JPWO2006040873A1 - Flame retardant synthetic fibers, flame retardant fiber composites and upholstered furniture products using the same - Google Patents

Abstract

A flame resistant synthetic fiber having advanced flame resistance is provided. Furthermore, the flame resistant synthetic fiber may preferably be used in textiles used for furniture, such as beddings and chairs, such as mattress, and sofa, etc. that need extremely high carbonizability rendered highly flame resistant by flame resistant agents and advanced flame resistance. The present invention also aims at obtaining upholstered furniture products using the flame resistant fiber composite having advanced flame resistance. That is, the present invention relates to a flame resistant fiber composite consisting of a flame resistant synthetic fiber (A) not less than 10 parts by weight, and at least one fiber (B) selected from a natural fiber and/or a chemical fiber (B) not more than 90 parts by weight, the flame resistant synthetic fiber (A) comprising 100 parts by weight of a polymer containing halogen atom of not less than 17% by weight, 3 to 50 parts by weight of a zinc compound, 0 to 30 parts by weight of an antimony compound, and 3 to 30 parts by weight of an other inorganic compound, a total amount of these compounds being not less than 15 parts by weight, and also relates to upholstered furniture products using the flame resistant fiber composite.

Description

  The present invention has a very high carbonization ability made highly flame retardant with a flame retardant, and can be suitably used for textiles used for bedding such as bed mattresses and chairs, furniture such as sofas that require high flame retardancy. The present invention relates to a flame retardant synthetic fiber having a high flame retardancy, a flame retardant fiber composite, a nonwoven fabric comprising the flame retardant fiber composite, and a upholstered furniture product using them.

  In recent years, demands for ensuring the safety of clothing, food and housing have increased, and the need for flame retardant materials has increased from the viewpoint of flameproofing. Under such circumstances, in order to prevent a fire during sleeping, which causes great human damage at the time of occurrence, there is an increasing need for imparting flame retardancy to materials used for bedding and furniture.

  In products such as bedding and furniture, flammable materials such as cotton, polyester, and urethane foam are often used on the inside and the surface for comfort and design at the time of use. In order to ensure their flameproofness, the use of appropriate flame retardant materials in these products can provide a high level of flame retardancy that prevents flames from being applied to the flammable materials for a long period of time. is important. In addition, the flame retardant material must not impair the comfort and design of products such as bedding and furniture.

  In these textile products, flammable materials such as cotton, urethane foam, and polyester are used for comfort during use. It is important to prevent this. In addition, the flameproof material must not impair the comfort and design of bedding such as mattresses and furniture such as chairs and sofas.

  Various flame retardant synthetic fibers and flame retardants have been studied in the past for the fiber products used in this flame retardant material. The high flame retardancy and comfort required for products such as bedding and furniture There has not yet been a product that fully combines requirements such as design.

  For example, there is a so-called post-processing flame-proofing method, which applies a flameproofing agent to cotton cloth, but there are problems such as uniform adhesion of the flameproofing agent, curing of the fabric due to adhesion, detachment by washing, safety, etc. .

  In addition, when polyester, which is an inexpensive material, is used, polyester cannot become a carbonizing component, so when forcedly burned, it melts and has holes, and the structure cannot be maintained. The cotton and urethane foam used for furniture and the like were flared, and the performance was quite inadequate.

  In addition, fabrics made from organic heat-resistant fibers have excellent flame retardancy but are extremely expensive. Further, they have a design property due to problems of processability at the time of opening, poor hygroscopicity and touch, and poor dyeability. There is also a problem that it is difficult to obtain a high color pattern.

Materials that improve the defects of flame retardant fiber materials used in furniture and bedding, have excellent texture, moisture absorption, and tactile sensation required as general characteristics, and have stable flame retardant properties As a proposal, a flame retardant fiber composite (Patent Document 1) in which a highly flame retardant halogen-containing fiber to which a large amount of a flame retardant is added is combined with other fibers that are not flame retardant has been proposed. In addition, it is a highly flame-retardant fiber composite (Patent Document 2) that can be used for work clothes by mixing a small amount of organic heat-resistant fiber, and is excellent in texture and moisture absorption and has high flame retardancy. However, since the organic heat-resistant fiber is generally colored, the whiteness of the fabric is insufficient, and there is a problem in coloring due to dyeing, and the flame-retardant fiber composite has a problem in design. Furthermore, they have also proposed a flame-retardant nonwoven fabric (Patent Document 3) having a bulkiness from essentially flame-retardant fibers and halogen-containing fibers. In these methods, a plurality of fibers are combined. High flame retardancy cannot be obtained unless used, and the manufacturing process of the product becomes complicated. Organic heat-resistant fibers and fibers that are inherently flame retardant are generally expensive and disadvantageous in terms of cost. There was a problem that there was.
JP 61-89339 A JP-A-8-218259 WO03 / 023108

  The present invention is a problem difficult to solve with conventional flame retardant materials, that is, a flame retardant synthetic fiber suitably used for upholstered furniture products having good processability, texture, and touch and having a good design. The present invention has been made in order to obtain a flame retardant composite, a nonwoven fabric made of the flame retardant fiber composite, and upholstered furniture products using them.

As a result of intensive studies to solve the above problems, the present inventors have made it possible to incorporate a zinc compound, an antimony compound, and other inorganic compounds into a flame retardant synthetic fiber containing 17% by weight or more of a halogen, thereby processing it. It has been found that a high degree of flame retardancy can be obtained while maintaining good properties, texture and touch. As a result, there is provided a flame-retardant synthetic fiber capable of obtaining a textile product used for furniture, bedding, etc. having flame retardancy and self-extinguishing properties that can withstand a long flame without impairing the design. It was found that it can be obtained at low cost. Moreover, it discovered that the problem of workability and a price which was a problem at the time of using a heat resistant fiber alone could be improved, and came to complete this invention.
More specifically, by using a fiber containing a zinc compound, an antimony compound, and other inorganic compounds in combination with a flame retardant synthetic fiber containing 17% by weight or more of halogen, the workability, texture, and touch are good and the design is not impaired. It is used for furniture, bedding, etc. that require high flame retardance as a result of having high flame retardancy that maintains the fiber form after combustion by expressing extremely high carbonization and self-extinguishing properties during combustion. It has been found that a flame retardant synthetic fiber (A) capable of obtaining a textile product and a flame retardant fiber composite obtained by combining this with at least one kind of natural fiber and / or chemical fiber (B) are obtained. It was. Moreover, it discovered that the problem of workability and a price which was a problem when using a heat-resistant fiber alone was able to be improved, and came to complete this invention.

That is, the present invention includes 3 to 50 parts by weight of a zinc compound, 0 to 30 parts by weight of an antimony compound, and 3 to 30 parts by weight of other inorganic compounds with respect to 100 parts by weight of a polymer containing 17% by weight or more of a halogen atom. It is a flame retardant fiber composite comprising a flame retardant synthetic fiber (A) of 10 parts by weight or more and a natural fiber and / or a chemical fiber (B) of 90 parts by weight or less, the total of these compounds being 15 parts by weight or more. Preferably, the polymer containing 17% by weight or more of halogen atom is 30 to 70% by weight of acrylonitrile, 70 to 30% by weight of halogen-containing vinyl and / or halogen-containing vinylidene monomer, and a vinyl monomer copolymerizable therewith. It is a flame retardant synthetic fiber (A) comprising 0 to 10% by weight of the body. The zinc compound contained in the flame retardant synthetic fiber (A) is a compound selected from zinc, zinc oxide, zinc borate, zinc stannate and zinc carbonate, and the inorganic compound is kaolin, zeolite, montmorillonite, talc, pearlite. Natural or synthetic mineral products such as bentonite, vermiculite, diatomaceous earth, graphite, aluminum compounds such as aluminum hydroxide, aluminum sulfate, aluminum silicate, magnesium compounds such as magnesium hydroxide, magnesium oxide, silicate, glass, etc. It is a compound selected from silicon compounds. The present invention relates to a flame retardant fiber composite using 0 to 40 parts by weight of a polyester fiber as the flame retardant synthetic fiber (A) and natural fiber and / or chemical fiber fiber (B), particularly a low melting point binder fiber. Furthermore, the present invention relates to nonwoven fabrics composed of these flame retardant fiber composites, particularly flame retardant barrier nonwoven fabrics, and further relates to upholstered furniture products using these flame retardant fiber composites, nonwoven fabrics, and flame shield barrier nonwoven fabrics.
Hereinafter, the fiber (A) used for the flame-retardant fiber composite means the above-described flame-retardant synthetic fiber.

  The flame-retardant synthetic fiber composite of the present invention and interior fiber products obtained from the composite are excellent in design properties such as texture, touch and sight, and processability, and are highly advanced by maintaining the fiber form even for a long flame. It is possible to have excellent flame retardancy.

  The lower limit of the preferable halogen content in the polymer containing 17% or more of the halogen atom of the present invention is 20%, more preferably 26%, the upper limit is 86%, more preferably 73%, and particularly preferably 48%. When the halogen content is less than 17%, it is difficult to make the fiber flame-retardant, which is not preferable. The upper limit of the halogen content is 86% is the halogen content of the vinylidene bromide homopolymer, and this value is the upper limit of the halogen content. In order to obtain a higher halogen content, it is necessary to increase the number of halogen atoms in the monomer, which is not technically practical.

  Examples of the polymer containing a halogen atom of 17% or more include, for example, a polymer of a monomer containing a halogen atom, and a copolymer of a monomer containing a halogen atom and a monomer not containing a halogen atom. A mixture of a polymer containing a halogen atom and a polymer not containing a halogen atom, a monomer or polymer containing no halogen atom during polymerization, and after polymerization, Examples include, but are not limited to, coalescence.

  Specific examples of such a polymer containing 17% by weight or more of halogen atoms include halogen-containing vinyl-based or vinylidene-based polymers such as vinyl chloride, vinylidene chloride, vinyl bromide, vinylidene bromide, vinyl fluoride, vinylidene fluoride, and the like. Monomer homopolymer or two or more copolymers; acrylonitrile-vinyl chloride, acrylonitrile-vinylidene chloride, acrylonitrile-vinyl bromide, acrylonitrile-vinyl fluoride, acrylonitrile-vinyl chloride-vinylidene chloride, acrylonitrile-vinyl chloride -Vinyl bromide, acrylonitrile-vinylidene chloride-vinyl bromide, acrylonitrile-vinylidene chloride-vinylidene fluoride copolymer of acrylonitrile and vinyl chloride, vinylidene chloride, A copolymer of at least one halogen-containing vinyl-based or vinylidene-based monomer such as vinyl chloride, vinylidene bromide, vinyl fluoride, vinylidene fluoride, and a vinyl monomer copolymerizable with acrylonitrile; Examples include polymers obtained by adding and polymerizing halogen-containing compounds to acrylonitrile homopolymers; halogen-containing polyesters; copolymers of vinyl alcohol and vinyl chloride; polymers obtained by chlorination treatment of polyethylene, polyvinyl chloride, and the like. It is not limited to these. Moreover, you may use the said homopolymer and copolymer suitably mixing.

  The polymer containing 17% by weight or more of the halogen atom is 30 to 70 parts by weight of acrylonitrile, 70 to 30 parts by weight of halogen-containing vinyl and / or halogen-containing vinylidene monomer, and vinyl monomer 0 copolymerizable therewith. 10 to 10 parts by weight, preferably 40 to 60 parts by weight of acrylonitrile, 60 to 40 parts by weight of a halogen-containing vinyl and / or halogen-containing vinylidene monomer, and 0 to 10 parts by weight of a vinyl monomer copolymerizable therewith. In the case of a polymer, the obtained fiber is particularly preferable because it has a desired performance (strength, flame retardancy, dyeability, etc.) and has an acrylic fiber texture.

  Examples of the vinyl monomers copolymerizable therewith include acrylic acid, its ester, methacrylic acid, its ester, acrylamide, methacrylamide, vinyl acetate, vinyl sulfonic acid, its salt, methallyl sulfonic acid, its salt Styrene sulfonic acid, a salt thereof, 2-acrylamido-2-methylsulfonic acid, a salt thereof, and the like, 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.

  Examples of the vinyl monomers copolymerizable therewith include acrylic acid, its ester, methacrylic acid, its ester, acrylamide, methacrylamide, vinyl acetate, vinyl sulfonic acid, its salt, methallyl sulfonic acid, its salt Styrene sulfonic acid, a salt thereof, 2-acrylamido-2-methylsulfonic acid, a salt thereof, and the like, 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.

Specific examples of the copolymer containing the halogen-containing vinyl monomer and / or the halogen-containing vinylidene monomer and a unit from acrylonitrile include, for example, 50 parts of vinyl chloride, 49 parts of acrylonitrile, and 1 part of sodium styrenesulfonate. A copolymer comprising 47 parts of vinylidene chloride, 51.5 parts of acrylonitrile, 1.5 parts of sodium styrenesulfonate, 41 parts of vinylidene chloride, 56 parts of acrylonitrile, sodium 2-acrylamido-2-methylsulfonate There are 3 parts. This can be obtained by known polymerization methods.

  Examples of the zinc compound used in the present invention include, but are not limited to, zinc, zinc oxide, zinc borate, zinc stannate, and zinc carbonate. Moreover, there is no problem even if these are used in combination. The amount used is 3 to 50 parts by weight, preferably 4 to 40 parts by weight, and more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the polymer containing 17% or more of halogen atoms. When the amount is less than 3 parts by weight, the effect of carbonizing a polymer containing 17% or more of halogen atoms during combustion (carbonization effect) tends to be reduced, and a necessary carbonization effect for obtaining a desired high flame retardancy is obtained. I can't. If it exceeds 50 parts by weight, a sufficient carbonization effect and shape retention effect can be obtained, but this is not preferable because yarn breakage and the like occur in the production process during fiberization. The average particle size of the zinc compound is 3 μm or less, avoiding troubles such as nozzle clogging in the fiber production process by adding a zinc compound component to a halogen-containing polymer, improving the strength of the fiber, From the viewpoint of dispersion of the zinc compound component particles. Further, the zinc compound component may be chemically modified to improve the blocking property.

  Examples of the antimony compounds include, but are not limited to, antimony oxide compounds such as antimony trioxide, antimony tetraoxide, and antimony pentoxide, inorganic antimony compounds such as antimonic acid and salts thereof, and antimony oxychloride. is not. Moreover, there is no problem even if these are used in combination. The amount is 0 to 30 parts by weight, preferably 0 to 25 parts by weight, and more preferably 0 to 20 parts by weight with respect to 100 parts by weight of a polymer containing 17% or more of halogen atoms. If the amount exceeds 30 parts by weight, the effect is saturated and the cost is increased. Even if it is 0 part by weight, the desired flame retardant performance may be achieved, but since the self-extinguishing effect is small, it is 3 parts by weight or more when used for applications that require a higher level of self-extinguishing effect. It is preferable to add.

  Examples of the inorganic compound include kaolin, zeolite, montmorillonite, talc, pearlite, bentonite, vermiculite, diatomaceous earth, graphite and other natural or synthetic mineral compounds, aluminum hydroxide, aluminum sulfate, aluminum silicate and other aluminum compounds, water Examples thereof include, but are not limited to, magnesium compounds such as magnesium oxide and magnesium oxide, and silicon compounds such as silicate and glass. Moreover, there is no problem even if these are used in combination. The amount is 3 to 30 parts by weight, preferably 5 to 25 parts by weight, and more preferably 7 to 20 parts by weight with respect to 100 parts by weight of a polymer containing 17% or more of halogen atoms. If the amount is less than 3 parts by weight, the amount of carbide remaining at the time of combustion is small, so that a sufficient shape retention effect cannot be obtained. If the amount exceeds 30 parts by weight, the effect is saturated and the cost increases and nozzle clogging occurs in the fiber manufacturing process. This is not preferable because it may cause troubles such as.

  The total amount of these zinc compound, antimony compound and other inorganic compounds is 15 parts by weight or more and 110 parts by weight or less, preferably 17 parts by weight or more and 70 parts by weight or less, with respect to 100 parts by weight of the polymer containing 17% or more of halogen atoms. Preferably they are 20 to 50 weight part. If it is less than 15 parts by weight, the amount of these additives is so small that it is difficult and difficult to obtain the intended high flame retardant effect.

  The flame retardant synthetic fiber of the present invention contains other additives such as an antistatic agent, a thermal coloring inhibitor, a light resistance improver, a whiteness improver, a devitrification agent, a colorant, and a flame retardant as necessary. You can squeeze it.

The flame-retardant synthetic fiber of the present invention is produced by a known production method such as a wet spinning method, a dry spinning method, a semi-dry semi-wet method, etc., using a polymer containing a halogen atom of 17% by weight or more. For example, in the wet spinning method, the above polymer is dissolved in a solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, acetone, or a rhodan salt aqueous solution, and then coagulated by extrusion through a nozzle into a coagulation bath, and then washed with water. , Drying, stretching, heat treatment, and if necessary, crimping and cutting to obtain a product.
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, it is a fiber to be combined with other natural fibers and chemical fibers to be processed. Approximate ones are preferable, and short fibers having a length of about 1.7 to 12 dtex and a cut length of about 38 to 128 mm are preferable in accordance with other natural fibers and chemical fibers used for textile products.

  The reason why the flame-retardant synthetic fiber of the present invention exhibits highly excellent flame retardancy is considered as follows. A fiber (A) containing 3 to 50 parts by weight of a zinc compound, 0 to 30 parts by weight of an antimony compound, and 3 to 30 parts by weight of another inorganic compound with respect to 100 parts by weight of a polymer containing 17% or more of a halogen atom. When burned by a flame source, first, halogen atoms in the polymer desorbed by the burning of the polymer easily react with the zinc compound and antimony compound contained in the fiber (A), and zinc chloride and antimony chloride. When the compound does not contain an antimony compound, hydrogen chloride is generated. Since zinc chloride acts as a catalyst for the cross-linking reaction between molecular chains in the polymer, the molecular chains in the polymer are cross-linked during combustion to form a strong carbide (carbonization effect). Further, antimony chloride compound or hydrogen chloride is a low boiling point compound and its gas is nonflammable, so it shuts off oxygen at the combustion site, suppresses combustion and extinguishes fire (self-extinguishing effect). Furthermore, since other inorganic compounds are not completely burned off during combustion, when the above-mentioned strong carbide is generated, the strength of the carbide is made stronger by remaining in the carbide (morphological retention effect). . As a result, the fiber (A) has a carbonization effect, a self-extinguishing effect, and a shape-holding effect, so that the shape of the fiber is maintained in the state of carbide without breaking the fiber shape even after combustion. Therefore, the flame is cut off, and the further spread of fire is suppressed, so that highly flame retardancy is exhibited.

  The natural fiber and / or chemical fiber (B) used in the present invention is for imparting excellent texture, touch, design, product strength, washing resistance and durability to the flame retardant fabric of the present invention. It is a component that improves processability when using a flame-retardant nonwoven fabric for bedding and furniture.

  Specific examples of the natural fibers include plant fibers such as cotton and hemp, animal fibers such as wool, camel hair, goat wool, and silk, and specific examples of chemical fibers include viscose rayon fibers. Examples thereof include, but are not limited to, recycled fibers such as cupra fibers, recycled fibers such as acetate fibers, and synthetic fibers such as nylon fibers, polyester fibers, polyester-based low melting point binder fibers, and acrylic fibers. These natural fibers and chemical fibers may be used alone with the flame retardant synthetic fiber (A), or two or more types may be used with the flame retardant synthetic fiber (A).

  In the present invention, a polyester-based fiber generates a melt upon combustion, and the carbonized layer formed by the flame-retardant nonwoven fabric becomes stronger by covering the flame-retardant nonwoven fabric, so that the bedding even if exposed to intense flames for a long time It can provide flame shielding barrier performance to prevent flames from being applied to cotton and urethane foam used in furniture and furniture, it is easy to obtain bulkiness when processed into non-woven fabric, and halogen-existing synthetic fibers in the opening machine (card) It is preferable to contain 15 to 25 parts by weight of polyester as B out of 100 parts by weight of the whole (A + B), because the fiber is less damaged due to the problem of strength. When a polyester-based low-melting-point binder fiber is used, a simple hot-melt bonding method can be adopted when forming a nonwoven fabric. The polyester-based low-melting-point binder fiber may be a low-melting-point polyester single-type fiber or a parallel-type or core-sheath type composite fiber made of polyester / low-melting-point polypropylene, low-melting-point polyethylene, or low-melting-point polyester. In general, the low melting point polyester has a melting point of about 110 to 200 ° C, the low melting point polypropylene has a melting point of about 140 to 160 ° C, and the low melting point polyethylene has a melting point of about 95 to 130 ° C. There is no particular limitation as long as it has a melting adhesive ability to the extent. In addition, when a polyester fiber having a low melting point is used, a simple needle punch method can be employed when forming a nonwoven fabric.

  In the present invention, 100 parts by weight of the flame-retardant fabric of the present invention is produced from 10 parts by weight or more of the flame-retardant synthetic fiber (A) and 90 parts by weight or less of the natural fiber and / or chemical fiber (B). The mixing ratio is the water resistance, texture, moisture absorption, touch, design, product strength, washing resistance, durability, as well as the flame resistance required for the final product manufactured from the resulting flame retardant nonwoven fabric. It is determined according to the quality. Generally, the total of synthetic fiber (A) 95 to 10 parts by weight, preferably 60 to 20 parts by weight, natural fiber and / or chemical fiber (B) 5 to 90 parts by weight, preferably 80 to 40 parts by weight is 100 parts by weight. It is compounded to become. When the hot melt bonding method is selected during the production of the nonwoven fabric, it is preferable that at least 10 parts by weight of polyester-based low-melting-point binder fibers are included as natural fibers and / or chemical fibers (B).

  When the amount of the flame retardant synthetic fiber (A) is less than 10 parts by weight, the formation of a carbonized layer for preventing flames from being applied to cotton and urethane foam used for bedding and furniture when exposed to intense flames for a long time. Insufficient and poor self-extinguishing properties make it difficult to obtain the desired high flame retardant performance.

  The flame retardant fiber composite of the present invention is a composite of the fibers (A) and (B) as described above, a fabric such as a woven fabric and a nonwoven fabric, a collection of fibers such as a sliver and a web, a spun yarn and a composite. It is in the form of a string-like material such as a thread or twisted yarn, a string-like material such as a braided string or a braided string.

  The composite means that the fibers (A) and (B) are mixed by various methods to obtain a cloth containing the fibers in a predetermined ratio, and each of the mixed cotton, spinning, twisting, weaving and knitting stages. It means combining fiber and yarn.

  The flame retardant fiber composite of the present invention is suitably used as a nonwoven fabric for flame shielding barriers. The flame-shielding barrier here means that when the flame-retardant nonwoven fabric is exposed to flame, the flame-retardant nonwoven fabric is carbonized while maintaining the fiber form to shield the flame, and the flame moves to the opposite side. Specifically, in the event of a fire, the flame-retardant nonwoven fabric of the present invention is sandwiched between a surface fabric such as a mattress or upholstered furniture and an internal structure such as urethane foam or stuffed cotton. This prevents flames from igniting internal structures and minimizes damage. As a method for producing a flame retardant nonwoven fabric, it is possible to use a nonwoven fabric creation method such as a general hot melt bonding method, chemical bond method, water jet method, needle punch method, stitch bond method, etc. After the cotton is blended, it is opened by a card, a web is created, and the web is applied to a nonwoven fabric manufacturing apparatus. From the viewpoint of simplicity of the apparatus, it is preferable to use a needle punch method or a polyester-based low-melting-point binder fiber because the production by the hot melt bonding method is general and the productivity is high, but it is not limited thereto.

  The flame retardant fiber composite of the present invention may contain an antistatic agent, a thermal coloring inhibitor, a light fastness improver, a whiteness improver, a devitrification preventive agent, and the like as necessary. There is no problem with coloring or dyeing with pigments.

  The flame retardant fiber composite of the present invention thus obtained has desired flame retardancy and has excellent properties such as texture, touch, hygroscopicity, and design.

  The upholstered furniture of the present invention relates to bedding such as a bed mattress, a chair, a sofa, a vehicle seat, and the like upholstered by the above-mentioned flame-retardant fiber composite.

  Examples of the bed mattress include a pocket coil mattress in which a metal coil is used, a box coil mattress, a mattress in which an insulator in which styrene, urethane resin, or the like is foamed is used. By exhibiting flame retardancy due to the flame retardant composite used in the present invention, it is possible to prevent the spread of fire to the internal structure of the mattress. A mattress with excellent texture and touch can be obtained.

  On the other hand, as chairs used indoors, tools, benches, side chairs, armchairs, lounge chairs and sofas, seat units (sectional chairs, separate chairs), rocking chairs, folding chairs, stacking chairs, swivel chairs, Or automobile seats, marine seats, aircraft seats, train seats, etc., used outdoors for vehicle seats, etc., but also in these, the internal fire spreads at the same time as the appearance and feel required for normal furniture It is possible to obtain a upholstered product having a function of preventing the above.

  In addition, in mattresses and chairs using low-resilience urethane foam having a pressure dispersion function typified by Tempur material (Tempur World, Inc.), foam materials made of foamed ordinary styrene or urethane resin are used. Although it is extremely flammable compared to the mattress and chair used, the flame retardant property of the flame retardant fiber composite used in the present invention demonstrates the low resilience urethane that is the internal structure of the mattress and chair Fire spread to foam can be prevented.

  As a method of using the flame-retardant fiber composite of the present invention for upholstered furniture products, the surface fabric may be used in the form of woven fabric or knit, or the surface fabric and internal structure such as urethane foam or stuffed cotton. It may be sandwiched in the form of woven fabric, knit or non-woven fabric. When used for the surface fabric, the fabric made of the flame retardant fiber composite of the present invention may be used instead of the conventional surface fabric. In addition, when a woven fabric or a knit is sandwiched between the surface fabric and the internal structure, the surface fabric may be sandwiched in the manner of overlapping two sheets, or the internal structure is a woven fabric made of the flame retardant fiber composite of the present invention. Or it may be covered with knit. When sandwiched between the surface fabric and the internal structure as a woven fabric for a flame-shielding barrier, the flame retardant fiber of the present invention must be placed on the entire internal structure, and at least the portion in contact with the surface fabric outside the internal structure. A non-woven fabric made of a composite is covered, and the surface fabric is stretched over it.

  When producing upholstered furniture using the flame retardant fiber composite of the present invention, the flame retardant fiber composite of the present invention has excellent characteristics, that is, highly excellent flame retardancy, texture, touch, and moisture absorption. Thus, a upholstered furniture product having excellent design characteristics can be obtained.

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 addition, the flame retardance of the fiber in an Example was measured and judged as follows. In addition, the comprehensive judgment was determined as pass ○, fail × by combining the results of these four methods, flame retardancy evaluation test (LOI value, flame retardance of nonwoven fabric, cogging fire extinguishing time), residual rate during heating, and the results of these four methods. .
(Flame retardance evaluation method 1)
(Flame resistance evaluation by LOI value)
Take 2g of the fiber prepared according to the following production example, divide this into 8 parts, and make 8 ridges of about 6cm to make an oxygen index measuring instrument (SUGA TEST INSTRUMENT Co., LTD. ON-1 The minimum oxygen concentration required for this sample to continue to burn for 5 cm was measured, and this was taken as the LOI value. It shows that it is hard to burn, so that a flame retardance is high, so that LOI value is large.
(Flame resistance evaluation by non-woven fabric)
1) Preparation of non-woven fabric for flame retardancy evaluation test Fibers prepared according to the following production examples were opened with a roller card, and then a non-woven fabric having a basis weight of 300 g / m 2 and a length of 20 cm × width 20 cm was prepared by a needle punch method.
2) Flame Retardancy Evaluation Test Method Prepare a pearlite plate with a length of 200 mm × width 200 mm × thickness 10 mm with a hole with a diameter of 15 cm at the center, and place a non-woven fabric for flame retardant evaluation test on it. Four sides were fixed with clips so that the nonwoven fabric for flame retardancy evaluation test did not shrink. With this sample facing the non-woven fabric for flame retardancy evaluation test, the center of the sample and the center of the burner are aligned with a gas stove (PA-10H-2 manufactured by Paloma Kogyo Co., Ltd.) 40 mm from the burner surface. I set it. The fuel gas used was propane with a purity of 99% or more, the flame height was 25 mm, and the flame contact time was 180 seconds.
At this time, a case where there was no hole penetrating through the carbonized layer of the non-woven fabric for flame retardancy evaluation test was marked with ◯, a case where the hole was cracked was marked with ×, and a mark was marked with ◯.
(Flame retardant evaluation by measuring fire extinguishing time)
2 g of the fiber prepared according to the following production example was taken, and this was divided into 8 equal parts to prepare 8 pieces of about 6 cm twist. After winding a mending tape (Scotch Mending Tape manufactured by Sumitomo 3M Co., Ltd.) twice with a width of 13 mm around one end of the coyori, 2
A second indirect flame. It was allowed to stand in that state, and the time until extinguishing the fire spontaneously (fire extinguishing time) was measured. The shorter the fire extinguishing time, the higher the self-extinguishing effect and the higher the flame retardancy.
(Measurement method of residual rate (carbide weight) during heating)
About 5 mg of the fiber prepared according to the following production example was taken and measured with a thermogravimetric measuring device (TG / DTA220 manufactured by Seiko Instruments Inc., used gas: air, gas flow rate: 200 ml / min, temperature increase rate: 3 ° C./min). did. The initial weight was 100%, and the weight of residue (carbide) at 500 ° C. was expressed as a ratio. The larger the number, the greater the amount of residue (carbide), indicating better performance.
(Measurement method of halogen content in fiber)
The obtained copolymer is subjected to elemental analysis on C element, H element, and N element by an elemental analyzer (CHN coder MT-5 manufactured by Yanaco Co., Ltd.), N atom is derived from acrylonitrile, and N atom is contained. The acrylonitrile component content in the polymer was determined from the amount. Further, it was assumed that the total amount of p-styrene sulfonic acid soda was copolymerized, the remainder was regarded as a component derived from a halogen monomer, and the halogen content in the halogen-containing copolymer obtained by calculation was determined.
(Production Example 1)
A resin obtained by dissolving a copolymer (halogen atom ratio: 35%) of 51% acrylonitrile, 48% vinylidene chloride and 1% p-styrenesulfonic acid soda in dimethylformamide so that the resin concentration is 30%. Zinc oxide (3 types of zinc oxide manufactured by Sakai Chemical Co., Ltd.), antimony trioxide as the antimony compound, and kaolin (Engelhard, Inc.) as the other inorganic compound in the addition amounts shown in Tables 1 and 2 with respect to the resin weight of the solution Kaolin ASP170) or aluminum hydroxide was added to prepare a spinning dope. This spinning dope was extruded into a 50% aqueous dimethylformamide solution using a nozzle with a nozzle hole diameter of 0.10 mm and a hole number of 1000 holes, washed with water, dried at 120 ° C., then stretched 3 times, and further at 150 ° C. A halogen-containing fiber was obtained by heat treatment for 5 minutes and further cutting. The obtained fiber was a fine fiber having a fineness of 5.6 dtex and a cut length of 51 mm.
(Production Example 2)
A copolymer of 49% acrylonitrile, 50.5% vinyl chloride and 0.5% sodium p-styrenesulfonate (halogen atom ratio: 34%) was dissolved in dimethylformamide so that the resin concentration was 30%. Zinc oxide (3 types of zinc oxide manufactured by Sakai Chemical Co., Ltd.), antimony trioxide as antimony compound, and kaolin as other inorganic compound in the addition amounts shown in Tables 3 and 4 with respect to the resin weight of the obtained resin solution (Kaolin ASP170 manufactured by Engelhard) or aluminum hydroxide was added to prepare a spinning dope.
This spinning dope was extruded into a 50% dimethylformamide aqueous solution using a nozzle having a nozzle hole diameter of 0.10 mm and a hole number of 1000 holes, washed with water, dried at 120 ° C., then stretched 3 times, and further at 130 ° C. A halogen-containing fiber was obtained by heat treatment for 5 minutes and further cutting. The obtained fiber was a fine fiber having a fineness of 5.6 dtex and a cut length of 51 mm.
(Examples 1-4, Comparative Examples 1-3)
According to Production Example 1, a halogen-containing fiber was prepared by adding zinc oxide as the zinc compound, antimony trioxide as the antimony compound, and kaolin as the other inorganic compound in the amounts shown in Table 1, and evaluated the LOI value, flame retardancy evaluation in the nonwoven fabric, and The residual rate at the time of combustion was measured by thermogravimetry. The results are shown in Table 1.

  The combustion test results of Examples 1 to 4 were good. The LOI value is high, and in non-woven fabric testing, after heating with a gas stove, it forms a good carbonized layer, passes without the occurrence of drilling or cracking, and has a high residual rate during heating, so it has high flame resistance. We judged that we were doing and passed general judgment. Although Example 4 also has a high flame retardancy, Example 3 has the same amount of zinc oxide and kaolin as Example 4, but contains antimony trioxide, so the fire extinguishing time is longer. It can be seen that it is short and has a higher degree of flame retardancy.

  In contrast, in Comparative Example 1, the amount of antimony trioxide and the total amount of additives was the same as in Example 1, but since there was no kaolin, a good carbonized layer could not be formed and holes were formed in the nonwoven fabric. Since the LOI value and the residual rate at the time of heating were low, the comprehensive judgment failed.

  In Comparative Example 2, the amount of antimony trioxide and the total amount of additives was the same as in Example 1, but because there was no zinc oxide, a good carbonized layer could not be formed, and a hole was formed in the nonwoven fabric. The overall judgment was rejected due to the low survival rate.

  In Comparative Example 3, since the total amount of zinc oxide and kaolin is small, a good carbonized layer cannot be formed, a hole is formed in the nonwoven fabric, and it cannot be determined that it has high flame retardancy, and a comprehensive judgment is made. It was rejected. The flame retardancy evaluation test results of Examples 1 to 4 and Comparative Examples 1 to 3 are shown in Table 1.

（実施例５〜９、比較例４、５）
製造例１に従い、亜鉛化合物として酸化亜鉛、アンチモン化合物として三酸化アンチモン、その他無機化合物として水酸化アルミニウムを表２の量で添加したハロゲン含有繊維を作成し、ＬＯＩ値、不織布での難燃性評価、及び熱重量測定による燃焼時の残存率測定を実施した。結果を表２に示す。

(Examples 5 to 9, Comparative Examples 4 and 5)
According to Production Example 1, a halogen-containing fiber was prepared by adding zinc oxide as the zinc compound, antimony trioxide as the antimony compound, and aluminum hydroxide as the other inorganic compound in the amounts shown in Table 2, and evaluated the LOI value and flame retardancy of the nonwoven fabric. And the residual rate measurement at the time of combustion was performed by thermogravimetry. The results are shown in Table 2.

  The combustion test results of Examples 5 to 9 were good. The LOI value is high, and in non-woven fabric testing, after heating with a gas stove, it forms a good carbonized layer, passes without the occurrence of drilling or cracking, and has a high residual rate during heating, so it has high flame resistance. We judged that we were doing and passed general judgment. Example 8 also has high flame retardancy, but Example 7 has the same amount of zinc oxide and aluminum hydroxide as Example 8, but contains antimony trioxide, so Is shorter and has a higher degree of flame retardancy.

  In Comparative Example 4, the amount of antimony trioxide and the total amount of additives was the same as in Example 4, but because there was no zinc oxide, a good carbonized layer could not be formed, and holes were formed in the nonwoven fabric, which remained after combustion. The overall judgment failed because the rate was low.

  In Comparative Example 5, since the total amount of zinc oxide and aluminum hydroxide is small, a good carbonized layer cannot be formed, holes are formed in the nonwoven fabric, and it cannot be determined that it has high flame retardancy. Judgment failed. The flame retardancy evaluation test results of Examples 5 to 9 and Comparative Examples 4 and 5 are shown in Table 2.

（実施例１０、１１、比較例６）
製造例２に従い、亜鉛化合物として酸化亜鉛、アンチモン化合物として三酸化アンチモン、その他無機化合物としてカオリンを表３の量で添加したハロゲン含有繊維を作成し、ＬＯＩ値、不織布での難燃性評価、及び熱重量測定による燃焼時の残存率測定を実施した。結果を表３に示す。

(Examples 10 and 11, Comparative Example 6)
According to Production Example 2, a halogen-containing fiber was prepared by adding zinc oxide as a zinc compound, antimony trioxide as an antimony compound, and kaolin as the other inorganic compound in the amounts shown in Table 3, and evaluated the LOI value, flame retardancy evaluation with a nonwoven fabric, and The residual rate at the time of combustion was measured by thermogravimetry. The results are shown in Table 3.

  The combustion test results of Examples 10 and 11 were good. The LOI value is high, and in non-woven fabric testing, after heating with a gas stove, it forms a good carbonized layer, passes without the occurrence of drilling or cracking, and has a high residual rate during heating, so it has high flame resistance. We judged that we were doing and passed general judgment.

  In contrast, in Comparative Example 6, the amount of antimony trioxide and the amount of kaolin were the same as those in Examples 9 and 10, but because there was no zinc oxide, a good carbonized layer could not be formed, and a hole was formed in the nonwoven fabric. Since the residual rate at the time of heating was low, the comprehensive judgment was rejected. Table 3 shows the results of the flame retardancy evaluation tests of Examples 10 and 11 and Comparative Example 6.

（実施例１２、１３、比較例７）
製造例２に従い、亜鉛化合物として酸化亜鉛、アンチモン化合物として三酸化アンチモン、その他無機化合物として水酸化アルミニウムを表４の量で添加したハロゲン含有繊維を作成し、ＬＯＩ値、不織布での難燃性評価、及び熱重量測定による燃焼時の残存率測定を実施した。結果を表３に示す。

(Examples 12 and 13, Comparative Example 7)
In accordance with Production Example 2, a halogen-containing fiber was prepared by adding zinc oxide as the zinc compound, antimony trioxide as the antimony compound, and aluminum hydroxide as the other inorganic compound in the amounts shown in Table 4, and evaluated for the LOI value and flame retardancy of the nonwoven fabric. And the residual rate measurement at the time of combustion was performed by thermogravimetry. The results are shown in Table 3.

  The combustion test results of Examples 12 and 13 were good. The LOI value is high, and in non-woven fabric testing, after heating with a gas stove, it forms a good carbonized layer, passes without the occurrence of drilling or cracking, and has a high residual rate during heating, so it has high flame resistance. We judged that we were doing and passed general judgment.

  In contrast, in Comparative Example 7, the amounts of antimony trioxide and kaolin were the same as in Examples 11 and 12, but because there was no zinc oxide, a good carbonized layer could not be formed and holes were formed in the nonwoven fabric. Since the residual rate at the time of heating was low, the comprehensive judgment was rejected. Table 4 shows the flame retardancy evaluation test results of Examples 12 and 13 and Comparative Example 7.

なお実施例における繊維の難燃性は、不織布を用いて下記のようにして測定した。難燃性合成繊維については前記難燃性評価法１にて、難燃繊維複合体に関しては難燃性評価法２にて、布張り製品家具製品に関しては難燃性評価法３にて評価した。これらは、ベッドマットレス、椅子、ソファー等の布張り家具等の表面生地と内部構造体であるウレタンフォームや詰め綿等との間に本発明の難燃性不織布をはさむことで、火災の際に内部構造物への炎の着火を防ぐことをイメージした簡易評価方法である。なお難燃性評価法２の場合、難燃性評価及び加工性評価を考慮し、総合評価を行った。合格の場合○、不合格の場合×とした。
（難燃性評価法２）
１）難燃性評価試験用不織布の作成
所定の割合で混合した繊維をカードにより開繊した後、ニードルパンチ法により、目付け２００ｇ／ｍ²、縦２０ｃｍ×横２０ｃｍの不織布を作成し、難燃性評価試験用不織布とした。
２）難燃性評価試験方法
縦２００ｍｍ×横２００ｍｍ×厚さ１０ｍｍのパーライト板の中心に直径１５ｃｍの穴をあけたものを準備し、その上に難燃性評価試験用不織布をセットし、加熱時に難燃性評価試験用不織布が収縮しないよう４辺をクリップで固定した。この試料を難燃性評価試験用不織布の面を上にして、株式会社パロマ工業製ガスコンロ（ＰＡ−１０Ｈ−２）にバーナー面より４０ｍｍの所に試料の中心とバーナーの中心が合うようにセットした。燃料ガスは純度９９％以上のプロパンを用い、炎の高さは２５ｍｍとし、着炎時間は１８０秒とした。この時に難燃性評価試験用不織布の炭化膜の厚み斑がなく全く穴やひびもない場合
を◎、炭化膜に貫通した穴があいていない場合、またはひびがない場合を○、穴やひびがある場合を×として評価を実施した。◎または○が合格である。
（難燃性評価法３）
１）難燃性評価試験用試料の作成
所定の割合で混合した繊維をカードにより開繊した後、ニードルパンチ法により、目付け２００ｇ／ｍ²、縦４５ｃｍ×横３０ｃｍの不織布を作成した。該不織布の下にウレタンフォーム（縦４５ｃｍ×横３０ｃｍ、厚み５３ｍｍ）を、該不織布の上に同サイズのポリエステル製不織布（目付け３００ｇ／ｍ²）、更にポリエステル製布帛（目付け１２０ｇ／ｍ²）を重ね、この４者をずれないようにホッチキス（登録商標）で固定し、難燃性評価試験用試料とした。
２）難燃性評価試験方法
米国カリフォルニア州のベッドの燃焼試験方法Ｔｅｃｈｎｉｃａｌ Ｂｕｌｌｅｔｉｎ ６０３（以下ＴＢ６０３）のうち、ベッド上面試験方法に準じて実施した。すなわち試料の上面から３９ｍｍの所に水平にＴ字型のバーナーをセットし、プロパンガスを燃焼ガスとして、ガス圧力１０１ＫＰａ、ガス流量１２．９Ｌ／分の条件にて、７０秒間接炎した。この時に不織布の炭化膜に厚み斑がなく全く穴やひびもない場合を◎、炭化膜に貫通した穴があいていない場合、またはひびがない場合を○、穴やひびがあり下部のウレタンフォームに着炎した場合を×として評価を実施した。◎または○が合格である。
（加工性評価）
該不織布作成時のカード通過性（加工の容易性）が良好な場合◎、可能な場合○、落綿等が発生し困難な場合×とした。◎または○が合格である。
（製造例３）
アクリロニトリル５１％、塩化ビニリデン４８％およびｐ−スチレンスルホン酸ソーダ１％よりなる共重合体（ハロゲン原子割合：３５％）をジメチルホルムアミドに樹脂濃度が３０％になるように溶解させ、得られた樹脂溶液の樹脂重量に対して表１、２、５、６に示す添加量において亜鉛化合物として酸化亜鉛（堺化学（株）製 酸化亜鉛３種）、アンチモン化合物として三酸化アンチモン、その他無機化合物としてカオリン（エンゲルハード社製 カオリンＡＳＰ１７０）または、水酸化アルミニウムを添加し、紡糸原液とした。この紡糸原液をノズル孔径０．１０ｍｍおよび孔数１０００ホールのノズルを用い、
５０％ジメチルホルムアミド水溶液中へ押し出し凝固させ、次いで水洗したのち１２０℃で乾燥し、ついで３倍に延伸してから、さらに１５０℃で５分間熱処理、さらに切断することでハロゲン含有繊維を得た。得られた繊維は繊度５．６ｄｔｅｘであり、カット長５１ｍｍの短繊維であった。
（製造例４）
アクリロニトリル４９％、塩化ビニル５０．５％およびｐ−スチレンスルホン酸ソーダ０．５％よりなる共重合体（ハロゲン原子割合：３４％）をジメチルホルムアミドに樹脂濃度が３０％になるように溶解させ、得られた樹脂溶液の樹脂重量に対して表３、４に示す添加量において亜鉛化合物として酸化亜鉛（堺化学（株）製 酸化亜鉛３種）、アンチモン化合物として三酸化アンチモン、その他無機化合物としてカオリン（エンゲルハード社製 カオリンＡＳＰ１７０）または、水酸化アルミニウムを添加し、紡糸原液とした。
この紡糸原液をノズル孔径０．１０ｍｍおよび孔数１０００ホールのノズルを用い、５０％ジメチルホルムアミド水溶液中へ押し出し、水洗したのち１２０℃で乾燥し、ついで３倍に延伸してから、さらに１３０℃で５分間熱処理、さらに切断することでハロゲン含有繊維を得た。得られた繊維は繊度５．６ｄｔｅｘであり、カット長５１ｍｍの短繊維であった。
（実施例１４〜１９、比較例８〜１１）
製造例３に従い、亜鉛化合物として酸化亜鉛、アンチモン化合物として三酸化アンチモン、その他無機化合物としてカオリンを表５の量で添加したハロゲン含有繊維を作成し、得られたハロゲン含有繊維、ポリエステル繊維（６．６ｄｔｅｘ、カット長５１ｍｍ）、レーヨン繊維（１．５ｄｔｅｘ、カット長３８ｍｍ）が所定の割合からなる不織布を作成し、難燃性評価法１に基づき実施した。結果を表５に示す。

In addition, the flame retardance of the fiber in an Example was measured as follows using the nonwoven fabric. The flame retardant synthetic fiber was evaluated by the above flame retardant evaluation method 1, the flame retardant fiber composite was evaluated by the flame retardant evaluation method 2, and the upholstered furniture products were evaluated by the flame retardant evaluation method 3. . In the event of a fire, the flame retardant nonwoven fabric of the present invention is sandwiched between surface fabrics such as upholstered furniture such as bed mattresses, chairs, sofas, etc. and urethane foam or stuffed cotton that is an internal structure. This is a simple evaluation method based on the image of preventing the ignition of internal structures. In addition, in the case of the flame retardancy evaluation method 2, comprehensive evaluation was performed in consideration of flame retardancy evaluation and workability evaluation. In the case of pass, it was marked as ◯, and in the case of fail, it was marked as x.
(Flame retardance evaluation method 2)
1) Preparation of non-woven fabric for flame retardancy evaluation test Fibers mixed at a predetermined ratio are opened with a card, and then a non-woven fabric having a basis weight of 200 g / m ² , 20 cm in length and 20 cm in width is prepared by a needle punch method. It was set as the nonwoven fabric for a property evaluation test.
2) Flame Retardancy Evaluation Test Method Prepare a pearlite plate with a length of 200 mm x width 200 mm x thickness 10 mm with a hole with a diameter of 15 cm, set a non-woven fabric for flame retardant evaluation test on it, and heat At times, the four sides were fixed with clips so that the nonwoven fabric for flame retardancy evaluation test did not shrink. Set this sample with the non-woven fabric for flame retardancy evaluation test facing up, and set it on a gas stove (PA-10H-2) manufactured by Paloma Industry Co., Ltd. so that the center of the sample is aligned with the center of the burner at 40 mm from the burner surface. did. The fuel gas used was propane with a purity of 99% or more, the flame height was 25 mm, and the flame time was 180 seconds. At this time, the case where there is no unevenness in the thickness of the carbonized film of the non-woven fabric for flame retardancy evaluation test and there are no holes or cracks, ◯ that there are no holes or cracks in the carbonized film, or there are no cracks. The evaluation was carried out with x when there was. ◎ or ○ is a pass.
(Flame retardance evaluation method 3)
1) Preparation of flame retardant evaluation test sample After the fibers mixed at a predetermined ratio were opened with a card, a nonwoven fabric having a basis weight of 200 g / m ² , a weight per unit area of 45 cm and a width of 30 cm was prepared. A urethane foam (length 45 cm × width 30 cm, thickness 53 mm) is placed under the nonwoven fabric, a polyester nonwoven fabric (weighing 300 g / m ² ) of the same size is placed on the nonwoven fabric, and a polyester fabric (weight is 120 g / m ² ). Again, these four were fixed with Stapler (registered trademark) so as not to deviate, and used as a flame retardant evaluation test sample.
2) Flame Retardancy Evaluation Test Method Of the bed combustion test method Technical Bulletin 603 (hereinafter referred to as TB603) in California, USA, the test was performed according to the bed top surface test method. That is, a T-shaped burner was set horizontally at a position 39 mm from the upper surface of the sample, and propane gas was used as a combustion gas, and an indirect flame was performed for 70 seconds under conditions of a gas pressure of 101 KPa and a gas flow rate of 12.9 L / min. At this time, ◎ if the carbonized film of the nonwoven fabric has no thickness spots and no holes or cracks, ○ if there is no through hole in the carbonized film, or if there are no cracks, ○, and there is a hole or crack in the lower urethane foam The case where the flame was ignited was evaluated as x. ◎ or ○ is a pass.
(Processability evaluation)
When the card passing property (ease of processing) at the time of producing the nonwoven fabric was good, it was marked as ◎, when possible, ◯, when cotton falling and the like were difficult, and x. ◎ or ○ is a pass.
(Production Example 3)
A resin obtained by dissolving a copolymer (halogen atom ratio: 35%) of 51% acrylonitrile, 48% vinylidene chloride and 1% p-styrenesulfonic acid soda in dimethylformamide so that the resin concentration is 30%. Zinc oxide (3 types of zinc oxide manufactured by Sakai Chemical Co., Ltd.), antimony trioxide as antimony compound, and kaolin as other inorganic compound in addition amounts shown in Tables 1, 2, 5, and 6 with respect to the resin weight of the solution (Kaolin ASP170 manufactured by Engelhard) or aluminum hydroxide was added to prepare a spinning dope. Using this spinning dope, a nozzle with a nozzle hole diameter of 0.10 mm and a hole number of 1000 holes,
It was extruded and coagulated in a 50% aqueous dimethylformamide solution, then washed with water, dried at 120 ° C., then stretched 3 times, further heat treated at 150 ° C. for 5 minutes, and further cut to obtain a halogen-containing fiber. The obtained fiber was a fine fiber having a fineness of 5.6 dtex and a cut length of 51 mm.
(Production Example 4)
A copolymer of 49% acrylonitrile, 50.5% vinyl chloride and 0.5% sodium p-styrenesulfonate (halogen atom ratio: 34%) was dissolved in dimethylformamide so that the resin concentration was 30%. Zinc oxide (3 types of zinc oxide manufactured by Sakai Chemical Co., Ltd.), antimony trioxide as antimony compound, and kaolin as other inorganic compound in the addition amounts shown in Tables 3 and 4 with respect to the resin weight of the obtained resin solution (Kaolin ASP170 manufactured by Engelhard) or aluminum hydroxide was added to prepare a spinning dope.
This spinning dope was extruded into a 50% dimethylformamide aqueous solution using a nozzle having a nozzle hole diameter of 0.10 mm and a hole number of 1000 holes, washed with water, dried at 120 ° C., then stretched 3 times, and further at 130 ° C. A halogen-containing fiber was obtained by heat treatment for 5 minutes and further cutting. The obtained fiber was a fine fiber having a fineness of 5.6 dtex and a cut length of 51 mm.
(Examples 14 to 19, Comparative Examples 8 to 11)
According to Production Example 3, a halogen-containing fiber was prepared by adding zinc oxide as the zinc compound, antimony trioxide as the antimony compound, and kaolin as the other inorganic compound in the amounts shown in Table 5, and the resulting halogen-containing fiber and polyester fiber (6. 6 dtex, cut length 51 mm) and non-woven fabric having rayon fibers (1.5 dtex, cut length 38 mm) in a predetermined ratio were prepared and carried out based on the flame retardancy evaluation method 1. The results are shown in Table 5.

  The combustion test results of Examples 14 to 19 were good, and the non-woven fabric for flame retardancy evaluation test was free of cracks and holes after heating with a gas stove, and formed a good carbonized film.

  On the other hand, in Comparative Examples 8 to 9, the total amount of the flame retardant is the same as Example 14, but Comparative Example 8 contains kaolin as another inorganic compound, and Comparative Example 9 contains zinc oxide as a zinc compound. As a result, a good carbonized film could not be formed, and holes were formed in the nonwoven fabric.

  In Comparative Example 11, a good carbonized film was not formed with a small amount of halogen-containing fibers.

  In Comparative Example 12, the ratio of the halogen-containing fiber is 100%, and thus the flame retardancy is good. However, since natural fibers and / or chemical fibers are not included, there is a problem in processability when creating a nonwoven fabric. . Table 5 shows the flame retardancy evaluation test results of Examples 14 to 19 and Comparative Examples 8 to 11.

（実施例２０〜２７、比較例１２〜１４）
製造例３に従い、亜鉛化合物として酸化亜鉛、アンチモン化合物として三酸化アンチモン、その他無機化合物として水酸化アルミニウムを表６の量で添加したハロゲン含有繊維を作成し、得られたハロゲン含有繊維、ポリエステル繊維（６．６ｄｔｅｘ、カット長５１ｍｍ）、レーヨン繊維（１．５ｄｔｅｘ、カット長３８ｍｍ）及び木綿繊維が所定の割合からなる不織布を作成し、難燃性評価法２に基づき実施した。結果を表６に示す。

(Examples 20 to 27, Comparative Examples 12 to 14)
According to Production Example 3, a halogen-containing fiber was prepared by adding zinc oxide as the zinc compound, antimony trioxide as the antimony compound, and aluminum hydroxide as the other inorganic compound in the amounts shown in Table 6, and the resulting halogen-containing fiber and polyester fiber ( A non-woven fabric having a predetermined ratio of 6.6 dtex, cut length 51 mm), rayon fiber (1.5 dtex, cut length 38 mm) and cotton fiber was prepared and carried out based on the flame retardancy evaluation method 2. The results are shown in Table 6.

  The combustion test results of Examples 20 to 27 were good, and the non-woven fabric for flame retardancy evaluation test did not generate cracks or holes after heating with a gas stove, and formed a good carbonized film.

  On the other hand, in Comparative Examples 12 to 14, the total amount of the flame retardant is the same as that in Example 14, but in Comparative Example 12, since a zinc oxide of a zinc compound is not included, a good carbonized film cannot be formed. A hole was formed in the nonwoven fabric.

  In Comparative Example 13, a good carbonized film was not formed with a small amount of halogen-containing fibers.

  In Comparative Example 14, the flame retardancy was good because the proportion of the halogen-containing fiber was 100%, but there was a problem in processability during the production of the nonwoven fabric because it did not contain natural fibers and / or chemical fibers. . Table 6 shows the flame retardancy evaluation test results of Examples 20 to 27 and Comparative Examples 12 to 14.

（実施例２８〜３０、比較例１５）
製造例４に従い、亜鉛化合物として酸化亜鉛、アンチモン化合物として三酸化アンチモン、その他無機化合物としてカオリンを表７の量で添加したハロゲン含有繊維を作成し、得られたハロゲン含有繊維、ポリエステル繊維（６．６ｄｔｅｘ、カット長５１ｍｍ）、レーヨン繊維（１．５ｄｔｅｘ、カット長３８ｍｍ）が所定の割合からなる不織布を作成し、難燃性評価法２に基づき実施した。結果を表７に示す。

(Examples 28 to 30, Comparative Example 15)
According to Production Example 4, a halogen-containing fiber was prepared by adding zinc oxide as the zinc compound, antimony trioxide as the antimony compound, and kaolin as the other inorganic compound in the amounts shown in Table 7, and the resulting halogen-containing fiber and polyester fiber (6. 6 dtex, cut length 51 mm) and a non-woven fabric comprising rayon fibers (1.5 dtex, cut length 38 mm) in a predetermined ratio were prepared and carried out based on the flame retardancy evaluation method 2. The results are shown in Table 7.

  The combustion test results of Examples 28 to 30 were good, and the non-woven fabric for flame retardancy evaluation test was free of cracks and holes after heating with a gas stove, and formed a good carbonized film.

  In Comparative Example 15, the amount of antimony compound and the amount of kaolin were the same as those in Examples 28 to 30, but since a zinc compound zinc oxide was not included, a good carbonized film could not be formed, and holes were formed in the nonwoven fabric. Table 7 shows the flame retardancy evaluation test results of Examples 28 to 30 and Comparative Example 15.

（実施例３１〜３３、比較例１６）
製造例４に従い、亜鉛化合物として酸化亜鉛、アンチモン化合物として三酸化アンチモン、その他無機化合物として水酸化アルミニウムを表８の量で添加したハロゲン含有繊維を作成し、得られたハロゲン含有繊維、ポリエステル繊維（６．６ｄｔｅｘ、カット長５１ｍｍ）、レーヨン繊維（１．５ｄｔｅｘ、カット長３８ｍｍ）が所定の割合からなる不織布を作成し、難燃性評価法２に基づき実施した。結果を表８に示す。

(Examples 31-33, Comparative Example 16)
According to Production Example 4, a halogen-containing fiber was prepared by adding zinc oxide as the zinc compound, antimony trioxide as the antimony compound, and aluminum hydroxide as the other inorganic compound in the amounts shown in Table 8, and the resulting halogen-containing fiber and polyester fiber ( A non-woven fabric having a predetermined ratio of 6.6 dtex, cut length 51 mm) and rayon fiber (1.5 dtex, cut length 38 mm) was prepared and carried out based on the flame retardancy evaluation method 2. The results are shown in Table 8.

  The combustion test results of Examples 31 to 33 were good, and the non-woven fabric for flame retardancy evaluation test was free of cracks and holes after heating with a gas stove, and formed a good carbonized film.

  In Comparative Example 16, the amount of the antimony compound and the amount of kaolin were the same as those in Examples 18 to 20, but since the zinc compound zinc oxide was not included, a good carbonized film could not be formed, and holes were formed in the nonwoven fabric. Table 8 shows the flame retardancy evaluation test results of Examples 31 to 33 and Comparative Example 16.

（実施例３４〜３６、比較例１７）
製造例３に従い、亜鉛化合物として酸化亜鉛、アンチモン化合物として三酸化アンチモン、その他無機化合物としてカオリンを表９の量で添加したハロゲン含有繊維を作成し、得られたハロゲン含有繊維、ポリエステル繊維（６．６ｄｔｅｘ、カット長５１ｍｍ）、レーヨン繊維（１．５ｄｔｅｘ、カット長３８ｍｍ）が所定の割合からなる不織布を作成し、難燃性評価法３に基づき実施した。結果を表９に示す。

(Examples 34 to 36, Comparative Example 17)
According to Production Example 3, a halogen-containing fiber was prepared by adding zinc oxide as the zinc compound, antimony trioxide as the antimony compound, and kaolin as the other inorganic compound in the amounts shown in Table 9, and the resulting halogen-containing fiber and polyester fiber (6. 6 dtex, cut length 51 mm) and a non-woven fabric having rayon fibers (1.5 dtex, cut length 38 mm) in a predetermined ratio were prepared and carried out based on flame retardancy evaluation method 3. The results are shown in Table 9.

  The combustion test results of Examples 34 to 36 were good, a good carbonized film was formed, and no flame was found on the urethane foam.

  In Comparative Example 17, the amount of the antimony compound and the amount of kaolin were the same as those in Examples 33 to 35, but since the zinc compound zinc oxide was not included, a good carbonized film could not be formed and the urethane foam was flared. Table 9 shows the results of the flame retardancy evaluation tests of Examples 34 to 36 and Comparative Example 17.

（実施例３７〜３９、比較例１８）
製造例３に従い、亜鉛化合物として酸化亜鉛、アンチモン化合物として三酸化アンチモン、その他無機化合物としてカオリンを表９の量で添加したハロゲン含有繊維を作成し、得られたハロゲン含有繊維、ポリエステル繊維（６．６ｄｔｅｘ、カット長５１ｍｍ）、レーヨン繊維（１．５ｄｔｅｘ、カット長３８ｍｍ）が所定の割合からなる不織布を作成し、難燃性評価法３に基づき実施した。結果を表１０に示す。

(Examples 37 to 39, Comparative Example 18)
According to Production Example 3, a halogen-containing fiber was prepared by adding zinc oxide as the zinc compound, antimony trioxide as the antimony compound, and kaolin as the other inorganic compound in the amounts shown in Table 9, and the resulting halogen-containing fiber and polyester fiber (6. 6 dtex, cut length 51 mm) and a non-woven fabric having rayon fibers (1.5 dtex, cut length 38 mm) in a predetermined ratio were prepared and carried out based on flame retardancy evaluation method 3. The results are shown in Table 10.

  The combustion test results of Examples 37 to 39 were good, a good carbonized film was formed, and no flame was found on the urethane foam.

  In Comparative Example 18, the amount of the antimony compound and the amount of kaolin were the same as those in Examples 37 to 38, but since the zinc compound zinc oxide was not included, a good carbonized film could not be formed and the urethane foam was flared. Table 10 shows the results of the flame retardancy evaluation tests of Examples 37 to 39 and Comparative Example 18.

Claims (16)

  It consists of 3 to 50 parts by weight of a zinc compound, 0 to 30 parts by weight of an antimony compound, and 3 to 30 parts by weight of another inorganic compound with respect to 100 parts by weight of a polymer containing 17% by weight or more of halogen atoms. A flame retardant synthetic fiber having a total of 15 parts by weight or more of an antimony compound and other inorganic compounds.   The polymer containing 17% by weight or more of halogen atom is 30 to 70 parts by weight of acrylonitrile, 70 to 30 parts by weight of halogen-containing vinyl and / or halogen-containing vinylidene monomer, and vinyl monomer 0 copolymerizable therewith. The flame-retardant synthetic fiber according to claim 1, comprising from 10 to 10 parts by weight.   The flame-retardant synthetic fiber according to claim 1 or 2, wherein the zinc compound is a compound selected from zinc, zinc oxide, zinc borate, zinc stannate, and zinc carbonate.   Said other inorganic compounds are kaolin, zeolite, montmorillonite, talc, perlite, bentonite, vermiculite, diatomaceous earth, graphite or other natural or synthetic mineral compounds, aluminum hydroxide, aluminum sulfate, aluminum silicate and other aluminum compounds, The flame-retardant synthetic fiber according to claim 3, which is a compound selected from magnesium compounds such as magnesium hydroxide and magnesium oxide, and silicon compounds such as silicate and glass.   It consists of 3 to 30 parts by weight of a zinc compound, 0 to 30 parts by weight of an antimony compound, and 3 to 30 parts by weight of kaolin or aluminum hydroxide as another inorganic compound with respect to 100 parts by weight of a polymer containing 17% by weight or more of a halogen atom. The flame retardant synthetic fiber according to claim 3, wherein the total of the zinc compound, the antimony compound and the inorganic compound is 20 to 50 parts by weight.   3 to 50 parts by weight of a zinc compound, 0 to 30 parts by weight of an antimony compound, 3 to 30 parts by weight of another inorganic compound, and 3 to 30 parts by weight of another inorganic compound with respect to 100 parts by weight of a polymer containing 17% by weight or more of a halogen atom. Difficulty consisting of 10 parts by weight or more of fibers (A) in which the total amount of the compound and other inorganic compounds is 15 parts by weight or more, and 90 parts by weight or less of at least one kind of fiber (B) among natural fibers and / or chemical fibers Fuel fiber composite.   A polymer containing 17% by weight or more of halogen atom is 30 to 70% by weight of acrylonitrile, 70 to 30% by weight of halogen-containing vinyl and / or halogen-containing vinylidene monomer, and vinyl monomer 0 to copolymerize with these. The flame-retardant fiber composite according to claim 6, which is a copolymer comprising 10% by weight. The flame retardant fiber composite according to claim 7, wherein the zinc compound is a compound selected from zinc, zinc oxide, zinc borate, zinc stannate, and zinc carbonate.   The other inorganic compounds are natural or synthetic mineral compounds such as kaolin, zeolite, montmorillonite, talc, perlite, bentonite, vermiculite, diatomaceous earth, graphite, aluminum compounds such as aluminum hydroxide, aluminum sulfate, aluminum silicate, water, etc. The flame retardant fiber composite according to claim 6, 7 or 8, wherein the flame retardant fiber composite is a compound selected from magnesium compounds such as magnesium oxide and magnesium oxide, and silicon compounds such as silicate and glass.   The flame-retardant fiber composite according to claim 9, comprising 40 parts by weight or less of a polyester fiber as a chemical fiber of at least one kind of natural fiber and / or chemical fiber (B).   The flame-retardant fiber composite according to claim 10, wherein the polyester fiber is a low-melting-point binder fiber.   A nonwoven fabric comprising the flame retardant fiber composite according to any one of claims 6, 7 and 8.   The nonwoven fabric for flame shielding barriers of Claim 12.   A upholstered furniture product using the flame retardant fiber composite according to any one of claims 6, 7 and 8.   The upholstered furniture product using the nonwoven fabric of Claim 12.   The upholstered furniture product using the nonwoven fabric for flame shielding barriers of Claim 13.