JP2015067925A - Halogen-containing flame-retardant fiber and method for producing the same, and flame-retardant fiber composite and flame-retardant fiber product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a halogen-containing flame-retardant fiber capable of efficiently suppressing the elimination of an antimony compound from a halogen-containing flame-retardant fiber to which the antimony compound is added and a method for producing the same and to provide a flame-retardant fiber composite and a fiber product.SOLUTION: There are provided: a halogen-containing flame-retardant fiber which comprises 2 to 100 pts.mass of a compound (A) containing at least two adjacent hydroxyl groups in a single molecule, 1.2 to 20 pts.mass of an epoxy group-containing compound (B) and 2 to 15 pts.mass of an antimony compound, based on 100 pts.mass of a polymer obtained by polymerization of a monomer composition containing 30 to 70 mass% of acrylonitrile, 30 to 70 mass% of a halogen-containing vinylidene monomer and/or a halogen-containing vinyl monomer and 0 to 10 mass% of a vinyl monomer copolymerizable with these monomers, when the amount of the monomer composition is 100 mass%; a method for producing the halogen-containing flame-retardant fiber; and a flame-retardant fiber composite and a fiber product using the same.

Description

  The present invention relates to a halogen-containing flame retardant fiber having high flame retardancy and antimony detachment suppressing performance, a method for producing the same, a flame retardant fiber composite, and a flame retardant fiber product.

  In recent years, there has been an increase in demands for ensuring safety in clothing, food and living, and environmental awareness. For materials used in clothing, bedding, and other interiors, flameproofing is required, and there is a risk of causing problems for human safety. There is a growing movement to regulate the elution of substances. Regarding the flame resistance, some composites or fiber products using halogen-containing fibers to which an antimony compound is added have been known as fiber products exhibiting high flame retardancy. For example, Patent Document 1 discloses a cover material such as a cushion composed of 85 to 15% by mass of an antimony compound-added halogen-containing fiber and at least one fiber of 85 to 15% by mass selected from wool and cellulose. Patent Document 2 discloses a hair fiber comprising a halogen-containing fiber to which an antimony compound as a flame retardant is added and a polyester fiber. However, just adding an antimony compound to a halogen-containing fiber as in the techniques disclosed in Patent Documents 1 and 2, there is a risk that antimony may be detached at the time of dyeing, as well as harmful effects due to gastric juice and sweat. In tests such as EN71part3 and Ocotex standards assuming the elution of substances, antimony above the specified value may be eluted. As a method for solving this, Patent Document 3 discloses a technique in which the amount of antimony added is reduced or not added by adding magnesium hydroxide into a halogen-containing fiber. Patent Document 4 discloses a technique in which the addition amount of antimony is reduced or not added by adding a glass component to a halogen-containing fiber. Patent Document 5 describes at least one selected from the group consisting of tannins, mercapto group-containing carboxylic acids, polyvalent carboxylic acids, and polyvalent hydroxycarboxylic acids as halogen-containing fibers to which antimony compounds are added as antimony compound elimination inhibitors. A technique for preventing elution of antimony is disclosed by contact treatment with a treatment solution containing two compounds. Further, apart from the study to prevent the elution of antimony, Non-Patent Document 1 discloses a technique for capturing the eluted antimony.

JP-A-11-001842 JP 2002-227019 A JP 2005-314817 A JP 2005-314816 A International Publication No. WO2009 / 093562

Hydrometallurgy 81, 190-196 (2006)

  The techniques disclosed in Patent Documents 3 and 4 have room for improvement in flame retardancy, and in addition, magnesium hydroxide and glass components are added to the spinning bath when spinning the halogen-containing fiber. Has become difficult and has not been improved sufficiently. In addition, the technique disclosed in Patent Document 5 requires blending with cellulosic fibers such as cotton in order to bind tannins when using tannins as an anti-detachment agent. Since it becomes high, the problem remains in practical use. In addition, the technique disclosed in Non-Patent Document 1 irradiates a polyethylene porous hollow fiber membrane with an electron beam, starts the generated radical as a starting point, grafts glycidyl methacrylate, and then bonds the epoxy group with N-methyl group. As a result of passing an antimony (III) solution through a membrane chemically introduced with camin, it has succeeded in adsorbing high concentrations of antimony, but this technology suppresses antimony elution from fibers containing antimony oxide. In order to impart glycidyl methacrylate to a substrate, it is necessary to irradiate an electron beam and then graft polymerize it, which is not practical.

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

  One of the features of the present invention is that when the monomer composition is 100% by mass, acrylonitrile 30 to 70% by mass, halogen-containing vinylidene monomer and / or halogen-containing vinyl monomer 30 to 70% by mass, And 100 parts by mass of a polymer obtained by polymerizing a monomer composition containing 0 to 10% by mass of a vinyl monomer copolymerizable therewith, at least two adjacent hydroxy groups are contained in a single molecule. 2 to 100 parts by mass of the compound (A) to be contained, 1.2 to 20 parts by mass of the epoxy group-containing compound (B), and 2 to 15 parts by mass of the antimony compound (C).

  Another feature of the present invention is a method for producing a halogen-containing flame retardant fiber, wherein the following steps (1) to (5) are sequentially performed. Step (1): A step of dissolving the polymer and the epoxy group-containing compound (B) in a solvent and further adding the antimony compound (C) to prepare a spinning dope. Step (2): A step in which the spinning solution is extruded from a nozzle into a water-organic solvent coagulation bath and solidified, and then passed through a water washing bath to obtain water washing yarn. Step (3): impregnating the washed thread with an aqueous solution containing the compound (A) containing at least two adjacent hydroxy groups in a single molecule, and further reacting with the epoxy group-containing compound (B) A step of obtaining a water-washed yarn in which the compound (A) is bonded via the compound (B). Step (4): A step of removing the unreacted compound (A) by passing the washed thread through a washing bath. Step (5): A step of drying and heat-treating the water-washed yarn.

  Another feature of the present invention is that the halogen-containing flame retardant fiber is 10% by mass or more, and a group consisting of natural fiber, regenerated fiber, semi-synthetic fiber, and synthetic fiber other than the flame retardant halogen-containing flame retardant fiber It is a halogen-containing flame retardant fiber composite comprising 90% by mass or less of at least one selected fiber.

  Another feature of the present invention is a fiber product including the halogen-containing flame retardant fiber or the halogen-containing flame retardant fiber composite.

  According to the present invention, in the elution test of heavy metal in artificial sweat fluid defined in ISO 105-E4 (Test Solution II) based on Ocotex Standard 100 while having flame retardancy, the test result of antimony is a regulated value (30 mg / kg The halogen-containing flame retardant fiber, the flame retardant fiber composite, and the flame retardant fiber product can be obtained.

  As a result of intensive studies to solve the above problems, the present inventors have determined that when the monomer composition is 100% by mass, acrylonitrile is 30 to 70% by mass, halogen-containing vinylidene monomer and / or halogen-containing At least two parts per 100 parts by weight of a polymer obtained by polymerizing a monomer composition containing 30 to 70% by weight of a vinyl monomer and 0 to 10% by weight of a vinyl monomer copolymerizable therewith. 2-100 parts by mass of compound (A) containing adjacent hydroxy groups in a single molecule, 1.2-20 parts by mass of epoxy group-containing compound (B), and 2-15 parts by mass of antimony compound (C) As a result, it was found that high flame retardancy and antimony elution suppression performance can be imparted, and the present invention has been completed.

  The polymer used in the present invention has an acrylonitrile of 30 to 70% by mass, a halogen-containing vinylidene monomer and / or a halogen-containing vinyl monomer of 30 to 70% by mass when the monomer composition is 100% by mass, and It is obtained by polymerizing a monomer composition containing 0 to 10% by mass of a vinyl monomer copolymerizable with these.

  When the content of acrylonitrile in the monomer composition is 30 to 70% by mass, heat resistance necessary for fiberization can be obtained, and flame retardancy can be achieved. A particularly preferable lower limit of the acrylonitrile content is 40% by mass or more, more preferably 50% by mass or more, and an upper limit is preferably 69.7% by mass or less and 69.5% by mass or less. More preferably, they are 60 mass% or less, 59.7 mass% or less, and 59.5 mass% or less. Especially preferably, they are 57 mass% or less, 56.7 mass% or less, and 56.5 mass% or less. If it is the said preferable range, the heat resistance of a fiber will become higher.

  The lower limit of the content of the halogen-containing vinylidene monomer and / or halogen-containing vinyl monomer in the monomer composition is preferably 40% by mass or more, more preferably 43% by mass or more, and the upper limit is preferably It is 69.7 mass% or less, 69.5 mass% or less, More preferably, it is 60 mass% or less, 59.7 mass% or less, 59.5 mass% or less, Most preferably, it is 50 mass% or less, 49. They are 7 mass% or less and 49.5 mass% or less.

  The lower limit of the copolymerizable vinyl monomer in the monomer composition is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and the upper limit is preferably 7% by mass or less. Preferably it is 3 mass% or less.

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

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

  Examples of the vinyl monomer copolymerizable with these 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 styrene sulfonic acid and its salt, allyl sulfonic acid and its salt, 2-acrylamido-2-methylpropane sulfonic 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.

  When such a monomer composition is 100% by mass, acrylonitrile 30 to 70% by mass, halogen-containing vinylidene monomer and / or halogen-containing vinyl monomer 30 to 70% by mass, and copolymerizable therewith Examples of the polymer obtained by polymerizing a monomer composition containing 0 to 10% by mass of a vinyl monomer include, for example, halogen-containing vinylidene such as acrylonitrile-vinylidene chloride and acrylonitrile-vinylidene chloride-vinylidene fluoride. Copolymers of acrylonitrile and acrylonitrile, one or more halogen-containing vinylidene monomers such as vinylidene chloride, vinylidene bromide, vinylidene fluoride, acrylonitrile and vinylidene monomers copolymerizable therewith However, it is not limited to these. Moreover, you may use the said homopolymer and copolymer suitably mixing.

Specific examples of the polymer include the following examples;
(1) a copolymer obtained by polymerizing a monomer composition comprising 51% by mass of acrylonitrile, 48% by mass of vinylidene chloride, and 1% by mass of sodium styrenesulfonate;
(2) a copolymer obtained by polymerizing a monomer composition consisting of 57% by mass of acrylonitrile, 41% by mass of vinylidene chloride, and 2% by mass of sodium allyl sulfonate;
(3) a copolymer obtained by polymerizing a monomer composition consisting of 60% by mass of acrylonitrile, 30% by mass of vinylidene chloride, and 10% by mass of sodium 2-acrylamido-2-methylpropanesulfonate;
(4) a copolymer obtained by polymerizing a monomer composition consisting of 55% by weight of acrylonitrile, 43% by weight of vinylidene chloride, and 2% by weight of sodium methallylsulfonate;
(5) A copolymer obtained by polymerizing a monomer composition consisting of 56% by mass of acrylonitrile, 42% by mass of vinylidene chloride, and 2% 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 compound (A) containing at least two adjacent hydroxy groups in a single molecule refers to a compound in which two atoms bonded to a hydroxy group are covalently bonded to each other. For example, sugar alcohols such as glycerin, erythritol, xylitol, sorbitol, mannitol, tannins such as gallotannin, pentaploid tannin, gallic tannin, tannic acid, ellagic acid, N-methylglucamine, 3-amino-1,2-propane Although diol etc. are mentioned, it is not limited to these.

  It is more preferable that the compound containing at least two adjacent hydroxy groups in a single molecule includes a functional group capable of reacting with an epoxy group separately from the two adjacent hydroxy groups.

  The type of the functional group capable of reacting with the epoxy group is not particularly limited. For example, the functional group can be selected from the group consisting of an amino group, a hydroxy group, a carboxy group, a thiol group, and a salt thereof, a fluoro group, a chloro group, a bromo group, and an iodo group. One or more functional groups selected are preferred.

  Among the compounds containing at least two adjacent hydroxy groups in a single molecule, N-methylglucamine and / or tannic acid are more preferable.

  When the monomer composition is 100% by mass, 30 to 70% by mass of acrylonitrile, 30 to 70% by mass of the halogen-containing vinylidene monomer and / or halogen-containing vinyl monomer, and a vinyl monomer copolymerizable therewith. The lower limit of the content of the compound containing at least two adjacent hydroxy groups in a single molecule with respect to 100 parts by mass of the polymer obtained by polymerizing the monomer composition containing 0 to 10% by mass of the monomer, It is 2 parts by mass or more, preferably 4 parts by mass or more, more preferably 7 parts by mass or more, and the upper limit is 100 parts by mass or less, preferably 20 parts by mass or less, more preferably 15 parts by mass or less.

  In the present specification, the content of the compound containing at least two adjacent hydroxy groups in a single molecule means the content of the compound reacted with the epoxy group-containing compound contained in the halogen-containing flame retardant fiber of the present invention. To do.

  As an epoxy group containing compound, the polymer containing an epoxy group is mentioned, For example, the glycidyl ether, glycidyl amine, glycidyl ester, cycloaliphatic, or the copolymer containing these may be sufficient. Considering elution into the spinning bath and the number of reactive groups (epoxy groups) per unit weight, for example, polyglycidyl methacrylate (weight average molecular weight 3000 to 100,000) is preferably used as the glycidyl ester type.

  When the monomer composition is 100% by mass, 30 to 70% by mass of acrylonitrile, 30 to 70% by mass of the halogen-containing vinylidene monomer and / or halogen-containing vinyl monomer, and a vinyl monomer copolymerizable therewith. The lower limit of the content of the epoxy group-containing compound with respect to the polymer obtained by polymerizing the monomer composition containing 0 to 10% by mass of the monomer is 1.2 parts by mass or more with respect to 100 parts by mass of the polymer. The upper limit is preferably 20 parts by mass or less, preferably 15 parts by mass or less, and more preferably 10 parts by mass or less.

  Examples of the antimony compound used in the present invention include antimony oxide compounds such as antimony trioxide, antimony tetroxide, and antimony pentoxide, antimonic acid and salts thereof, and inorganic antimony compounds such as antimony oxychloride. It is not limited. These may be used in combination.

  When the monomer composition is 100% by mass, 30 to 70% by mass of acrylonitrile, 30 to 70% by mass of the halogen-containing vinylidene monomer and / or halogen-containing vinyl monomer, and a vinyl monomer copolymerizable therewith. The lower limit of the amount of the antimony compound added to 100 parts by mass of the polymer obtained by polymerizing the monomer composition containing 0 to 10% by mass of the monomer is 2 parts by mass or more, preferably 4 parts by mass or more. Preferably it is 7 mass parts or more, and an upper limit is 15 mass parts or less, Preferably it is 10 mass parts or less.

  The halogen-containing flame retardant fiber of the present invention has an acrylonitrile of 30 to 70% by mass, a halogen-containing vinylidene monomer and / or a halogen-containing vinyl monomer of 30 to 70% by mass when the monomer composition is 100% by mass. , And 100 parts by mass of a polymer obtained by polymerizing a monomer composition containing 0 to 10% by mass of a vinyl monomer copolymerizable therewith, at least two adjacent hydroxy groups are contained in a single molecule. 2 to 100 parts by mass of the compound, 1.2 to 20 parts by mass of the epoxy group-containing compound, and 2 to 15 parts by mass of the antimony compound, and produced by a wet spinning method.

  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 coagulated by being extruded into a coagulation bath through a nozzle. And then washed with water, dried, stretched, heat treated, and if necessary, crimped and cut to obtain a product. 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 method for introducing a compound containing at least two adjacent hydroxy groups in a single molecule is not particularly limited. An antimony compound is added to a spinning stock solution in which the polymer and the epoxy group-containing compound are dissolved in a solvent, and then the mixture is extruded and solidified from a nozzle into a coagulation bath containing water and an organic solvent, and then passed through a water washing bath. Is impregnated in an aqueous solution containing a compound containing at least two adjacent hydroxy groups in a single molecule, and reacted with an epoxy group-containing compound to thereby form at least two adjacent hydroxy groups in a single molecule. A method of introducing a compound containing an antimony compound into a spinning stock solution in which the polymer and the epoxy group-containing compound are dissolved in a solvent, then extruding from a nozzle into a coagulation bath containing water and an organic solvent, and then coagulating, Impregnating the water-washed yarn obtained by passing through a solution containing a compound containing at least two adjacent hydroxy groups in a single molecule; Ide, a method of introducing by reacting with an epoxy group-containing compound is preferably a dryer or heat treatment machine above 100 ° C.. In particular, a compound containing at least two adjacent hydroxy groups in a single molecule is introduced by reacting with an epoxy group-containing compound in an aqueous solution containing a compound containing at least two adjacent hydroxy groups in a single molecule. In this case, the temperature of the aqueous solution to be impregnated is preferably 70 ° C. or higher, and preferably 100 ° C. or lower. The lower limit of the temperature of the aqueous solution to be impregnated is more preferably 75 ° C or higher, and still more preferably 80 ° C or higher. The upper limit of the temperature of the aqueous solution to be impregnated is more preferably 95 ° C. or less, and still more preferably 90 ° C. or less. Further, the time for impregnation in the aqueous solution is preferably 1 minute or more, and preferably 60 minutes or less. The lower limit of the time for impregnation in the aqueous solution is more preferably 2 minutes or more, and even more preferably 3 minutes or more. The upper limit of the time of impregnation with the aqueous solution is more preferably 50 minutes or less, and even more preferably 40 minutes or less. The impregnated fiber is more preferable because it can remove unreacted compounds containing at least two adjacent hydroxy groups in a single molecule by passing through a washing bath again.

  The halogen-containing flame retardant 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, in the case of processing by combining with other natural fibers, regenerated fibers, or synthetic fibers, those similar to the fibers to be combined are preferable. The fineness of the halogen-containing flame retardant fiber of the present invention is appropriately selected depending on the composite used, other natural fibers used in the application of the fiber product, regenerated fiber, semi-synthetic fiber or synthetic fiber, but 1-30 dtex. Is preferred, 1 to 10 dtex is more preferred, and 1 to 3 dtex is even more preferred. 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 halogen-containing flame retardant fiber of the present invention has high flame retardancy, and antimony can be removed even if it is exposed to antimony during refining / bleaching, dyeing, or gastric juice, sweat, 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 antimony dissolution test result is less than the regulation value (30 mg / kg). As a result of the antimony dissolution test, fibers of 29 mg / kg or less can be obtained, and fibers with a high degree of antimony desorption, such as 20 mg / kg or less and 10 mg / kg or less, can be obtained.

  The halogen-containing flame-retardant fiber of the present invention can of course be used alone, and is at least one fiber selected from the group consisting of natural fibers, regenerated fibers, semi-synthetic fibers, and other synthetic fibers other than the flame-retardant fibers. It is also possible to use in combination. 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 halogen-containing flame retardant fiber of the present invention. The lower limit of the content of the halogen-containing flame retardant fiber is preferably 30% by mass or more, and the upper limit is 90% by mass or less, preferably 70% by mass or less. Further, it is preferable to contain 90% by mass or less of at least one fiber selected from the group consisting of natural fiber, regenerated fiber, semi-synthetic fiber and synthetic fiber other than the flame retardant fiber, and a preferable lower limit is 30% by mass or more. There is a particularly preferred upper limit of 70% by mass or less.

  Examples of the form of the flame-retardant fiber composite of the present invention include mixed cotton, mixed spinning, mixed fiber, aligned yarn, composite yarn, core-sheathed composite yarn, union, union, lamination, and the like. , Non-woven fabrics, woven fabrics, knitted fabrics, lace nets, braids and the like.

  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 Examples include weaving. Plain weave, satin weave, and woven weave are particularly preferable because they are excellent in texture and strength as a product.

  Examples of knitting include round knitting, weft knitting, warp knitting, pile knitting, flat knitting, tengu knitting, rib knitting, smooth knitting (both sides knitting), rubber knitting, pearl knitting, denby knitting, cord knitting, atlas knitting. , Chain tissue, inserted tissue and the like. Tendon knitting and rib knitting are particularly preferred because they have excellent texture as a product.

  Examples of 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. It is done.

  As the regenerated fiber, regenerated cellulose fiber (rayon, polynosic, trade name “Cupra (registered trademark)” manufactured by Asahi Kasei Co., Ltd., product name “Tencel (registered trademark)” manufactured by Lenzing Co., Ltd., “lenting modal (registered trademark)”), Examples include regenerated collagen fibers and regenerated protein fibers. Furthermore, as a regenerated fiber, special regenerated cellulose fiber (rayon fiber containing water glass: trade name “Vigil (registered trademark)” manufactured by Satellite, trade name “FR Corona (registered trademark)” manufactured by Daiwabo), flame retardant The post-processed flame-retardant cellulose fiber and the raw material flame-retardant rayon fiber (trade name “Lentining FR (registered trademark)” manufactured by Lenzing Co., Ltd.) can also be mentioned.

  Examples of semisynthetic fibers include cellulose acetate fibers such as acetate and triacetate, and promix fibers.

  Synthetic fibers other than the flame retardant fiber 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 Co., Ltd. Registered trademark) ”), polyclar fiber, polyethylene fiber (trade name“ Dyneema (registered trademark) ”manufactured by Toyobo Co., Ltd.), polyurethane fiber, polyoxymethylene fiber, polytetrafluoroethylene fiber, aramid fiber (trade name“ Kevlar manufactured by DuPont ”) (Registered trademark) ”,“ Nomex (registered trademark) ”, trade name“ Technola (registered trademark) ”,“ Twaron (registered trademark) ”,“ Conex (registered trademark) ”manufactured by Teijin Limited), benzoate fiber , Polyphenylene sulfide fiber (trade name “Procon” (registered by Toyobo Co., Ltd.) Standard) ”), polyetheretherketone fiber, polybenzazole fiber, polyimide fiber (trade name“ P84 (registered trademark) ”manufactured by Toyobo Co., Ltd.), polyamide imide fiber (trade name“ Kelmer (registered trademark) ”manufactured by Kelmer) Etc. In addition, flame-retardant polyester (trade name “Hheim (registered trademark)” manufactured by Toyobo Co., Ltd., product name “Trevira CS (registered trademark)” manufactured by Trevira), polyethylene naphthalate fiber (trade name “Teonex (registered trademark) manufactured by Teijin Limited) ), Melamine fiber (trade name “Bazofil (registered trademark)” manufactured by Vasofil Fiber), acrylate fiber (trade name “Moiscare (registered trademark)” manufactured by Toyobo Co., Ltd.), polybenzoxide fiber (trade name “manufactured by Toyobo Co., Ltd.”) Zylon (registered trademark) "). 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. Cellulosic fibers used in the present invention may be natural fibers, regenerated fibers, semi-synthetic fibers, or cellulose fibers belonging to synthetic fibers other than the flame retardant 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 halogen-containing flame retardant 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, pants, 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 Example 1)
A polymer obtained by dissolving a copolymer obtained by polymerizing a monomer composition comprising 51% acrylonitrile, 48% vinylidene chloride and 1% sodium p-styrenesulfonate in acetone so that the polymer concentration is 30%. A solution was obtained. 10 parts by mass of polyglycidyl methacrylate and 4 parts by mass of antimony trioxide were added to 100 parts by mass of the polymer in the obtained polymer solution to obtain a spinning dope. The spinning solution 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, and washed with water while drawing to obtain a washed yarn. The water-washed yarn was impregnated in an aqueous 0.1 mol / L N-methylglucamine solution at 80 ° C. for 5 minutes, washed again with water, then dried at 120 ° C., and further stretched 3 times at 150 ° C. Heat treatment was carried out in supersaturated steam at 30 ° C. for 30 seconds to obtain a halogen-containing flame-retardant fiber having a fineness of 2 dtex. The obtained halogen-containing flame-retardant fiber was coated with a finishing oil for spinning (manufactured by Takemoto Yushi Co., Ltd.), crimped, and cut into a length of 38 mm.

(Production Example 2)
Manufactured in the same manner as in Production Example 1 except that the impregnation time of the water-washed yarn in the 0.1 mol / L N-methylglucamine aqueous solution was 30 minutes to obtain a halogen-containing flame-retardant fiber having a fineness of 2 dtex. The obtained halogen-containing flame-retardant fiber was coated with a finishing oil for spinning (manufactured by Takemoto Yushi Co., Ltd.), crimped, and cut into a length of 38 mm.

(Production Example 3)
Manufactured in the same manner as in Production Example 1 except that the condition of impregnation of water-washed yarn into 0.1 mol / L N-methylglucamine aqueous solution was set at 98 ° C. for 30 minutes to obtain a halogen-containing flame-retardant fiber having a fineness of 2 dtex. It was. The obtained halogen-containing flame-retardant fiber was coated with a finishing oil for spinning (manufactured by Takemoto Yushi Co., Ltd.), crimped, and cut into a length of 38 mm.

(Production Example 4)
The amount of antimony trioxide added in the spinning dope was 10/100 by mass with respect to the polymer in the polymer solution, and impregnation of the water-washed yarn into a 0.1 mol / L N-methylglucamine aqueous solution A halogen-containing flame-retardant fiber having a fineness of 2 dtex was obtained in the same manner as in Production Example 1 except that the conditions were 98 ° C. for 30 minutes. The obtained halogen-containing flame-retardant fiber was coated with a finishing oil for spinning (manufactured by Takemoto Yushi Co., Ltd.), crimped, and cut into a length of 38 mm.

(Production Example 5)
The addition amount of polyglycidyl methacrylate and antimony trioxide in the spinning dope was 20 parts by mass and 10 parts by mass with respect to 100 parts by mass of the polymer in the polymer solution, respectively, and 0.1 mol / L of the washing thread Manufactured in the same manner as in Production Example 1 except that the impregnation condition into the N-methylglucamine aqueous solution was set at 98 ° C. for 30 minutes to obtain a halogen-containing flame-retardant fiber having a fineness of 2 dtex. The obtained halogen-containing flame-retardant fiber was coated with a finishing oil for spinning (manufactured by Takemoto Yushi Co., Ltd.), crimped, and cut into a length of 38 mm.

(Production Example 6)
The addition amount of antimony trioxide in the spinning dope was set to 10 parts by mass with respect to 100 parts by mass of the polymer in the polymer solution, and the water-washed yarn was added to the 0.1 mol / L N-methylglucamine aqueous solution. A halogen-containing flame-retardant fiber having a fineness of 2 dtex was obtained in the same manner as in Production Example 1 except that the impregnation condition was 50 ° C. for 30 minutes. The obtained halogen-containing flame-retardant fiber was coated with a finishing oil for spinning (manufactured by Takemoto Yushi Co., Ltd.), crimped, and cut into a length of 38 mm.

(Production Example 7)
Manufactured in the same manner as in Production Example 1 except that the amount of antimony trioxide added in the spinning dope was 10 parts by mass with respect to 100 parts by mass of the polymer in the polymer solution, and a washed thread was obtained. This washed thread was impregnated in a 140 g / L tannic acid aqueous solution at 98 ° C. for 30 minutes, washed again with water, then dried at 120 ° C., further stretched 3 times at 150 ° C., and then at 180 ° C. for 30 seconds. Heat treatment was performed in supersaturated steam to obtain a halogen-containing flame-retardant fiber having a fineness of 2 dtex. The obtained halogen-containing flame-retardant fiber was coated with a finishing oil for spinning (manufactured by Takemoto Yushi Co., Ltd.), crimped, and cut into a length of 38 mm.

(Production Example 8)
Manufactured in the same manner as in Production Example 1 except that the addition amounts of polyglycidyl methacrylate and antimony trioxide in the spinning dope were 2 parts by mass and 10 parts by mass, respectively, with respect to 100 parts by mass of the polymer in the polymer solution. I got a thread. This washed thread was impregnated in a 140 g / L tannic acid aqueous solution at 98 ° C. for 30 minutes, washed again with water, then dried at 120 ° C., further stretched 3 times at 150 ° C., and then at 180 ° C. for 30 seconds. Heat treatment was performed in supersaturated steam to obtain a halogen-containing flame-retardant fiber having a fineness of 2 dtex. The obtained halogen-containing flame-retardant fiber was coated with a finishing oil for spinning (manufactured by Takemoto Yushi Co., Ltd.), crimped, and cut into a length of 38 mm.

(Production Example 9)
Manufactured in the same manner as in Production Example 1 except that the amount of antimony trioxide added in the spinning dope was 10 parts by mass with respect to 100 parts by mass of the polymer in the polymer solution, and a washed thread was obtained. The washed yarn was impregnated in distilled water at 98 ° C. for 30 minutes, then dried at 120 ° C., further stretched 3 times at 150 ° C., and heat-treated in supersaturated steam at 180 ° C. for 30 seconds to obtain a halogen having a fineness of 2 dtex. A contained flame retardant fiber was obtained. The obtained halogen-containing flame-retardant fiber was coated with a finishing oil for spinning (manufactured by Takemoto Yushi Co., Ltd.), crimped, and cut into a length of 38 mm.

(Production Example 10)
The addition amount of antimony trioxide in the spinning dope was set to 10 parts by mass with respect to 100 parts by mass of the polymer in the polymer solution, and the water-washed yarn was added to the 0.1 mol / L N-methylglucamine aqueous solution. A halogen-containing flame-retardant fiber having a fineness of 2 dtex was obtained in the same manner as in Production Example 1 except that the impregnation condition was 30 ° C. for 30 seconds. The obtained halogen-containing flame-retardant fiber was coated with a finishing oil for spinning (manufactured by Takemoto Yushi Co., Ltd.), crimped, and cut into a length of 38 mm.

(Production Example 11)
Manufactured in the same manner as in Production Example 1 except that the amount of antimony trioxide added in the spinning dope was 10 parts by mass with respect to 100 parts by mass of the polymer in the polymer solution, and a washed thread was obtained. This water-washed yarn was impregnated in a 0.1 mol / L citric acid aqueous solution at 98 ° C. for 30 minutes, washed again with water, then dried at 120 ° C., further stretched 3 times at 150 ° C., and 30 times at 180 ° C. Second, heat treatment in supersaturated steam was performed to obtain a halogen-containing flame-retardant fiber having a fineness of 2 dtex. The obtained halogen-containing flame-retardant fiber was coated with a finishing oil for spinning (manufactured by Takemoto Yushi Co., Ltd.), crimped, and cut into a length of 38 mm.

(Production Example 12)
Manufactured in the same manner as in Production Example 1 except that the amount of antimony trioxide added in the spinning dope was 10 parts by mass with respect to 100 parts by mass of the polymer in the polymer solution, and a washed thread was obtained. This washed thread was impregnated in a 0.1 mol / L lactic acid aqueous solution at 98 ° C. for 30 minutes, washed again with water, then dried at 120 ° C., further stretched 3 times at 150 ° C., and then at 180 ° C. for 30 seconds. Then, heat treatment was carried out in supersaturated steam to obtain a halogen-containing flame-retardant fiber having a fineness of 2 dtex. The obtained halogen-containing flame-retardant fiber was coated with a finishing oil for spinning (manufactured by Takemoto Yushi Co., Ltd.), crimped, and cut into a length of 38 mm.

(Production Example 13)
The addition amount of antimony trioxide in the spinning dope was 20 parts by mass with respect to 100 parts by mass of the polymer in the polymer solution, and the impregnation of the water-washed yarn into a 0.1 mol / L N-methylglucamine aqueous solution. A halogen-containing flame-retardant fiber having a fineness of 2 dtex was obtained in the same manner as in Production Example 1 except that the conditions were 98 ° C. for 30 minutes. The obtained halogen-containing flame-retardant fiber was coated with a finishing oil for spinning (manufactured by Takemoto Yushi Co., Ltd.), crimped, and cut into a length of 38 mm.

(Production Example 14)
The addition amount of antimony trioxide in the spinning dope is 1 part by mass with respect to 100 parts by mass of the polymer in the polymer solution, and the impregnation of the water-washed yarn into the 0.1 mol / L N-methylglucamine aqueous solution A halogen-containing flame-retardant fiber having a fineness of 2 dtex was obtained in the same manner as in Production Example 1 except that the conditions were 98 ° C. for 30 minutes. The obtained halogen-containing flame-retardant fiber was coated with a finishing oil for spinning (manufactured by Takemoto Yushi Co., Ltd.), crimped, and cut into a length of 38 mm.

  Table 1 shows a method for producing a halogen-containing flame retardant fiber, and a compound (A) containing at least two adjacent hydroxy groups in a single molecule in the obtained halogen-containing flame retardant fiber, an epoxy group-containing compound (B ) And the content of the antimony compound (C) are collectively shown.

(Experimental example 1) Content calculation method of epoxy group containing compound (B) Content of epoxy group containing compound (B) was calculated | required with the following calculation methods. That is, in the FT-IR (Perkin Elmer: Spectrum One, Fourier transform infrared spectrophotometer) peak of the fibers prepared in Production Examples 1 to 14 of the halogen-containing flame retardant fiber, the epoxy group of the compound (N) The height of the peak derived from (908 cm ⁻¹ ) is defined as B, and the height N of the peak derived from the nitrile group (2243 cm ⁻¹ ) is defined as B. On the other hand, under the same conditions as in Production Examples 1 to 14 of the halogen-containing flame retardant fiber, but instead of the aqueous solution containing the epoxy group-containing compound (B), FT-IR of the fiber produced by simply impregnating with distilled water If the height of the peak at 908 cm ⁻¹ is b and the height of the peak at 2243 cm ⁻¹ is n, it can be calculated by the following formula.
[Content of epoxy group-containing compound (B) (parts by mass)] = [Content of compound (N) (parts by mass)]
× [(Molecular weight of epoxy group-containing compound (B)) / (Molecular weight of compound (N))] × [1- (B × n) / (N × b)]

(Experimental example 2) Evaluation method of Ocotex test Ocotex test is based on Ocotex Standard 100, and the ISO 105-E04 (Test Tecishi, Katsushika-ku, Tokyo, Japan) was established by the Ocotex International Community Foundation. We asked Solution II) 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 3) Preparation method of flame retardant evaluation test specimens Halogen containing flame retardant fibers and cotton produced in Production Examples 1 to 14 of halogen containing fibers were mixed at a ratio of 55:45, and MDPA (MDPA3 manufactured by Worcester) ) Produced a sliver. 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). Based on. 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 1-8)
With respect to the halogen-containing flame-retardant fibers produced in Production Examples 1 to 8, antimony detachment evaluation in artificial sweat was performed based on the evaluation method of the Ocotex test. In addition, the halogen-containing flame retardant fibers produced in Production Examples 1 to 8 were mixed with cotton, and the knitted fabric produced based on the method for producing a flame retardant evaluation specimen was evaluated according to the flame retardant evaluation method. Carried out.

(Comparative Examples 1-6)
With respect to the halogen-containing flame-retardant fibers produced in Production Examples 9 to 14, the antimony detachment evaluation in the artificial sweat was performed based on the evaluation method of the Ocotex test. In addition, the halogen-containing flame retardant fibers produced in Production Examples 9 to 14 were mixed with cotton, and the knit fabric produced based on the method for producing a flame retardant evaluation specimen was evaluated according to the flame retardant evaluation method. Carried out.

  Table 2 summarizes the results of the ocotetex test and the flame retardancy evaluation of Examples 1 to 8 and Comparative Examples 1 to 6.

  In Examples 1 to 8, in any case, the antimony detachment evaluation in the artificial sweat solution based on the evaluation method of the Ocotex test was passed, and the flame retardancy was also good.

  In Comparative Example 1, a compound containing at least two adjacent hydroxy groups in a single molecule was not contained, and the antimony detachment evaluation in the artificial sweat solution based on the evaluation method of the Ocotex test failed. . Further, in Comparative Example 2, the content of the compound containing at least two adjacent hydroxy groups in a single molecule is small, and the antimony detachment evaluation in the artificial sweat solution based on the evaluation method of the Ocotex test failed. It was. Moreover, in Comparative Example 3 and Comparative Example 4, citric acid or lactic acid was contained instead of the compound containing at least two adjacent hydroxy groups in a single molecule. However, in artificial sweat based on the evaluation method of the Ocotex test. The antimony detachment evaluation failed. Further, in Comparative Example 5, although a compound containing at least two adjacent hydroxy groups in a single molecule is contained, the amount of antimony compound added is large, and antimony in artificial sweat fluid based on the evaluation method of the Ocotex test is included. It was rejected in the detachability evaluation. Further, in Comparative Example 6, a compound containing at least two adjacent hydroxy groups in a single molecule was contained, and the antimony detachment evaluation in the artificial sweat solution based on the evaluation method of the Ocotex test was passed. However, the content of the antimony compound was as small as 1 part by mass, the flame retardancy was insufficient, and it was rejected.

Claims (20)

  When the monomer composition is 100% by mass, 30 to 70% by mass of acrylonitrile, 30 to 70% by mass of the halogen-containing vinylidene monomer and / or halogen-containing vinyl monomer, and a vinyl monomer copolymerizable therewith. 2-100 mass of compound (A) containing at least two adjacent hydroxy groups in a single molecule with respect to 100 mass parts of a polymer obtained by polymerizing a monomer composition containing 0-10 mass% of a monomer Halogen-containing flame retardant fiber containing 1.2 to 20 parts by mass of an epoxy group-containing compound (B) and 2 to 15 parts by mass of an antimony compound (C).   2. The halogen-containing difficulty according to claim 1, wherein the compound (A) containing at least two adjacent hydroxy groups in a single molecule contains a functional group capable of reacting with an epoxy group separately from the two adjacent hydroxy groups. Fibre.   The functional group capable of reacting with the epoxy group is at least one functional group selected from the group consisting of an amino group, a hydroxy group, a carboxy group, a thiol group, and salts thereof, a fluoro group, a chloro group, a bromo group, and an iodo group. The halogen-containing flame-retardant fiber according to claim 2.   The halogen-containing flame retardant fiber according to claim 3, wherein the compound (A) containing at least two adjacent hydroxy groups in a single molecule contains tannins and / or N-methylglucamine.   The halogen-containing flame-retardant fiber according to claim 1, wherein the epoxy group-containing compound (B) is polyglycidyl methacrylate.   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. Halogen-containing flame retardant 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. Halogen-containing flame retardant 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 salt, allylsulfonic acid and its salt, 2-acrylamido-2-methylpropanesulfonic acid and one or more vinyl monomers selected from the group consisting of the salt thereof. Halogen-containing flame retardant fiber.   The halogen-containing flame-retardant fiber according to claim 1, wherein the copolymerizable vinyl monomer is a vinyl monomer containing a sulfonic acid group-containing vinyl monomer.   The halogen-containing flame-retardant fiber according to any one of claims 1 to 9, wherein a test result is less than 30 mg / kg in an antimony elution test in artificial sweat fluid based on Ocotex Standard 100. The method for producing a halogen-containing flame retardant fiber according to any one of claims 1 to 10, wherein the following steps (1) to (5) are performed in order;
Step (1): A step of dissolving the polymer and the epoxy group-containing compound (B) in a solvent and further adding the antimony compound (C) to prepare a spinning dope,
Step (2): Step of obtaining the washed yarn by passing the spinning stock solution through a nozzle into a water-organic solvent coagulation bath and coagulating it, and then passing it through a water bath.
Step (3): impregnating the washed thread with an aqueous solution containing the compound (A) containing at least two adjacent hydroxy groups in a single molecule, and further reacting with the epoxy group-containing compound (B) A step of obtaining water-washed yarn in which the compound (A) is bonded via the compound (B),
Step (4): a step of removing the unreacted compound (A) by passing the washing thread through a washing bath,
Step (5): A step of drying and heat-treating the water-washed yarn.   The method for producing a halogen-containing flame retardant fiber according to claim 11, wherein in the step (3), the temperature of the aqueous solution containing the compound (A) is 70 ° C or higher and 100 ° C or lower.   The halogen-containing flame-retardant fiber according to claim 11 or 12, wherein in the step (3), the impregnation time of the washing thread into the aqueous solution containing the compound (A) is 1 minute or more and 60 minutes or less. Production method.   In the said process (5), the said drying and heat processing are performed in a 100 degreeC or more dryer or heat processing machine, The manufacturing method of the halogen containing flame-retardant fiber as described in any one of Claims 11-13 characterized by the above-mentioned.   The halogen-containing flame retardant fiber according to any one of claims 1 to 10 is selected from the group consisting of 10% by mass or more, natural fiber, regenerated fiber, semi-synthetic fiber, and synthetic fiber other than the halogen-containing flame retardant fiber. A halogen-containing flame-retardant fiber composite comprising at least one kind of fiber.   The halogen-containing flame-retardant fiber composite according to claim 15, comprising 30 to 70% by mass of the halogen-containing flame-retardant fiber.   17 or 16 mass% containing 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 halogen-containing flame-retardant fiber. Halogen-containing 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 halogen-containing flame retardant fiber. The halogen-containing flame retardant fiber composite according to claim 1.   The halogen-containing flame-retardant fiber composite according to claim 18, 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 fiber product comprising the halogen-containing flame retardant fiber according to any one of claims 1 to 10 or the halogen-containing flame retardant fiber composite according to any one of claims 15 to 19.