JP2011256496A - Flame-retardant synthetic fiber and method for producing the same, flame-retardant fiber composite and fiber product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant synthetic fiber capable of solving the problems hardly solved by the conventional flame-retardant synthetic fiber, i.e., capable of efficiently suppressing the elimination of an antimony compound from a halogen-containing fiber to which the antimony compound has been added, and to provide a method for producing the flame-retardant synthetic fiber, a flame-retardant fiber composite and a fiber product.SOLUTION: The flame-retardant synthetic fiber includes: a polymer obtained by polymerization of 30-70 pts.mass of acrylonitrile, 30-70 pts.mass of a halogen-containing vinylidene monomer and/or a halogen-containing vinyl monomer, and 0-10 pts.mass of a vinyl monomer copolymerizable with the monomers stated above, with the total monomer amount accounting for 100 pts.mass; and antimony tetroxide in an amount of 2/100 to 30/100 by mass based on the polymer. There is also provided a production method of the flame-retardant synthetic fiber. In addition, there are provided a flame-retardant fiber composite and a fiber product.

Description

  The present invention relates to a flame retardant synthetic fiber containing antimony tetroxide, a method for producing the same, a flame retardant fiber composite, and a fiber product.

  In recent years, demands for ensuring safety in clothing, food and living and environmental awareness have increased, and flame retardants are required for clothing, bedding, and other materials used in interiors, and harmful substances that may pose problems for human safety There is a growing movement to regulate elution. Regarding flameproofing, several composites or fiber products using halogen-containing fibers to which an antimony compound is added have been proposed as fiber products exhibiting high flame resistance. For example, Patent Document 1 proposes a cover material such as a cushion composed of 85 to 15% by mass of an antimony compound-added halogen fiber and 85 to 15% by mass of at least one fiber selected from wool and cellulose. . Patent Document 2 proposes a hair fiber comprising a halogen-containing fiber to which an antimony compound as a flame retardant is added and a polyester fiber. However, as in Patent Documents 1 and 2, simply adding an antimony compound into a halogen-containing fiber may cause problems such as elution of antimony during dyeing, as well as harmful effects on gastric juice and sweat. There are cases where the antimony concentration exceeds the specified value in tests such as EN71part3 and Ocotex standards assuming the elution of substances. As methods for solving this, Patent Documents 3 to 5 have been proposed. Patent Document 3 proposes that the addition amount of antimony be reduced or not added by adding magnesium hydroxide into the halogen-containing fiber. Patent Document 4 proposes that the addition amount of antimony is reduced or not added by adding a glass component to the halogen-containing fiber. In Patent Document 5, at least one compound selected from tannins, mercapto group-containing carboxylic acids, polyvalent carboxylic acids, and polyvalent hydroxycarboxylic acids as antimony compound elimination inhibitors is added to a halogen-containing fiber to which an antimony compound is added. It has been proposed to prevent elution of antimony by contact treatment with a treatment solution containing it.

JP-A-11-001842 JP 2002-227019 A JP 2005-314817 A JP 2005-314816 A WO2009 / 093562

  The proposals in Patent Documents 3 to 4 have room for improvement in flame retardancy, and in addition, magnesium hydroxide and glass components are added to the spinning bath when spinning halogen-containing fibers, making spinning difficult. Has not been improved sufficiently. In addition, in order to use tannins as an anti-detachment agent, Patent Document 5 proposes that in order to bind tannins, blending with cellulose fibers such as cotton is required, and a mercapto group-containing carboxylic acid is also required. Regarding the use of polyvalent carboxylic acid and polyvalent hydroxycarboxylic acid, antimony is eluted during the contact treatment, and the cost is increased by these treatments.

  In order to solve the above-described conventional problems, the present invention provides a flame-retardant synthetic fiber capable of efficiently suppressing the elimination of an antimony compound from a halogen-containing fiber to which an antimony compound is added, a method for producing the same, and a flame-retardant fiber composite And it made it a subject to provide a textile product.

  The flame-retardant synthetic fiber of the present invention is composed of 30 to 70 parts by mass of acrylonitrile, 30 to 70 parts by mass of a halogen-containing vinylidene monomer and / or a halogen-containing vinyl monomer, and copolymerizable with these, and the total amount of monomers The polymer obtained by polymerizing 0 to 10 parts by mass of a vinyl monomer having 100 parts by mass contains 2/100 to 30/100 by mass of antimony tetroxide.

  The method for producing a flame-retardant synthetic fiber of the present invention comprises 30 to 70 parts by mass of acrylonitrile, 30 to 70 parts by mass of a halogen-containing vinylidene monomer and / or a halogen-containing vinyl monomer, and a copolymer that can be copolymerized with a single amount. A flame-retardant synthetic fiber containing 2/100 to 30/100 by mass of antimony tetroxide with respect to a polymer obtained by polymerizing 0 to 10 parts by mass of a vinyl monomer having a total mass of 100 parts by mass It is characterized by obtaining.

  The flame-retardant fiber composite of the present invention is selected from the group consisting of 10% by mass or more of the above-mentioned flame-retardant synthetic fiber, and natural fibers, recycled fibers, semi-synthetic fibers, and synthetic fibers other than the above-mentioned flame-retardant synthetic fibers. It contains 90% by mass or less of at least one kind of fiber.

  The textile product of this invention is characterized by including the said flame-retardant synthetic fiber.

  According to the present invention, antimony detachment during refining / bleaching and dyeing, or exposure to gastric juice, sweat fluid, or artificial fluids assuming them can be suppressed while having high flame retardancy. Thus, it is possible to obtain a flame retardant synthetic fiber, a flame retardant fiber composite and a fiber product having high flame retardancy and antimony detachment suppressing performance.

  As a result of intensive studies to solve the above problems, the present inventors have made it possible to incorporate antimony tetraoxide in a synthetic fiber containing acrylonitrile and a halogen-containing vinylidene and / or a halogen-containing vinyl monomer. It has been found that flame retardancy and antimony detachment inhibiting performance can be obtained, and the present invention has been completed.

  The polymer of the present invention comprises 30 to 70 parts by mass of acrylonitrile, 30 to 70 parts by mass of a halogen-containing vinylidene monomer and / or halogen-containing vinyl monomer, and 100 parts by mass of the total amount of monomers copolymerizable therewith. It is obtained by polymerizing 0 to 10 parts by mass of the vinyl monomer. When 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 lower limit of the acrylonitrile content is particularly preferably 40 parts by mass or more, more preferably 50 parts by mass or more, and the upper limit is 60 parts by mass or less, more preferably 57 parts by mass or less. If it is the said preferable range, the heat resistance of a fiber will become higher. The lower limit of the particularly preferred halogen-containing vinylidene monomer and / or halogen-containing vinyl monomer is 40 parts by mass or more, more preferably 43 parts by mass or more, and the upper limit is 60 parts by mass or less, more preferably 50 parts by mass. It is as follows. In particular, the lower limit of the copolymerizable vinyl monomer is 0.3 parts by mass or more, more preferably 0.5 parts by mass or more, and the upper limit is 7 parts by mass or less, more preferably 3 parts by mass or less. .

  Examples of the halogen-containing vinylidene monomer include vinylidene chloride, vinylidene fluoride, vinylidene bromide, and one or more of them are used.

  Examples of the halogen-containing vinyl monomer include vinyl chloride, vinyl fluoride, and vinyl bromide, and one or more of them are used.

  30 to 70 parts by mass of such acrylonitrile, 30 to 70 parts by mass of a halogen-containing vinylidene monomer and / or a halogen-containing vinyl monomer, and a vinyl monomer that can be copolymerized with these and have a total monomer amount of 100 parts by mass. Specific examples of the polymer obtained by polymerizing 0 to 10 parts by mass of the monomer include, for example, a copolymer of a halogen-containing vinylidene monomer such as acrylonitrile-vinylidene chloride, acrylonitrile-vinylidene chloride-vinylidene fluoride, and acrylonitrile. And polymers and copolymers of one or more halogen-containing vinylidene monomers such as vinylidene chloride, vinylidene bromide, and vinylidene fluoride with acrylonitrile and vinylidene monomers copolymerizable therewith. However, it is not limited to these. Moreover, you may use the said homopolymer and copolymer suitably mixing.

  Examples of the vinyl monomer copolymerizable therewith include acrylic acid and its ester, methacrylic acid and its ester, acrylamide, methacrylamide, vinyl acetate, vinyl sulfonic acid and its salt, methallyl sulfonic acid and its salt, Examples thereof include styrenesulfonic acid and its salt, 2-acrylamido-2-methylsulfonic acid and its salt, and one or more of them are used. In addition, it is preferable that at least one of them is a sulfonic acid group-containing vinyl monomer because dyeability is improved.

30 to 70 parts by mass of the acrylonitrile, 30 to 70 parts by mass of a halogen-containing vinylidene monomer and / or a halogen-containing vinyl monomer, and a vinyl monomer that can be copolymerized with these and have a total monomer amount of 100 parts by mass Specific examples of the polymer obtained by polymerizing 0 to 10 parts by mass include the following examples:
(1) A copolymer comprising 51 parts by mass of acrylonitrile, 48 parts by mass of vinylidene chloride, and 1 part by mass of sodium styrenesulfonate,
(2) a copolymer comprising 57 parts by weight of acrylonitrile, 41 parts by weight of vinylidene chloride, and 2 parts by weight of sodium allyl sulfonate;
(3) a copolymer comprising 60 parts by mass of acrylonitrile, 30 parts by mass of vinylidene chloride, and 10 parts by mass of sodium 2-acrylamido-2-methylpropanesulfonate;
(4) a copolymer comprising 55 parts by mass of acrylonitrile, 43 parts by mass of vinylidene chloride, and 2 parts by mass of sodium methallylsulfonate;
(5) A copolymer comprising 56 parts by mass of acrylonitrile, 42 parts by mass of vinylidene chloride, and 2 parts by mass of sodium 2-acrylamido-2-methylpropanesulfonate.

  The copolymer can be obtained by a known polymerization method. For example, 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. Among these, from an industrial point of view, emulsion polymerization and solution polymerization are preferable as polymerization methods, and continuous and semi-batch methods are preferable as polymerization forms.

  The average particle diameter of the antimony tetroxide is preferably 4 μm or less, and more preferably 3 μm or less. When the average particle size of the antimony tetroxide is 4 μm or less, troubles such as nozzle clogging in the production process of the fiber made by adding antimony tetroxide to the halogen-containing polymer, improvement of the strength of the fiber, four in the fiber It is preferable from the viewpoint of dispersibility of the antimony oxide particles. When the dispersibility of the antimony tetraoxide particles in the fiber is improved, it is preferable that antimony detachment from the fiber is expected to be suppressed. The lower limit of the average particle diameter of antimony tetroxide is not particularly limited, but is preferably 0.01 μm or more and more preferably 0.05 μm or more from the viewpoint of handling properties. Furthermore, the antimony tetroxide can be used even if it is chemically modified on the particle surface for improving blocking properties or used in a dispersed state in water or an organic solvent. Here, the average particle diameter means a median diameter. As a method for measuring the median diameter, a light scattering method can be used.

  The production method of antimony tetroxide is not particularly specified, but when producing antimony tetroxide by baking antimony trioxide, which is a general method of producing antimony tetroxide, the antimony tetroxide particles are produced after the production. Although antimony may remain, in this case, it is considered that the residual amount of antimony trioxide is preferably 0 part by mass in order to suppress desorption of antimony from the halogen-containing fiber.

  The amount of the antimony tetroxide compound added is 30 to 70 parts by mass of acrylonitrile, 30 to 70 parts by mass of a halogen-containing vinylidene monomer and / or a halogen-containing vinyl monomer, and the total monomer amount can be copolymerized therewith. With respect to the polymer obtained by polymerizing 0 to 10 parts by mass of the vinyl monomer having 100 parts by mass, the mass is 2/100 or more, preferably 4/100 or more, and more preferably 7/100 or more. The upper limit is 30/100 or less, preferably 20/100 or less, more preferably 15/100 or less, and still more preferably 10/100 or less.

  The flame-retardant synthetic fiber of the present invention is composed of 30 to 70 parts by mass of acrylonitrile, 30 to 70 parts by mass of a halogen-containing vinylidene monomer and / or a halogen-containing vinyl monomer, and copolymerizable with these, and the total amount of monomers A polymer obtained by polymerizing 0 to 10 parts by mass of a vinyl monomer having 100 parts by mass contains 2/100 to 30/100 by mass of antimony tetroxide, and is subjected to wet spinning or dry spinning. It is produced by a known production method such as a method or a semi-dry semi-wet method. For example, in the wet spinning 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 solidifying with, 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, and acetone, and more preferably N, N-dimethylformamide and acetone can be handled industrially.

  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. For example, when combined with other natural fibers, regenerated fibers, or synthetic fibers, those similar to the fibers to be combined are preferred, and the fineness is the composite used, other natural used for textile products Although appropriately selected depending on fiber, regenerated fiber, semi-synthetic fiber or synthetic fiber, 1-30 dtex is preferable, 1-10 dtex is more preferable, and 1-3 dtex is more preferable. The cut length is appropriately selected depending on the use of the composite and the textile product. For example, a shortcut fiber (fiber length 0.1 to 5 mm), a short fiber (fiber length 38 to 128 mm), or a long fiber (filament) that is not cut at all. Among these, short fibers having a fiber length of about 38 to 76 mm are preferable. However, when combined with other fibers, 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 has a high flame retardancy, and antimony can be removed even if it is exposed to antimony during refining / bleaching, dyeing, or gastric juice, sweat fluid, or artificial fluids that assume them. Release is suppressed. In particular, in the elution test of heavy metals in artificial sweat fluid defined in ISO105-E4 (Test Solution II) based on Ocotex Standard 100, which is a test and certification system applied to raw materials, semi-finished products, and final products in all fiber processing stages, The test result of antimony is less than the regulation value (30 mg / kg). Moreover, in the elution test of heavy metals in acidic fluid based on EN71part3, which is a regulation that defines the safety of toys, the antimony test result is less than the regulation value (45 mg / kg).

  The flame-retardant synthetic fiber of the present invention can of course be used alone, and can also be used in combination with natural fibers, regenerated fibers, semi-synthetic fibers, other synthetic fibers other than the flame-retardant synthetic fibers, and the like. is there. A combination with other fibers is referred to as a “flame retardant fiber composite”. The flame retardant fiber composite preferably contains 10% by mass or more of the flame retardant synthetic fiber of the present invention. The lower limit of the content of the flame retardant synthetic fiber is preferably 30% by mass or more, and the upper limit is preferably 70% by weight or less. Composites include blended cotton, blended fibers, blended fibers, aligned yarns, synthetic yarns, core-sheathed composite yarns, woven fabrics, knitted fabrics, laminated fabrics, etc., and specific forms include nonwoven fabrics, woven fabrics, knitted fabrics, lace networks , There are braids.

  As the woven fabric, plain weave, oblique weave, satin weave, altered plain weave, altered oblique weave, altered satin weave, alter weave, crest weave, single layer weave, double structure, multiple structure, warp pile weft, weft pile weave, entanglement There are weaving etc. Plain weave, satin weave and crest weave are excellent in texture and strength as products.

  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 organization, cord organization, atlas organization, There are chain tissue, insertion tissue, etc. Tengu and ribs are excellent in texture as products.

  In the present invention, the flame-retardant fiber composite is composed of 10% by mass or more of the above-mentioned flame-retardant synthetic fiber and a group consisting of natural fibers, regenerated fibers, semi-synthetic fibers, and synthetic fibers other than the above-mentioned flame-retardant synthetic fibers. It contains 90% by mass or less of at least one selected fiber. The lower limit of the content of at least one fiber selected from the group consisting of natural fibers, regenerated fibers, semi-synthetic fibers and synthetic fibers other than the flame retardant synthetic fibers is preferably 30% by mass or more, and the upper limit value is Preferably it is 70 mass% or less.

  Natural fibers include cotton, kapok fiber, hemp, hemp fiber, ramie fiber, jute fiber, manila hemp fiber, kenaf fiber, wool fiber, mohair fiber, cashmere fiber, camel fiber, alpaca fiber, angora fiber, silk fiber, etc. .

  Examples of the 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, and the like.

  Semi-synthetic fibers include cellulose acetate fibers such as acetate and triacetate, and promix fibers.

  Synthetic fibers other than the flame-retardant synthetic fiber include polyester fiber, polyamide fiber, polylactic acid fiber, acrylic fiber, polyolefin fiber, polyvinyl alcohol fiber, polyvinyl chloride fiber, polyvinylidene chloride fiber (trade name “Asahi Kasei Fibers” Saran ”), 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 ”) , Teijin's product names "Technora", "Twaron", "Conex"), benzoate fibers, polyphenylene sulfide fibers (trade name "Procon" manufactured by Toyobo Co., Ltd.), polyether ether ketone fibers, polybenzazole fibers, Polyimide fiber (Toyobo Ltd. trade name "P84"), there is a polyamide-imide fiber (Kerumeru trade name "Kerumeru"), and the like.

  Furthermore, specially regenerated cellulose fibers (rayon fiber containing water glass: trade name “Vigil” manufactured by Satellite, trade name “FR Corona” manufactured by Daiwabo Co., Ltd.), a fire retardant, and a post-processed flame retardant cellulose fiber are applied as regenerated fibers. In addition, there is a material flame retardant rayon fiber (trade name “Lentining FR” manufactured by Lenzing). Synthetic fibers other than the above-mentioned flame-retardant synthetic fibers include flame-retardant polyester (trade name “Heim” manufactured by Toyobo Co., Ltd., trade name “Trevira CS” manufactured by Toraybo Co., Ltd.), polyethylene naphthalate fiber (trade name “Teonex” manufactured by Teijin Ltd.) , Melamine fiber (trade name “Bazofil” manufactured by Vasofil Fiber), acrylate fiber (trade name “Moiscare” manufactured by Toyobo Co., Ltd.), and polybenzoxide fiber (trade name “Zylon” manufactured by Toyobo Co., Ltd.). In addition, there are oxidized acrylic fiber, carbon fiber, glass fiber, activated carbon fiber and the like.

  The flame retardant fiber composite of the present invention can suitably contain cellulosic fibers. Cellulose fibers used in the present invention may be cellulose fibers belonging to any of natural fibers, regenerated fibers, semi-synthetic fibers, or synthetic fibers other than the flame-retardant synthetic fibers. Among these, at least one cellulosic fiber selected from the group consisting of cotton, hemp, rayon, polynosic, cupra, and cellulose acetate fiber is preferable, and cotton and rayon are particularly preferable in terms of hygroscopicity and comfort. Cellulosic fibers are preferably contained in the flame-retardant fiber composite in an amount of 30 to 70% by mass, and more preferably 40% by mass or more.

  The flame retardant synthetic fiber of the present invention may contain 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. It may be included.

Examples of the textile product of the present invention 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 clothing, work clothing, cold clothing, etc.
(3) Interior materials Chair upholstery, curtains, wallpaper, carpets, etc.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the examples. In the following examples, “%” means “mass%”.

(Production Examples 1 to 5): Production Example of Halogen-Containing Fiber A copolymer consisting of 51% acrylonitrile, 48% vinylidene chloride and 1% p-styrene sulfonic acid soda was dissolved in acetone to a resin concentration of 30%. The antimony tetroxide in an amount of 2/100, 4/100, 7/100, 10/100, or 1/100 by mass with respect to the resin of the obtained resin solution (ATE- manufactured by Yamanaka Sangyo Co., Ltd.) S) was added to obtain a spinning dope. This spinning dope was extruded into a 30% acetone aqueous solution using a nozzle having a nozzle hole diameter of 0.08 mm and a hole number of 2000 holes, washed with water while being stretched, dried at 120 ° C., further stretched three times at 150 ° C., 180 Heat treatment was performed in supersaturated steam at 30 ° C. for 30 seconds to obtain a halogen-containing fiber having a fineness of 2 dtex. A finishing oil for spinning (manufactured by Takemoto Yushi Co., Ltd.) was applied to the obtained halogen-containing fiber, crimped, and cut into a length of 38 mm.

(Production Examples 6 and 7): Production Example of Halogen-Containing Fiber A copolymer composed of 51% acrylonitrile, 48% vinylidene chloride and 1% p-styrene sulfonic acid soda was dissolved in acetone to a resin concentration of 30%. Then, 4/100 amount or 10/100 amount of antimony trioxide (MSF manufactured by Yamanaka Sangyo Co., Ltd.) was added to the resin of the obtained resin solution, respectively, to prepare a spinning dope. This spinning dope was extruded into a 30% acetone aqueous solution using a nozzle having a nozzle hole diameter of 0.08 mm and a hole number of 2000 holes, washed with water while being stretched, dried at 120 ° C., further stretched three times at 150 ° C., 180 Heat treatment was performed in supersaturated steam at 30 ° C. for 30 seconds to obtain a halogen-containing fiber having a fineness of 2 dtex. A finishing oil for spinning (manufactured by Takemoto Yushi Co., Ltd.) was applied to the obtained halogen-containing fiber, crimped, and cut into a length of 38 mm.

(Production Example 8): Production Example of Halogen-Containing Fiber A copolymer consisting of 51% acrylonitrile, 48% vinylidene chloride and 1% p-styrene sulfonic acid soda was dissolved in acetone so that the resin concentration was 30%. Antimony pentoxide (Sanpok NA-1030 manufactured by Nissan Chemical Co., Ltd.) in an amount of 10/100 by mass was added to the resin of the obtained resin solution to obtain a spinning dope. This spinning dope was extruded into a 30% acetone aqueous solution using a nozzle having a nozzle hole diameter of 0.08 mm and a hole number of 2000 holes, washed with water while being stretched, dried at 120 ° C., further stretched three times at 150 ° C., 180 Heat treatment was performed in supersaturated steam at 30 ° C. for 30 seconds to obtain a halogen-containing fiber having a fineness of 2 dtex. A finishing oil for spinning (manufactured by Takemoto Yushi Co., Ltd.) was applied to the obtained halogen-containing fiber, crimped, and cut into a length of 38 mm.

(Experimental example 1): Evaluation method of the Ocotex test The Ocotex test was conducted based on the Ocotex standard 100, and the ISO 105-E04 (Japan Tateishi, Katsushika-ku, Tokyo, 4-2-8), an international organization of Ocotex. Test solution II) was requested to measure the amount of antimony dissolved in the specified artificial sweat. Evaluation of the Ocotex test was evaluated as acceptable when the antimony test result in the Ocotex test was less than the specified value (30 mg / kg) defined in the Ocotex standard 100, and when it was 30 mg / kg or more, it was evaluated as unacceptable.

(Experimental example 2): Evaluation method of EN71part3 test The EN71part3 test method is based on EN71-3 (1995), and is based on Chemical Technology Strategy Promotion Organization Polymer Testing and Evaluation Center (1-5 Takaidanaka, Higashiosaka City, Osaka Prefecture). We requested measurement to 3). That is, first, the flame-retardant synthetic fiber of the present invention was cut to about 6 mm, weighed to about 3 g, and then in 0.07 mol / L hydrochloric acid aqueous solution (37 ± 2 ° C., sample amount (g): hydrochloric acid aqueous solution amount ( g) = 1: 50) and stir for 1 minute. Thereafter, the pH was adjusted to 1 to 1.5 using a 2 mol / L hydrochloric acid aqueous solution, stirred at 37 ± 2 ° C. for 1 hour, and further allowed to stand for 1 hour under the same conditions. Next, after filtering using a filter paper (45 μm membrane filter), the filtrate was measured by ICP-AES. From the measured value and the amount of fibers used for extraction, the antimony concentration was calculated from the following formula (Formula 1). Test results were obtained.
Test result = measured value-measured value x 60/100 (Equation 1)

(Experimental example 3): Preparation method of flame retardant test specimens Halogen-containing fibers (A) produced in Production Examples 1 to 8 were mixed in a ratio of 55:45 to MDPA (Worcester). A sliver was made with MDPA3). Next, using this sliver, a 20/1 first open end yarn was produced by a quick spin system (quick spin system manufactured by Worcester). Finally, a knit fabric was produced from the open end yarn using a one-neck knitting machine (16 gauge). This was used as a test piece for flame retardancy evaluation.

(Experimental example 4): Flame retardance evaluation method The flame retardance evaluation of the fabric in an Example uses the fabric produced with the preparation method of the test body for flame retardance evaluation, and a combustion test method is EN ISO15025: 2000 (Procedure A). ). As a flame retardancy evaluation standard, it evaluated based on ISO / FDIS11612: 2008 (E).

  The EN ISO 15025: 2000 (Procedure A) combustion test method consists of a method in which a flame of 25 ± 2 mm is lit for 10 seconds from a position 17 ± 1 mm perpendicular to the evaluation fabric set in a specified holder. ISO / FDIS 11612: 2008 (E) Flame Retardancy Evaluation Standard is EN ISO15025: 2000 Combustion Test Method (Procedure A), when the evaluation dough is heated or melted, when the average afterflame time exceeds 2 seconds If the average residual time exceeds 2 seconds, the sample burns up to the top or side of the sample, if any one of the conditions does not pass, the test fails. Become. As the pass / fail judgment of the flame retardancy of the fabrics in the examples, the test method of the above-mentioned combustion test method EN ISO15025: 2000 (Procedure A) is passed when the ISO / FDIS 11612: 2008 (E) flame retardancy evaluation standard is satisfied (○ ), Otherwise rejected (x).

(Examples 1-4)
The halogen-containing fibers produced in Production Examples 1 to 4 were mixed with cotton, and the knitted fabric produced based on the production method of the flame retardant evaluation specimen was subjected to flame retardant evaluation according to the flame retardant evaluation method. Moreover, about Example 3 and Example 4, the antimony detachment | desorption evaluation in artificial sweat liquid was implemented based on the evaluation method of an Ocotex test. Further, for Example 4, the antimony detachment evaluation at pH = 1 to 1.5 was performed based on the evaluation method of EN71part3 test.

(Comparative Example 1)
The halogen-containing fiber produced in Production Example 5 was blended with cotton, and the knitted fabric produced on the basis of the production method of the flame retardant evaluation specimen was subjected to flame retardant evaluation according to the flame retardant evaluation method.

(Comparative Examples 2 and 3)
The halogen-containing fibers produced in Production Examples 6 to 7 were mixed with cotton, and the knitted fabric produced based on the method for producing a flame retardant evaluation specimen was subjected to flame retardant evaluation according to the flame retardant evaluation method. In addition, antimony detachment in artificial sweat was evaluated based on the evaluation method of the Ocotex test. Further, based on the evaluation method of EN71part3 test, antimony detachment evaluation at pH = 1 to 1.5 was performed.

(Comparative Example 4)
The halogen-containing fiber produced in Production Example 8 was blended with cotton, and the knitted fabric produced based on the method for producing a flame retardant evaluation specimen was subjected to flame retardant evaluation according to the flame retardant evaluation method. In addition, antimony detachment in artificial sweat was evaluated based on the evaluation method of the Ocotex test. Further, based on the evaluation method of EN71part3 test, antimony detachment evaluation at pH = 1 to 1.5 was performed.

  Table 1 summarizes the Ocotex test evaluation results, EN71part3 test results, and flame retardancy evaluation results of Examples 1 to 4 and Comparative Examples 1 to 4.

  In Examples 1 to 4, the flame retardancy was good in any case. Further, in Examples 3 to 4, antimony detachment was suppressed, and the antimony detachment evaluation in the artificial sweat solution based on the evaluation method of the Ocotex test was acceptable. Further, in Example 4, the antimony detachment evaluation at pH = 1 to 1.5 based on the evaluation method of EN71part3 test was acceptable.

  In Comparative Example 1, the addition amount of antimony tetroxide, which is a flame retardant, was as small as 1 part by mass, and the flame retardancy was insufficient and was rejected. In Comparative Examples 2 to 4, the flame retardancy was good in any case, but failed in the antimony detachment evaluation in the artificial sweat solution based on the evaluation method of the Ocotex test.

Claims (20)

  30 to 70 parts by mass of acrylonitrile, 30 to 70 parts by mass of a halogen-containing vinylidene monomer and / or a halogen-containing vinyl monomer, and a vinyl monomer that can be copolymerized with these and has a total monomer amount of 100 parts by mass A flame-retardant synthetic fiber comprising 2/100 to 30/100 by mass of antimony tetroxide, based on 10 to 10 parts by mass of a polymer.   The flame-retardant synthetic fiber according to claim 1, wherein the antimony tetroxide is contained in an amount of 4/100 to 20/100 by mass with respect to the polymer.   The flame-retardant synthetic fiber according to claim 2, comprising 4/100 to 15/100 of the antimony tetroxide in mass relative to the polymer.   The halogen-containing vinylidene monomer is one or more halogen-containing vinylidene monomers selected from the group consisting of vinylidene chloride, vinylidene fluoride, and vinylidene bromide. Flame retardant synthetic fiber.   The halogen-containing vinyl monomer is one or more halogen-containing vinyl monomers selected from the group consisting of vinyl chloride, vinyl fluoride, and vinyl bromide. Flame retardant synthetic fiber.   The copolymerizable vinyl monomer is acrylic acid and its ester, methacrylic acid and its ester, acrylamide, methacrylamide, vinyl acetate, vinyl sulfonic acid and its salt, methallyl sulfonic acid and its salt, styrene sulfonic acid and The flame-retardant synthetic fiber according to any one of claims 1 to 5, which is one or more vinyl monomers selected from the group consisting of a salt thereof, 2-acrylamido-2-methylsulfonic acid and a salt thereof.   The flame-retardant synthetic fiber according to any one of claims 1 to 6, wherein the copolymerizable vinyl monomer is a vinyl monomer containing a sulfonic acid group-containing vinyl monomer.   The flame retardant synthetic fiber according to any one of claims 1 to 7, wherein an average particle diameter of the antimony tetroxide is 4 µm or less.   The flame retardant synthetic fiber according to claim 8, wherein the antimony tetroxide has an average particle size of 3 µm or less.   The flame-retardant synthetic fiber according to any one of claims 1 to 9, wherein the fineness is 1 to 30 dtex.   The flame-retardant synthetic fiber according to any one of claims 1 to 10, wherein the antimony dissolution test into artificial sweat fluid based on Ocotex Standard 100 has a test result of less than 30 mg / kg.   The flame-retardant synthetic fiber according to any one of claims 1 to 11, wherein the antimony dissolution test based on EN71part3 has a test result of less than 45 mg / kg.   The flame-retardant synthetic fiber according to any one of claims 1 to 12 is selected from the group consisting of 10% by mass or more and natural fiber, regenerated fiber, semi-synthetic fiber, and synthetic fiber other than the flame-retardant synthetic fiber. A flame retardant fiber composite comprising at least one kind of fiber.   The flame-retardant fiber composite according to claim 13, comprising 30 to 70% by mass of the flame-retardant synthetic fiber.   The at least 1 sort (s) of fiber chosen from the group which consists of synthetic fibers other than the said natural fiber, a regenerated fiber, a semi-synthetic fiber, and the said flame-retardant synthetic fiber is included 30-70 mass%, The characterized by the above-mentioned. Flame retardant fiber composite.   The cellulosic fiber is included as at least one fiber selected from the group consisting of the natural fiber, the regenerated fiber, the semi-synthetic fiber, and the synthetic fiber other than the flame-retardant synthetic fiber. The flame retardant fiber composite according to claim 1.   The flame retardant fiber composite according to claim 16, wherein the cellulosic fiber is at least one fiber selected from the group consisting of cotton, hemp, rayon, polynosic, cupra, and cellulose acetate fiber.   A textile product comprising the flame-retardant synthetic fiber according to any one of claims 1 to 12.   30 to 70 parts by mass of acrylonitrile, 30 to 70 parts by mass of a halogen-containing vinylidene monomer and / or a halogen-containing vinyl monomer, and a vinyl monomer that can be copolymerized with these and has a total monomer amount of 100 parts by mass A flame-retardant synthetic fiber characterized by obtaining a flame-retardant synthetic fiber containing antimony tetroxide in an amount of 2/100 to 30/100 by mass with respect to a polymer obtained by polymerizing 10 to 10 parts by mass. Production method. 20. The method for producing a flame-retardant synthetic fiber according to claim 19, wherein the test result is less than 30 mg / kg in an antimony dissolution test in artificial sweat based on Ocotex Standard 100.