation shrinkage rate indicated by an arrow (shrinking fluctuation ⁇ when extending and contracting). 4).
  • Point a in the figure is the softening start point. Between points a and b, shrinkage due to stress relaxation, shrinkage due to dehalogenation, and “elongation” due to softening occur, but shrinkage prevails over elongation.
  • the shrinkage pattern may be such that carbonization occurs again at a certain temperature or higher and shrinks (maintains the shape).
  • the shrinkage rate at the point b ′ in the figure is more preferably 0% or more. 6).
  • the contraction pattern of the fiber of the comparative example is shown in FIGS.
  • FIG. 7 is not preferable because it will be stretched or cut when the temperature is raised.
  • FIG. 8 shows excellent carbonization ability and monotonically shrinks with temperature, but the shrinkage due to stress relaxation (points a and b in the figure) is too large. Since it becomes above, it is not preferable.
  • the flame retardant synthetic fiber of the present invention may include other additives such as an antistatic agent, a thermal coloring inhibitor, a light resistance improver, a whiteness improver, a devitrification inhibitor, a colorant, and a flame retardant as necessary. May be included.
  • the flame-retardant synthetic fiber of the present invention comprises 30 to 70 parts by mass of acrylonitrile, 70 to 30 parts by mass of a halogen-containing vinylidene monomer and / or a halogen-containing vinyl monomer, and a copolymer thereof with 100 parts by mass of the polymer.
  • a polymer containing 0 to 10 parts by mass of a vinyl-based monomer that can be used is produced by a known production method such as a wet spinning method, a dry spinning method, or a semi-dry semi-wet method.
  • the above polymer is dissolved in a solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, acetone, rhodium salt aqueous solution, dimethyl sulfoxide, nitric acid aqueous solution, and then extruded into a coagulation bath through a nozzle.
  • the product is obtained by coagulation with water, followed by washing with water, drying, stretching and heat treatment, and if necessary, crimping and cutting.
  • the solvent is preferably N, N-dimethylformamide, N, N-dimethylacetamide, or acetone, and more preferably N, N-dimethylformamide or acetone because of industrial handling.
  • the flame-retardant synthetic fiber of the present invention may be a short fiber or a long fiber, and can be appropriately selected in the method of use.
  • the fineness is appropriately selected depending on the use of the composite used and the fiber product, but is preferably 1 to 50 dtex, more preferably 1.5 to 30 dtex, and still more preferably 1.7 to 15 dtex.
  • the cut length is appropriately selected depending on the use of the composite and the textile product.
  • a short-cut fiber fiber length 0.1 to 5 mm
  • a short fiber fiber length 38 to 128 mm
  • a long fiber (filament) that is not cut at all can be mentioned.
  • short fibers having a fiber length of about 38 to 76 mm are preferable.
  • the fineness of other fibers may be the same, and it may be thin or thick.
  • the flame-retardant synthetic fiber of the present invention can be combined with other fibers, particularly polyester fibers.
  • Metal compound (2-1) As the metal compound (2-1), for example, zinc oxide, zinc oxide is said to have a function of promoting the dehalogenation reaction of the flame-retardant synthetic fiber. .
  • zinc halide produced by dehalogenation or dehydrohalogenation in the case of chlorine, zinc chloride (ZnCl 2 ) acts catalytically on the polyene structure to promote carbonization (the residue during combustion is a form-retaining component)
  • it is thought to contribute to the triazine ring formation reaction of acrylonitrile (fibers shrink by cyclization).
  • Such an effect is exhibited not only in zinc oxide but also in other zinc compounds, organic zinc compounds such as zinc carbamate and zinc octylate, or some metal oxides such as tin oxide and copper oxide.
  • the carbide generated as a result of the carbonization and cyclization promoting action by the metal compound (2-1) is strong and allows the presence of a residue, particularly a residue retaining the fiber form.
  • shrinkage factors during heating include: a. Shrinkage due to carbonization; b. There are two possible causes: shrinkage due to spinning residual stress. Of these, a. Shrinkage due to carbonization is caused by dehalogenation reaction from the copolymer and triazine ring formation of acrylonitrile. This is a chemical reaction derived from the copolymer composition, and it is difficult to suppress shrinkage due to this reaction.
  • Shrinkage due to spinning residual shrinkage stress is due to residual strain applied to the fiber during solidification and drawing operations in the fiber manufacturing process, and the fiber manufacturing conditions, particularly the heat treatment conditions in the fiber manufacturing process, should be selected as appropriate. Can be suppressed.
  • the heat treatment method include relaxation heat treatment, tension heat treatment at 150 ° C. or higher in wet heat, and tension heat treatment at 180 ° C. or higher in dry heat. Of these, relaxation heat treatment is preferred as a heat treatment method for sufficiently suppressing the spinning residual stress. By applying these heat treatments, the residual shrinkage stress in spinning can be suppressed, and the shrinkage fluctuation during heating (combustion), that is, when the temperature is raised from 50 ° C. to 300 ° C.
  • the flame-retardant synthetic fiber of the present invention has a softening temperature and a dehalogenation start temperature (decomposition point) close to each other, the dehalogenation reaction occurs when the heat treatment temperature is raised, or the fiber is colored or given sufficient heat treatment. May be difficult.
  • the heat treatment temperature can be set to the decomposition temperature or lower.
  • sufficient heat treatment can be performed even at a temperature equal to or lower than the softening point temperature under a pressurized moist heat condition.
  • the flame retardant synthesis of the present invention after spinning and before heat treatment.
  • the fiber may be stretched.
  • the total draw ratio ( stretch ratio (%) ⁇ (100 ⁇ relaxation ratio (%)) ⁇ 0.01) obtained by multiplying the stretch ratio by the relaxation ratio (magnification), which is the ratio at which the fiber shrinks during heat treatment, It is preferably less than 4.8 times, and more preferably less than 4.2 times.
  • the flame-retardant synthetic fiber of the present invention can be used alone or in combination with natural fiber, recycled fiber, other synthetic fiber, or the like.
  • the flame retardant fiber composite of the present invention means a composite formed by combining the flame retardant synthetic fiber of the present invention and other fibers.
  • the flame-retardant fiber composite is 10% by mass or more of the above-mentioned flame-retardant synthetic fiber and 90 masses of at least one kind of fiber selected from natural fibers, recycled fibers, and synthetic fibers other than the above-mentioned flame-retardant synthetic fibers. % Or less included.
  • the upper limit of the content of the flame retardant synthetic fiber in the flame retardant fiber composite is preferably 90% by mass or less, and at least one selected from natural fibers, recycled fibers, and synthetic fibers other than the flame retardant synthetic fibers.
  • the lower limit of the fiber content is preferably 10% by mass or more.
  • Natural fibers include cotton fiber, kapok fiber, flax fiber, cannabis fiber, ramie fiber, jute fiber, manila fiber, kenaf fiber, wool fiber, mohair fiber, cashmere fiber, camel fiber, alpaca fiber, angora fiber, silk fiber, etc.
  • regenerated fibers include regenerated cellulose fibers (rayon, polynosic, trade name “Cupura” manufactured by Asahi Kasei Co., Ltd., product names “Tencel” and “lenting modal” manufactured by Asahi Kasei), regenerated collagen fibers, regenerated protein fibers, cellulose acetate fibers, There are promix fibers.
  • Synthetic fibers include polyester fiber, polyamide fiber, polylactic acid fiber, acrylic fiber, polyolefin fiber, polyvinyl alcohol fiber, polyvinyl chloride fiber, polyvinylidene chloride fiber (trade name "Saran” manufactured by Asahi Kasei Fibers), polyclar fiber, polyethylene Fiber (trade name “Dyneema” manufactured by Toyobo Co., Ltd.), polyurethane fiber, polyoxymethylene fiber, polytetrafluoroethylene fiber, aramid fiber (trade names “Kevlar” manufactured by DuPont, “Nomex”), “Technola” manufactured by Teijin Limited ”,“ Twaron ”,“ Conex ”), benzoate fiber, polyphenylene sulfide fiber (trade name“ Procon ”manufactured by Toyobo Co., Ltd.), polyether ether ketone fiber, polybenzazole fiber, polyimide fiber (trade name, manufactured by Toyobo Co., Ltd.) “
  • Synthetic fibers include flame retardant polyester (trade name “Hheim” manufactured by Toyobo Co., Ltd., product name “Trevira CS” manufactured by Trevira), polyethylene naphthalate fiber (trade name “Teonex” manufactured by Teijin Limited), and melamine fiber (Vasofil Fibers).
  • cotton fiber, rayon fiber, water glass-containing rayon fiber, polyester fiber, and aramid fiber are preferable, polyester fiber is particularly preferable, the cost is low, and in the case of a nonwoven fabric, it is bulky.
  • cotton fiber, rayon fiber, water glass-containing rayon fiber, and aramid fiber are preferable in that they can further impart flame retardancy.
  • the synthetic fiber other than the flame-retardant synthetic fiber is a polyester fiber, and the content in the flame-retardant fiber composite is 40% by mass or more. The upper limit is preferably 90% by mass or less.
  • the flame retardant fiber composite includes mixed cotton, mixed spinning, mixed fiber, aligned yarn, synthetic yarn, core sheath and other composite yarn, union, union, lamination, etc.
  • Examples of cotton for filling include open cotton, ball cotton, web, and molded cotton.
  • Nonwoven fabrics include wet papermaking nonwoven fabrics, carded nonwoven fabrics, airlaid nonwoven fabrics, thermal bond nonwoven fabrics, chemically bonded nonwoven fabrics, needle punched nonwoven fabrics, hydroentangled nonwoven fabrics, and stitch bond nonwoven fabrics.
  • Thermal bond nonwoven fabric and needle punched nonwoven fabric are industrially inexpensive.
  • the nonwoven fabric may have any of a uniform structure, a clear laminated structure, and an unclear laminated structure in the thickness, width, and length directions.
  • the knitting includes round knitting, weft knitting, warp knitting, pile knitting, etc., flat knitting, tengu knitting, rib knitting, smooth knitting (double-sided knitting), rubber knitting, pearl knitting, denby knitting, cord knitting, atlas knitting, There are chain structures, inserted tissues, and the like. Tengu and ribs are excellent in texture as products.
  • the textile product contains the flame retardant synthetic fiber.
  • the textile products include the following. (1) Clothing and daily necessities Clothing (including outerwear, underwear, sweaters, vests, trousers, etc.), gloves, socks, mufflers, hats, bedding, pillows, cushions, stuffed animals, etc. (2) Special clothing Protective clothing, fire fighting clothing (3) Interior materials Chair upholstery, curtains, wallpaper, carpets, etc. (4) Industrial materials Filters, flameproof stuffing, lining materials, etc.
  • a textile product of the present invention is used to produce bedding or furniture such as a bed mattress, pillow, comforter, bed spread, mattress pad, futon, cushion, chair, etc.
  • a fabric upholstered product having excellent properties such as texture, touch, color tone, and hygroscopicity can be obtained.
  • the bed mattress include a pocket coil mattress in which a metal coil is used, a box coil mattress, an insulator in which styrene or urethane resin is foamed, or a mattress in which low-rebound urethane is used. . Due to the flame retardancy of the flame retardant synthetic fiber of the present invention, it is possible to prevent the spread of fire to the internal structure of the mattress.
  • any mattress of the structure a mattress excellent in texture and touch as well as flame retardancy is obtained.
  • chairs used indoors, tools, benches, side chairs, armchairs, lounge chairs / sofas, seat units (sectional chairs, separate chairs), rocking chairs, folding chairs, stacking chairs, swivel chairs, or outdoors Automotive seats, marine seats, aircraft seats, train seats, etc. used for vehicle seats, etc., but these also prevent the spread of internal fire as well as the appearance and feel required for normal furniture It is possible to obtain a flame retardant product having the function of
  • the fabric containing the flame retardant synthetic fiber and / or the flame retardant fiber composite of the present invention (hereinafter referred to as the fabric of the present invention) for a flame retardant upholstered product is as follows. It may be used in a form, or may be sandwiched in the form of a woven fabric, a knitted fabric or a non-woven fabric between a fabric on the surface and an internal structure such as urethane foam or stuffed cotton. When used for the surface fabric, the fabric of the present invention may be used instead of the conventional surface fabric.
  • the surface fabric when a woven fabric or a knitted fabric is sandwiched between the surface fabric and the internal structure, the surface fabric may be sandwiched in a manner of overlapping two sheets, or the internal structure may be covered with the fabric of the present invention.
  • sandwiching the fabric of the present invention between the surface fabric and the internal structure be sure to cover the entire internal structure with the fabric of the present invention on the outside of the internal structure at least for the part that contacts the surface fabric. Apply the surface fabric from above.
  • the evaluation method for promoting the dehalogenation reaction was carried out as follows using a differential heat / thermogravimetry (trade name “TG / DTA220” manufactured by Seiko Instruments Inc.).
  • evaluation method for carbonization reaction promotion The evaluation method of carbonization reaction acceleration was carried out as follows using a differential heat / thermogravimetry (trade name “TG / DTA220” manufactured by Seiko Instruments Inc.).
  • This spinning dope was extruded into a 30% acetone aqueous solution using a nozzle having a nozzle hole diameter of 0.10 mm and a hole number of 1000 holes, washed with water while being stretched, dried at 120 ° C., and further at 123 ° C. in wet heat and pressurized steam for 15 minutes. Then, a relaxation treatment was performed in a non-tensioned state, and a halogen-containing fiber was obtained by further cutting. At this time, the total draw ratio was 2.6 times. The obtained fiber was a fine fiber having a fineness of 7.8 dtex and a cut length of 64 mm.
  • This spinning dope is extruded into a 30% acetone aqueous solution using a nozzle having a nozzle hole diameter of 0.10 mm and a hole number of 1000 holes, washed with water while being stretched, dried at 120 ° C., and then at 170 ° C. for 2 minutes in a state of no tension.
  • the total draw ratio was 3.0 times.
  • the obtained fiber was a fine fiber having a fineness of 7.8 dtex and a cut length of 64 mm.
  • This spinning dope is extruded into a 30% acetone aqueous solution using a nozzle having a nozzle hole diameter of 0.10 mm and a hole number of 1000 holes, washed with water while being stretched, dried at 120 ° C., and then at 170 ° C. for 2 minutes in a state of no tension.
  • the total draw ratio was 3.0 times.
  • the obtained fiber was a fine fiber having a fineness of 7.8 dtex and a cut length of 64 mm.
  • This spinning stock solution was extruded into a 30% acetone aqueous solution using a nozzle having a nozzle hole diameter of 0.10 mm and a hole number of 1000 holes, washed with water while being stretched, dried at 120 ° C., and further dried at 185 ° C. for 2 minutes.
  • the total draw ratio was 3.0 times.
  • the obtained fiber was a fine fiber having a fineness of 7.8 dtex and a cut length of 64 mm.
  • This spinning dope was extruded into a 30% acetone aqueous solution using a nozzle with a nozzle hole diameter of 0.10 mm and a hole number of 1000 holes, washed with water while being stretched, dried at 120 ° C., and further dried at 150 ° C. for 15 minutes in wet heat pressurized steam.
  • the halogen-containing fiber was obtained by further heat-cutting and heat-treating. At this time, the total draw ratio was 4.5 times.
  • the obtained fiber was a fine fiber having a fineness of 7.8 dtex and a cut length of 64 mm.
  • This spinning dope is extruded into a 30% acetone aqueous solution using a nozzle with a nozzle hole diameter of 0.10 mm and a hole number of 1000 holes, washed with water while being stretched, dried at 120 ° C., and further cut without performing a relaxation treatment. To obtain a halogen-containing fiber. At this time, the total draw ratio was 3.0 times. The obtained fiber was a fine fiber having a fineness of 7.8 dtex and a cut length of 64 mm.
  • This spinning dope was extruded into a 30% acetone aqueous solution using a nozzle having a nozzle hole diameter of 0.10 mm and a hole number of 1000 holes, washed with water while being stretched, dried at 120 ° C., and further at 123 ° C. in wet heat and pressurized steam for 15 minutes. Then, a relaxation treatment was performed in a non-tensioned state, and a halogen-containing fiber was obtained by further cutting. At this time, the total draw ratio was 2.6 times. The obtained fiber was a fine fiber having a fineness of 7.8 dtex and a cut length of 64 mm.
  • This spinning dope was extruded into a 30% acetone aqueous solution using a nozzle having a nozzle hole diameter of 0.10 mm and a hole number of 1000 holes, washed with water while being stretched, dried at 120 ° C., and further at 123 ° C. in wet heat and pressurized steam for 15 minutes. Then, a relaxation treatment was performed in a non-tensioned state, and a halogen-containing fiber was obtained by further cutting. At this time, the total draw ratio was 2.6 times. The obtained fiber was a fine fiber having a fineness of 7.8 dtex and a cut length of 64 mm.
  • This spinning dope was extruded into a 30% acetone aqueous solution using a nozzle having a nozzle hole diameter of 0.10 mm and a hole number of 1000 holes, washed with water while being stretched, dried at 120 ° C., and further at 123 ° C. in wet heat and pressurized steam for 15 minutes. Then, a relaxation treatment was performed in a non-tensioned state, and further cut to obtain a halogen-containing fiber. At this time, the total draw ratio was 2.6 times. The obtained fiber was a fine fiber having a fineness of 7.8 dtex and a cut length of 64 mm.
  • This spinning dope was extruded into a 30% acetone aqueous solution using a nozzle with a nozzle hole diameter of 0.10 mm and a hole number of 1000 holes, washed with water while being stretched, dried at 120 ° C., and further dried at 15 ° C. at 123 ° C.
  • a halogen-containing fiber was obtained by performing a relaxation treatment in a state of no tension for a minute and further cutting. At this time, the total draw ratio was 2.6 times.
  • the obtained fiber was a fine fiber having a fineness of 7.8 dtex and a cut length of 64 mm.
  • This spinning dope was extruded into a 30% acetone aqueous solution using a nozzle having a nozzle hole diameter of 0.10 mm and a hole number of 1000 holes, washed with water while being stretched, dried at 120 ° C., and further at 123 ° C. in wet heat and pressurized steam for 15 minutes. Then, a relaxation treatment was performed in a non-tensioned state, and further cut to obtain a halogen-containing fiber. At this time, the total draw ratio was 2.6 times. The obtained fiber was a fine fiber having a fineness of 7.8 dtex and a cut length of 64 mm.
  • This spinning dope is extruded into a 30% acetone aqueous solution using a nozzle having a nozzle hole diameter of 0.10 mm and a hole number of 1000 holes, washed with water while being stretched, dried at 120 ° C., and then at 170 ° C. for 2 minutes in a state of no tension.
  • the total draw ratio was 2.6 times.
  • the obtained fiber was a fine fiber having a fineness of 7.8 dtex and a cut length of 64 mm.
  • This spinning stock solution was extruded into a 30% acetone aqueous solution using a nozzle having a nozzle hole diameter of 0.10 mm and a hole number of 1000 holes, washed with water while being stretched, dried at 120 ° C., and further dried at 170 ° C. for 2 minutes.
  • the total draw ratio was 5.0 times.
  • the obtained fiber was a fine fiber having a fineness of 7.8 dtex and a cut length of 64 mm.
  • This spinning dope was extruded into a 55% dimethylformamide aqueous solution using a nozzle having a nozzle hole diameter of 0.06 mm, washed with water while being stretched, dried at 130 ° C., stretched, and further subjected to wet heat tension treatment at 140 ° C. for 15 minutes. Further, a halogen-containing fiber was obtained by cutting. At this time, the total draw ratio was 4.8 times. Further, the obtained fiber was a short fiber having a fineness of 1.7 dtex and a cut length of 64 mm.
  • This spinning dope is extruded into a 60% dimethylformamide aqueous solution using a nozzle having a nozzle hole diameter of 0.06 mm, washed with water while being stretched, dried at 130 ° C., further subjected to wet heat tension treatment at 130 ° C. for 15 minutes, and further cut. Thus, a halogen-containing fiber was obtained. At this time, the total draw ratio was 5.1 times. The obtained fiber was a fine fiber having a fineness of 2.2 dtex and a cut length of 64 mm.
  • the obtained fiber was a fine fiber having a fineness of 7.8 dtex and a cut length of 64 mm.
  • Tetron fineness 6 dtex, cut length 51 mm
  • TORAY which is a general-purpose polyester fiber as a polyester fiber
  • SAFMET a fineness of 4.4 dtex, a cut length of 51 mm, a melting point of 110 ° C.
  • General purpose rayon and / or para-aramid fiber (trade name “Kevlar” manufactured by Dupont).
  • FIGS. 3 The structure of a pillow top type mattress is shown in FIGS. Two polyurethane foams (type 360S manufactured by Toyo Rubber Industries Co., Ltd.) (1), 30 cm long x 45 cm wide x 1.9 cm thick x 1.9 cm thick, density 1.27 cm, density 30 cm long
  • One 22 kg / m3 polyurethane foam type 360S manufactured by Toyo Tire & Rubber Co., Ltd.
  • one non-woven fabric (3) prepared by the method for preparing a non-flammability evaluation test non-woven fabric
  • outer surface fabric 4)
  • a nylon thread (5) is used to quilt at a quilting interval of 20 cm, and the polyurethane foam having a thickness of 15 cm (type 360 manufactured by Toyo Tire & Rubber Co., Ltd.) S) (6) was laminated to produce a pillow top type mattress specimen.
  • FIGS. 4 Method for Producing Tight Top Type Mattress Specimen
  • the structure of a tight top type mattress specimen is shown in FIGS.
  • One piece of fabric (weight per unit area: 120 g / m 2 ) selected from cloth and a structure laminated as shown in FIG. 4 is quilted with a nylon thread (5) at a quilting interval of 20 cm, and this is polyurethane foam (Toyo
  • a tight top type mattress test specimen was prepared by pasting onto a rubber industry type 360S) (6).
  • Pillow specimen preparation method Manufacture of batting
  • Product name “Tetron” fineness 6 dtex, cut length 51 mm
  • TORAY which is a general-purpose polyester fiber as a halogen-containing fiber and a polyester-based fiber produced by the production methods shown in Production Examples 5, 11, and 22 above.
  • It was used. These fibers were opened with a card at a blending ratio shown in Table 3 below to form a web, and multilayered to produce batting.
  • a spun yarn with a metric count of 34 was obtained by blending 50% by weight of cotton fiber and 50% by weight of polyester fiber.
  • a plain weave fabric having a basis weight of 120 g / m 2 was produced from this spun yarn by a known method.
  • the produced batting is cut into a length of about 30.5 cm and a width of about 30.5 cm.
  • the batting is sandwiched between fabrics (side ground) cut to about 38.1cm in length and 38.1cm in width, and a plate with a weight of 325g is placed on it, and the height of the cushion is 89mm (3.5inch) or more and 102mm (4.0inch) ) Was adjusted so as to be within the range, and the four sides were closed with a cut yarn to produce a flame retardant evaluation cushion.
  • Specimen preparation method assuming fabric
  • the halogen-containing fibers and cotton prepared by the production methods shown in the above Production Examples 5, 11, and 22 are mixed so as to have a predetermined mixture ratio shown in Table 3 below, and opened by a card.
  • a needle punched nonwoven fabric with a predetermined basis weight was produced by a normal needle punch method.
  • the prepared needle punched nonwoven fabric was thermally compressed at 150 ° C. for 300 seconds with a hot press machine to prepare a test specimen having a thickness of 2 mm, which was used as a specimen assuming a cloth.
  • Method for preparing test specimen of knit fabric A predetermined amount of the halogen-containing fiber and cotton fiber prepared in the production example are mixed to produce a spun yarn (meter count 34), and a predetermined circular knitting machine is used. A knit fabric having
  • Panel test evaluation method The test was conducted according to the combustion test method for the upper surface of the bed of 16 CFR 1633 in the United States. Briefly explaining the combustion test method on the upper surface of the bed of US 16CFR1633, a T-shaped burner was set horizontally at 39 mm from the upper surface of the bed, propane gas was used as the combustion gas, the gas pressure was 101 KPa, The flow rate is 12.9 L / min, and it is a test method for flaming for 70 seconds. The evaluation of flame retardancy was as follows. A rank pass: When tested by the above test method, self-extinguishing and no cracks or holes were found in the exposed part.
  • Rank B Same as above, but self-extinguishing, but a crack of less than 1 cm occurred in the part exposed to flame.
  • C rank Same as above, but self-extinguishing, but a crack of 1 cm or more occurred in the part exposed to the flame.
  • D rank pass Same as above, once ignited the internal flammable urethane, but immediately disappeared and finally self-extinguished. Fail: Same as above, the internal flammable urethane was ignited, the fire was forcibly extinguished, and the test was stopped.
  • a pearlite plate with a length of 200 mm ⁇ width 200 mm ⁇ thickness 10 mm was prepared by making a hole with a diameter of 15 cm at the center, and was prepared based on a method for preparing a thermal bond nonwoven fabric for flame retardant evaluation test.
  • a nonwoven fabric was placed, and four sides were fixed with clips so that the nonwoven fabric for flame retardancy evaluation test did not shrink during heating.
  • the sample is placed on the gas stove (trade name “PA-10H-2”, manufactured by Paloma Kogyo Co., Ltd.) with the surface of the non-woven fabric for flame retardant evaluation test facing upward, and the center of the sample and the center of the burner are 40 mm from the burner surface. Set to fit.
  • the fuel gas used was propane with a purity of 99% or more, the flame height was 25 mm, and the flame contact time was 180 seconds. At this time, the case where there was no through hole or crack in the carbonized layer of the non-woven fabric for flame retardancy evaluation test, or the case where there was no through hole but there was a crack, was accepted, and the case where there was a hole or crack was rejected.
  • JIS L1091 A-4 Test Evaluation Method The evaluation of the fabric was performed based on the JIS L1091 A-4 method. Five test specimens (8.9 cm long ⁇ 25.4 cm wide) prepared by a test specimen preparation method assuming a cloth were prepared and set on a support frame. Next, the test body is vertically held in a vertical combustion tester compliant with the JIS L1091 A-4 test, and the distance from the tip of the Bunsen burner mounted at an angle of 25 ° to the center of the lower end of the test body is 17 mm. The positions of the burner and the specimen were adjusted so that A flame was contacted to the sample, and when the sample ignited, it was measured with a stopwatch.
  • a halogen-containing fiber was prepared by adding the metal compound (2-1), metal compound (2-2), and epoxy group compound in the amounts shown in Table 2 below, and a thermal bond for flame retardancy evaluation test
  • the halogen-containing fiber is 0.05 to 50 parts by weight of metal oxide (2), particularly 0.05 to 0.05 parts by weight of metal compound (2-1), relative to 100 parts by weight of polymer (1).
  • the temperature was raised from 50 ° C. to 300 ° C. under a load of 0.0054 mN / dtex by containing 50 parts by mass and being subjected to relaxation treatment at 123 ° C. for 15 minutes in wet heat and pressurized steam under no tension.
  • the shrinkage fluctuation was 45% or less, the combustion test result using the flame retardant test specimen was good, and the pass / fail judgment was acceptable.
  • the halogen-containing fiber is 0.05 to 50 parts by mass of the metal oxide (2), particularly 0.05 to 0.05 parts by mass of the metal compound (2-1) with respect to 100 parts by mass of the polymer (1). It contains ⁇ 50 parts by mass and is subjected to dry heat treatment at 170 ° C for 2 minutes in a no-tension state, so that the shrinkage variation when the temperature is raised from 50 ° C to 300 ° C under a load of 0.0054 mN / dtex. It became 45% or less, the combustion test result using the flame retardant evaluation specimen was good, and the pass / fail judgment was acceptable.
  • Example 12 as described above, the combustion test result using the flame retardant evaluation specimen was good and the pass / fail judgment was acceptable, but the halogen-containing fiber was acrylonitrile 38%, vinylidene chloride 61. Since a copolymer comprising 1% and p-styrene sulfonic acid soda 0.9% was used, the heat resistance was inferior to that of the other examples, and the fibers were fused to each other during spinning, particularly during the relaxation treatment. Since it became hard, when the nonwoven fabric for flame-retardant evaluation was produced, the opening property was bad, and the nonwoven fabric in which the halogen-containing fiber, the polyester fiber, and the heat-fused polyester fiber were uniformly mixed could not be produced.
  • the halogen-containing fiber is 0.05 to 50 parts by mass of the metal oxide (2), particularly 0.05 to 50 parts by mass of the metal compound (2-1) with respect to 100 parts by mass of the polymer (1). Contained in parts by mass and subjected to a dry heat treatment in tension at 185 ° C for 2 minutes, the shrinkage variation when the temperature is raised from 50 ° C to 300 ° C under a load of 0.0054 mN / dtex is 45% or less. The combustion test results using the flame retardant test specimen were good, and the pass / fail judgment was acceptable.
  • the halogen-containing fiber is 0.05 to 50 parts by mass of the metal oxide (2), particularly 0.05 to 50 parts by mass of the metal compound (2-1) with respect to 100 parts by mass of the polymer (1). Contained in parts by mass and subjected to wet heat treatment at 150 ° C. for 15 minutes in a tension state, the shrinkage variation when the temperature is raised from 50 ° C. to 300 ° C. under a load of 0.0054 mN / dtex is 45% or less. Thus, the result of the combustion test using the flame retardant evaluation specimen was good, and the pass / fail judgment was acceptable.
  • the halogen-containing fiber is 0.05 to 50 parts by mass of the metal oxide (2), particularly 0.05 to 50 parts by mass of the metal compound (2-1) with respect to 100 parts by mass of the polymer (1).
  • the halogen-containing fiber has a shrinkage variation of 45% or less when the temperature is raised from 50 ° C. to 300 ° C., and a combustion test using a flame retardant test specimen The result was good, the result of the combustion test using the flame retardant test specimen was good, and the pass / fail judgment was acceptable.
  • cresol novolac epoxy resin was used as the epoxy group compound instead of polyglycidyl methacrylate, but the shrinkage variation when the temperature was increased from 50 ° C. to 300 ° C. under a load of 0.0054 mN / dtex was 45%.
  • the results of the combustion test using the flame retardant evaluation specimen were good, and the pass / fail judgment was acceptable.
  • antimony pentoxide and copper iodide were used in place of antimony trioxide, respectively.
  • a load of 0.0054 mN / dtex 50 ° C. to 300 ° C.
  • the shrinkage variation when the temperature was increased to 45% or less the combustion test result using the flame retardant evaluation specimen was good, and the pass / fail judgment was acceptable.
  • Examples 19 and 20 tin oxide and zinc carbonate were used instead of zinc oxide as the metal compound (2-1), respectively, but the temperature was increased from 50 ° C. to 300 ° C. under a load of 0.0054 mN / dtex. The shrinkage fluctuation when raised was 45% or less, the combustion test result using the flame retardant evaluation specimen was good, and the pass / fail judgment was acceptable.
  • Comparative Examples 1 to 10 In Comparative Example 1, relaxation heat treatment was applied. However, since the flame-retardant synthetic fiber does not contain the metal compound (2-1), the temperature was increased from 50 ° C. to 300 ° C. under a load of 0.0054 mN / dtex. The shrinkage fluctuation when it was raised was 47%, which was 45% or more. Therefore, in the combustion test evaluation using the flame retardant test specimen, a hole is formed in the flame retardant nonwoven fabric used in the flame retardant test specimen during the combustion test, and the internal flammable urethane is ignited. However, because the test was stopped by forcibly extinguishing the fire, it failed.
  • the flame-retardant synthetic fiber had a shrinkage variation of 28% and 45% or less, but does not contain the metal compound (2-1).
  • the combustion test evaluation used at the time of the combustion test, there was a hole in the non-woven fabric for flame retardant evaluation used in the test specimen for flame retardant evaluation, the internal flammable urethane was ignited, the fire was forcibly extinguished, and the test was stopped. As a result, it was rejected.
  • the halogen-containing fiber contains zinc oxide as the metal compound (2-1).
  • the halogen-containing fiber was subjected to a dry heat treatment at 170 ° C. for 2 minutes in a tension state, so that the load was 0.0054 mN / dtex.
  • the shrinkage variation was 67%, which was 45% or more. Therefore, during the combustion test, a crack occurred in the test body, and fire started from there and ignited the internal flammable urethane.
  • the halogen-containing fiber contains zinc oxide as the metal compound (2-1), but under a load of 0.0054 mN / dtex by wet heat treatment at 140 ° C. for 15 minutes in a tension state.
  • the shrinkage variation was 48%, which was 45% or more. Therefore, during the combustion test, a crack occurred in the test body, and fire started from there and ignited the internal flammable urethane.
  • the halogen-containing fiber did not contain the metal compound (2-1), and was wet-heat treated in a tension state at 130 ° C. for 15 minutes. Therefore, under a load of 0.0054 mN / dtex, Shrinkage fluctuations when the temperature was raised from 50 ° C. to 300 ° C. were 93% and 68%, respectively, and were 45% or more. Therefore, in the combustion test evaluation using the flame retardant test specimen, a hole is formed in the flame retardant nonwoven fabric used in the flame retardant test specimen during the combustion test, and the internal flammable urethane is ignited. However, because the test was stopped by forcibly extinguishing the fire, it failed.
  • the halogen-containing fiber contains metastannic acid as the metal compound (2-1).
  • the moisture-containing fiber was subjected to a wet heat treatment at 130 ° C. for 15 minutes to obtain a load of 0.0054 mN / dtex.
  • the shrinkage variation when the temperature was raised from 50 ° C. to 300 ° C. was 62%, which was 45% or more. Therefore, during the combustion test, a crack occurred in the test body, and fire started from there, and the internal flammable urethane was ignited.
  • the halogen-containing fiber had a total draw ratio of less than 4.8 times during spinning, but was wet-heat treated under tension at 130 ° C. for 15 minutes and further contained a metal compound (2-1). Therefore, the shrinkage variation when the temperature was increased from 50 ° C. to 300 ° C. under a load of 0.0054 mN / dtex was 63%, which was 45% or more. Therefore, in the combustion test evaluation using the flame retardant test specimen, a hole is formed in the flame retardant nonwoven fabric used in the flame retardant test specimen during the combustion test, and the internal flammable urethane is ignited. However, the test was stopped because the fire was forcibly extinguished, so it failed.
  • Comparative Example 10 contains aluminum hydroxide as the metal compound but does not contain the metal compound (2-1), so the temperature was raised from 50 ° C. to 300 ° C. under a load of 0.0054 mN / dtex. The shrinkage fluctuation at that time was 46%, which was 45% or more. Therefore, in the combustion test evaluation using the flame retardant test specimen, a hole is formed in the flame retardant nonwoven fabric used in the flame retardant test specimen during the combustion test, and the internal flammable urethane is ignited. However, the test was stopped because the fire was forcibly extinguished, so it failed.
  • Example 21 to 47 the mixing ratio of the halogen-containing fiber produced in Production Example 5 or 11 which is the flame-retardant synthetic fiber of the present invention in the fiber composite is 10% or more, and other components included in the fiber composite are included. Regardless of the type of fiber and the structure of the product, in various tests, excellent flame retardancy was exhibited, and all passed.
  • Comparative Examples 11 to 20 since the halogen-containing fiber produced in Production Example 22 that does not contain the metal compound (2-1) that promotes carbonization during combustion of the polymer (1) is used, The exam also failed.
  • Comparative Examples 21 to 26 the halogen-containing fiber produced in Production Example 5 which is the flame-retardant synthetic fiber of the present invention is used, but the mixture ratio of the halogen-containing fiber in the fiber composite is less than 10%. Both tests failed.
  • Table 2 summarizes the flame retardant combustion test results of Examples 1 to 20 and Comparative Examples 1 to 10.
  • Table 3 summarizes the results of flame retardant combustion tests of Examples 21 to 47 and Comparative Examples 11 to 26.
  • FIG. 5 shows the halogen-containing fiber (A) obtained in Production Example 10 which is a flame-retardant synthetic fiber of the present invention, the current product modacrylic fiber (trade name “Protex-M” manufactured by Kaneka Corporation) (B),
  • Each of the halogen-containing fibers (C) obtained in Production Example 29, which is a comparative product in the present invention, takes about 3 mm of 3333 dtex (decitex), and is heated in the atmosphere at a rate of temperature increase of 20 ° C./min, 18 mN.
  • the results of measuring the shrinkage behavior from 50 ° C. to 300 ° C. or higher under load are shown.
  • the current product (B) as a comparative product shrinks from around about 180 ° C., peaks at about 205 ° C., then turns into elongation and cuts at about 250 ° C.
  • the fiber (C) obtained in Production Example 29 as a comparative example product greatly shrinks to about 200 ° C. when it exceeds about 180 ° C.
  • the fiber (A) obtained in Production Example 10 which is a product of the present invention gradually shrinks from above about 170 ° C., but the shrinkage rate is lower than that of the fiber (C), and It remains without being carbonized and cut.

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Abstract

L'invention concerne une fibre synthétique ignifuge présentant une importante résistance à la flamme et d'importantes propriétés barrière aux flammes, un processus de fabrication de la fibre, et des composites de fibre ignifugeants. Une fibre synthétique ignifugeante comprenant 100 parts en masse d'un polymère (1) comprenant 30 à 70 parts en masse d'acrylonitrile, 70 à 30 parts en masse d'un vinylidène monomère contenant de l'halogène, et 0 à 10 parts en masse d'un monomère vinyle pouvant être copolymérisé avec les deux et au moins un composé métallique (2) capable d'accélérer la déshalogénation et la carbonisation lors de la combustion du polymère (1) et laissant apparaître une variation de rétrécissement de 45 % ou moins déterminée par une élévation de la température de 50°C à 300°C sous l'effet d'une charge de 0,0054 mN/dtex.
PCT/JP2008/065832 2008-07-24 2008-09-03 Fibre synthétique ignifuge, son processus de fabrication, composites et produits textiles formés de fibres ignifuges Ceased WO2010010639A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
PCT/JP2009/062454 WO2010010815A1 (fr) 2008-07-24 2009-07-08 Fibre synthétique ignifuge, ensemble de fibre ignifuge, leur processus de fabrication, et articles textiles
CN2009801227804A CN102066625B (zh) 2008-07-24 2009-07-08 阻燃性合成纤维和阻燃纤维集合体及它们的制造方法、以及纤维制品
JP2009549329A JP4457182B2 (ja) 2008-07-24 2009-07-08 難燃性合成繊維と難燃繊維集合体及びそれらの製造方法、並びに繊維製品
TW98123876A TWI408266B (zh) 2008-07-24 2009-07-15 難燃性合成纖維與難燃纖維集合體及該等之製造方法、與纖維製品
US12/506,647 US8003555B2 (en) 2008-07-24 2009-07-21 Flame retardant synthetic fiber, flame retardant fiber composite, production method therefor and textile product

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2008-191311 2008-07-24
JP2008191311 2008-07-24

Related Parent Applications (1)

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PCT/JP2009/062454 Continuation WO2010010815A1 (fr) 2008-07-24 2009-07-08 Fibre synthétique ignifuge, ensemble de fibre ignifuge, leur processus de fabrication, et articles textiles

Related Child Applications (1)

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US12/506,647 Continuation US8003555B2 (en) 2008-07-24 2009-07-21 Flame retardant synthetic fiber, flame retardant fiber composite, production method therefor and textile product

Publications (1)

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WO2010010639A1 true WO2010010639A1 (fr) 2010-01-28

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PCT/JP2008/065832 Ceased WO2010010639A1 (fr) 2008-07-24 2008-09-03 Fibre synthétique ignifuge, son processus de fabrication, composites et produits textiles formés de fibres ignifuges

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WO (1) WO2010010639A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012207331A (ja) * 2011-03-29 2012-10-25 Tb Kawashima Co Ltd 難燃性カーペット

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5182023A (ja) * 1974-12-23 1976-07-19 Kanegafuchi Chemical Ind Nannenseinisuguretaakurirukeigoseiseni
JPS53106825A (en) * 1977-02-28 1978-09-18 Kanegafuchi Chem Ind Co Ltd Production of crimp-self developing fiber
JPS61282420A (ja) * 1985-05-31 1986-12-12 Asahi Chem Ind Co Ltd 難燃性アクリル系合成繊維
JPH06287806A (ja) * 1993-04-01 1994-10-11 Kanebo Ltd 難燃強化アクリル系合成繊維及びその製造方法
WO2000070133A1 (fr) * 1999-05-18 2000-11-23 Kaneka Corporation Fibre creuse thermoretractable pour tissu a poils, procede de production de celle-ci et produit a poils
WO2001032968A1 (fr) * 1999-11-04 2001-05-10 Kaneka Corporation Tissu allie ignifuge
JP2004197255A (ja) * 2002-12-18 2004-07-15 Kanegafuchi Chem Ind Co Ltd 耐候性に優れた高難燃性のアクリル系繊維および布帛

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5182023A (ja) * 1974-12-23 1976-07-19 Kanegafuchi Chemical Ind Nannenseinisuguretaakurirukeigoseiseni
JPS53106825A (en) * 1977-02-28 1978-09-18 Kanegafuchi Chem Ind Co Ltd Production of crimp-self developing fiber
JPS61282420A (ja) * 1985-05-31 1986-12-12 Asahi Chem Ind Co Ltd 難燃性アクリル系合成繊維
JPH06287806A (ja) * 1993-04-01 1994-10-11 Kanebo Ltd 難燃強化アクリル系合成繊維及びその製造方法
WO2000070133A1 (fr) * 1999-05-18 2000-11-23 Kaneka Corporation Fibre creuse thermoretractable pour tissu a poils, procede de production de celle-ci et produit a poils
WO2001032968A1 (fr) * 1999-11-04 2001-05-10 Kaneka Corporation Tissu allie ignifuge
JP2004197255A (ja) * 2002-12-18 2004-07-15 Kanegafuchi Chem Ind Co Ltd 耐候性に優れた高難燃性のアクリル系繊維および布帛

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012207331A (ja) * 2011-03-29 2012-10-25 Tb Kawashima Co Ltd 難燃性カーペット

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