TW201134992A - Flame retardant fiber assembly, method for producing same, and fiber product - Google Patents

Abstract

Disclosed are: a flame retardant fiber assembly which has satisfactorily high flame retardancy and satisfactorily high flame shielding performance; a method for producing the flame retardant fiber assembly; and a fiber product. Specifically disclosed is a flame retardant fiber assembly, which contains 3-30% by mass of halogen-containing fibers, 20-50% by mass of polyester fibers and 30-77% by mass of flame retardant fibers other than the halogen-containing fibers. The halogen-containing fibers contain a polymer (1) that contains 30-70% by mass of acrylonitrile, 70-30% by mass of a halogen-containing vinylidene monomer and/or a halogen-containing vinyl monomer, and 0-10% by mass of a vinyl monomer that is copolymerizable with the aforementioned compounds, and at least one metal compound (2) that promotes a dehalogenation reaction of the polymer (1) during combustion or a carbonization reaction of the polymer (1) during combustion. The halogen-containing fibers have a shrinkage variation of not more than 65% when the temperature thereof is raised from 50 DEG C to 300 DEG C under a load of 0.0054 mN/dtex.

Description

201134992 VI. Description of the Invention: [Technical Field] The present invention relates to a flame-retardant fiber assembly having high flame retardancy and a method of manufacturing the same, and a fiber product by which the flame-retardant fiber assembly is It exhibits extremely high carbonization, form retention, and self-tanning properties when burned, and can be suitably used for a highly resistant flame retardant fiber product used for bedding or furniture. [Prior Art] In recent years, the demand for ensuring the safety of clothing, food, and shelter has increased, and the necessity of flame retardant materials is increasing in view of fire prevention. Among them, in particular, in order to prevent the fire in the bed when the person is injured, the necessity of imparting flame retardancy to the raw materials used for bedding or furniture is increasing. In the fabrics such as beddings or furniture, in order to achieve comfort or design during use, flammable materials such as cotton or polyester or urethane foams are often used for the interior or surface thereof. . In order to ensure their flame retardancy, it is important to have a high level of flame retardancy against ignition of the flammable material by using suitable flame retardant materials in such products. X, the flame retardant material must also maintain the comfort or design of the products such as bedding or furniture. 4乍 is a flame-retardant fiber raw material using the fiber of one of the smoldering materials. In the past, various flame-retardant fibers and fire-retardant agents have been studied, but they have not yet appeared to make the height of the flame retardant and sleepy. The necessary conditions such as comfort or design required for products such as furniture or furniture are adequately balanced. For example, there is a so-called post-fire protection method for applying a fireproofing agent to a cotton cloth, but there is a problem of uniformity of the adhesion of the fireproofing agent, hardening of the cloth caused by the adhesion, detachment caused by the cleaning of the 152753.doc 201134992, and safety. (2) As a cheap raw material, (4) the fiber is melted into a cloth (4) when it is burned, which will create holes and cannot maintain the structure, but the fire, the furniture used in f furniture, etc., or the urethane (4) bubble body. The words are not sufficient. There are also difficult-to-do fibers containing (iv) atoms, but the behavior at the time of burning is the same as above, and eventually it is not sufficient. The method of obtaining a high flame-retardant modacrylic fiber by adding a trioxide or pentaoxane (tetra) or oxygen domain # to a spinning dope can impart flame retardancy, but has a barrier property against fire or heat. A problem that did not reach a satisfactory level. Among these properties, there is a crosslinked high flame retardant acrylic fiber to which a polymer containing glycidyl methacrylate is added, which is difficult to ignite and satisfies the barrier property against fire or heat (Patent Document). However, when the field is exposed to a strong flame such as a burner fire, there is a case where the fiber itself decomposes and eventually ignites. Further, there is a high flame retardant flame barrier property to which a solid phase flame retardant represented by water glass or zinc oxide is added. Improved acrylic fiber (Patent Document 2), but there are cases where the fibers have excellent fire-extinguishing properties or flame barrier properties, but the carbonized film formed during burning is hard, depending on the type of furniture or bedding or the shape of the burning portion. When the shrinkage of the fiber is large, stress is applied to the carbonized film during combustion to cause cracks in the carbonized film, or pores are formed in the carbonized film due to a small load. As a method for solving this problem, it is proposed to borrow An improved acrylic fiber which is difficult to produce cracks by controlling the carbonization rate at the time of shrinkage by adding an oxidized word and a condensed phosphate compound (Patent Document 152753.doc) 201134992 3), but when using these fibers, there are problems with non-complex and limited types of fibers, and limited fiber mixing. '彳', the law is not difficult to burn, but also borrowed A method for producing an acrylic synthetic fiber having excellent heat shrinkage resistance is obtained by performing a moist heat stress treatment (Patent Document 4). However, there is a problem in that the heat shrinkage is prevented in a state of tension, so that the residual shrinkage cannot be sufficiently removed. Although the stress can suppress the shrinkage at a relatively low temperature of 16 〇C, it shrinks remarkably at a high temperature such as 2Gn of the flame, resulting in poor flame retardancy. Moreover, it is necessary for other fibers as a practical fiber product. Mixing is also completely unconsidered. Therefore, it cannot be tolerated as a practical and difficult-to-burn material. It has been proposed to combine the highly flame-retardant (4) fiber and non-flammable fiber with a large amount of flame retardant added. Aggregate (Patent Document 5), and a flame-retardant non-woven fabric composed of a fiber which is inherently flame-retardant and a material-containing fiber Patent Document 6). However, these methods have problems in that the shape before burning such as cloth or fabric cannot be maintained during combustion, and the required flame retardancy, particularly flame barrier properties cannot be ensured; usually heat-resistant fibers or essence Fiber which is incombustible: It is easy to obtain the desired properties, but the fiber itself is mostly hard and brittle, and the operation of the raw material is extremely difficult to operate and manufacture, and the cost is high. [Prior Art Document] [Patent Literature] [Patent Document 1 Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Patent Laid-Open Publication No. SHO-58-156014 [Patent Document 5] Japanese Patent Laid-Open Publication No. SHO 61-89339 [Patent Document 6] US Patent No. 7,259,117 [Invention] [Problems to be Solved by the Invention] In order to solve the above problems, the present invention provides a flame-retardant fiber assembly which satisfies a high flame retardancy and a flame barrier property, a method for producing the same, and a fiber product. [Technical means for solving the problem] The flame-retardant fiber assembly of the present invention contains a dentate-containing fiber, a poly-branded fiber, and a flame-retardant fiber other than the dentate-containing fiber. When the total amount of the above flame-retardant fiber aggregate is 100% by mass, the content of the halogen-containing fiber is 3 to 30% by mass, and the content of the polyester-based fiber is 2 Å to 5 Å by mass. Further, the content of the flame retardant fiber other than the halogen-containing fiber is from 3 to 77% by mass. The dentate-containing fiber is characterized in that it contains acrylonitrile 3〇~7〇 mass/〇3 halogen vinylidene monomer and/or halogen-containing vinyl monomer 7〇30% by mass, and can be co-operated with The polymer (1) having a total amount of 100% by mass of the polymerized vinyl monomer 〇1 to 1% by mass, and at least one metallization port for promoting the decoking reaction at the time of combustion of the polymer (1) and the carbonization reaction at the time of combustion The object (2), and under a load of 0.0054 mN/dtex, the shrinkage change when the temperature is increased from the thief to 300 t is 65% or less. The method for producing a flame-retardant fiber assembly according to the present invention is characterized in that the flame-retardant fiber assembly system comprises a non-flammable fiber containing a sulphide fiber, a polyester fiber, and a 152753.doc 201134992 fiber; The manufacturing method includes the step of setting the total amount of the above-mentioned flame retardant fiber aggregate to 100 mass. /. In the case of 3 to 30% by mass of the above-mentioned dentate-containing fibers, 20 to 50% by mass of the above-mentioned polyester fibers, and 30 to 77% by mass of the flame-retardant fibers other than the halogen-containing fibers; The fiber has a shrinkage variation of 55% or less at a load of 0.0054 mN/dtex from 3 ° C to 3 ° C; the halogen-containing fiber is made to contain a mass of 3 〇 to 70 of acrylonitrile. %, the content of the halogenated vinyl monomer and/or the halogen-containing vinyl monomer 7〇~3〇0/〇, and the copolymerizable vinyl monomer 〇~1〇% by mass Polymer of 1% by mass of polymer (1) 'after spinning with a composition of at least a metal compound (2) which promotes a dehalogenation reaction during combustion of the above polymer (1) and a carbonization reaction during combustion 'Achieved by heat treatment. The fibrous product of the present invention is characterized by comprising the above-mentioned flame retardant fiber assembly. [Effect of the Invention] According to the present invention, a fiber product having high flame retardancy and high flame barrier property can be obtained. [Embodiment] The inventors of the present invention have made intensive studies to solve the above problems, and as a result, they have been prepared to contain γ-containing fibers, poly-S-fibers, and dentate-containing fibers, and non-flammable fibers. The flame-retardant fiber assembly exhibits a high degree of flame retardance. The above-mentioned 3 halogen fibers contain 30 to 70 masses of acrylonitrile. /〇, halogen-containing divinyl monomer and/or hydroxyl-containing vinyl monomer 7. ~30 quality. /. And the total amount of the copolymerized vinyl monomer 〇~1〇 mass% ι 152 152753.doc 201134992 % by weight of the polymer (1), and promote the above polymer (1) At least the metal compound (2) in the decoupling reaction during combustion and the carbonization reaction during combustion, and the shrinkage change when the temperature is increased from 5〇t to 3〇〇t under a load of 0.0054 mN/dtex is 65% The present invention is completed as follows ((halogen-containing fiber). In the present invention, the halogen-containing fiber contains the polymer (1), at least a denture reaction for promoting combustion of the polymer (1), and at least carbonization reaction upon combustion. 1 metal compound (2). The above polymer 〇) comprises acrylonitrile 3〇~7〇 mass 4, halogen-containing vinylidene monomer and/or halogen-containing vinyl monomer 〜3〇 mass/. The copolymerized vinyl monomer 〇 丨〇 丨〇 丨〇 mass %, the total amount is 100% by mass. Further, the above polymer (1) preferably contains acrylonitrile 4 〇 to 65 mass%. 60% to 35% by mass of the base monomer and/or the dentate-containing vinyl monomer, and A may be copolymerized with the vinyl group In the above polymer (1), if the acrylonitrile content is 4 g to 65% by mass, the heat resistance necessary for the fiberization can be easily obtained, and the flame retardation can be achieved. More preferably, the acrylonitrile content is 5 G to (4)% by weight, and if it is in this range, the color of the fiber becomes less. As the above polymer (1), for example, acrylonitrile-diene gas (ene, acrylonitrile) is exemplified. a copolymer of one or more kinds of monomers containing succinylethylene and other monomers, such as a second gas, a second ethylene, or a acetonitrile; a dentate containing ethylene, a vinylidene fluoride or a vinylidene fluoride a copolymer of a vinylidene monomer, a acrylonitrile, and a copolymerizable ethylene monomer, but not limited to these. The above copolymer is appropriately mixed and used as 152753.doc 201134992 as the above-mentioned ethylene-based monomer copolymerizable with the above, and examples thereof include acrylic acid and its ester, methacrylic acid and its ester, acrylamide, and methamine. Acrylic amine, ethyl acetate 6, vinyl (tetra) and its salts, methyl propyl i acid and its salts, styrene And a salt thereof, 2, (tetra) decylamine 2 - methyl phthalic acid, a salt thereof, etc., may be used in the above-mentioned species or in a mixture of two or more. In addition, at least one of them is a compound containing a vinyl group-containing monomer. The copolymer (1) can be obtained by a known polymerization method. For example, examples of the polymerization method include bulk polymerization, m-type polymerization, emulsion polymerization, > Examples of the polymerization form include a continuous form, a batch type, and a half batch type, but are not limited thereto. Among them, from the industrial viewpoint, as a polymerization method, emulsion polymerization and solution polymerization are preferred, and the polymerization form is used. 'Let's preferably a continuous type and a half batch type. As the at least one metal compound (2) which promotes the decoupling reaction at the time of combustion of the polymer (1) and the carbonization reaction at the time of combustion, a dehalogenation reaction can be used. The two reactions of the carbonization reaction are selected from the group consisting of oxidation, zinc carbonate, zinc sulfide, zinc borate, zinc stannate, metastannic acid, tungsten oxide, zirconium oxide, tin oxide, copper oxide, copper phosphate, indium trioxide, barium titanate. a metal compound in zinc p-toluenesulfonate ( 2-i) 'or the above metal compound (2-1) is selected from the group consisting of ruthenium compound, iron oxide, iron phosphate, iron oxalate, iron sulfide, oxidized ruthenium, antimony trioxide, osmium oxide, iodine The metal compound (2-2) in copper is used in combination. The present inventors believe that the above-mentioned metal compound (2-1) promotes the de-tonation reaction at the time of combustion of the polymer (1), and promotes the formation of polyene which is a precursor of 152753.doc 201134992 before the carbonization reaction at the time of combustion, and further The metal complex formed by the de-toothing promotes carbonization by exerting a catalytic action on the multi-dilute structure. As the metal compound (2 1)', in order to promote subsequent carbonization, it is preferred to react the degumming reaction to a compound which is produced at 200 C or less. More preferably, it is at least one selected from the group consisting of oxidized words, zinc stannate, zinc carbonate, and tin oxide. The above-mentioned metal compound (2-1) may be used alone or in combination of two or more kinds, and the above metal compound (2_j) may be selected from the group consisting of iron oxide, iron phosphate, iron oxalate, iron sulfide, The metal compound (2_2) which is used for the dehalogenation reaction in the combustion of the polymer (1) in the molybdenum oxide, the trioxide secret, the osmium oxide, and the Wei steel is used in combination. The metal compound (2_2) which promotes the dehalogenation reaction of the polymer promotes the formation of a polyene which is a precursor of the carbonization reaction by promoting the dehalogenation reaction of the polymer (1), but on the other hand, since it does not have both promotion The ability to carbonize the resulting polyene structure is not effective for the individual use of the metal compound (2-2). As the metal compound (2-2), a ruthenium compound is particularly preferable. The ruthenium compound not only promotes the de-energization of the combustion of the polymer (1), but also the dentate formed by the de-tooth formation forms a gas in a wide temperature region at the time of combustion, and the gas functions to capture the radicals and suppress the combustion, that is, Fire extinguishing performance. Examples of the ruthenium compound include ruthenium oxide compounds such as antimony trioxide, osmium tetroxide, and antimony pentoxide; ruthenium acid or a salt thereof; and an inorganic ruthenium compound such as ruthenium oxide, but are not limited thereto. Also, these combinations can be used. Among them, in terms of performance and industrial availability, it is preferred to be a trioxide recording and a pentoxide recording. The amount of the metal compound (2) is preferably 152753.doc -10- 201134992, and is preferably 0.05 to 50 parts by mass based on 100 parts by mass of the above polymer (1). The lower limit value is more preferably "quality": and further preferably 1 part by mass. Further, regarding the upper limit value, it is more preferably 40 mass damage, and more preferably 30 mass parts. When the amount of the metal compound (7) used is (4) 5 to 50 parts by mass 'the effect of carbonizing the polymer upon combustion (carbonization effect), the carbonization effect necessary for obtaining the desired high flame retardancy can be obtained, and the desired The shrinkage rate. If it is a preferred range, the above effect becomes higher. The amount of the metal compound added is preferably G.G5 to 5G parts by mass based on 1 part by mass of the polymer (1). The lower limit value is more preferably 〇1 mass damage and further preferably 1 part by mass. Further, the upper limit value is more preferably a mass damage' and more preferably 3 parts by mass. When the amount of the metal compound (2_i) used is 0.05 50 parts by weight, the effect of carbonizing the polymer at the time of combustion (carbonization effect) can be obtained, and the stone anaging effect necessary for obtaining the desired high flame retardancy can be obtained. And obtain the desired shrinkage. If it is a preferable range, the above effect becomes higher. The amount of the metal compound added is 0 to 50 parts by mass, preferably 3 to 4 parts by mass, more preferably 5 to 3 parts by mass, based on 100 parts by mass of the above polymer (丨). There is also a case where the required flame retardancy can be achieved even for the mass fraction, but the self-extinguishing effect is small, so when used for applications requiring a higher self-extinguishing effect, it is preferable to add 3 parts by mass or more. Below the mass. The average particle diameter of the metal compound (2) is preferably 3 μm or less, more preferably 2 μm or less. When the average particle diameter of the metal compound (2) is 3 μm or less, the failure of the nozzle, such as nozzle clogging, in the manufacturing step of the fiber in which the metal compound component is added to the _-containing polymer is 152753.doc • 11- 201134992 degree increase, metal compound component particles in fiber =: gold: the lower limit of the average particle size of compound (7) is not special: : in terms of sex 2, 'preferably-upper, better 1 incense The above metal compound (7) may be chemically modified to improve the agglomeration property, and may be used in a state of being dispersed in water or an organic solvent. Here, the so-called average (four) refers to the middle diameter. As a method of measuring the median diameter, a light scattering method can be used. The above-mentioned fiber-containing fiber is preferably contained in an amount of from 0.1 to 20 parts by mass based on 100 parts by mass of the polymer (1). The crosslinking of the fibers can be further suppressed by forming a polymer crosslinked structure in the fibers by using the epoxy group-containing compound and crosslinking by heat or heat in the fiber production step. The epoxy group-containing compound may be, for example, a glycidyl (tetra) type, a glycidylamine type, a glycidyl group, a cyclic aliphatic type, or a copolymer containing the epoxy group-containing compound. . When considering the amount of the reaction group (epoxy group) per unit weight of the dissolution in the spinning, the glycidyl ester is preferably used, for example, polyglycidyl methacrylate (the weight average molecular weight is 3000~100000). Further, the above-mentioned dentate-containing fibers may contain other additives such as an antistatic agent, a thermal coloring inhibitor, a light resistance improving agent, a whiteness improving agent, a devitrification preventing agent, a coloring agent, and a flame retardant. The above-mentioned halogen-containing fiber has a shrinkage variation of 65 °/ when the temperature is raised from 50 C to 300 ° C under a load of 0.0054 mN/dtex. the following. In the above, the so-called shrinkage change from 50 ° C to 30 ° t 152753.doc 12 · 201134992 movement, refers to the highest and lowest point of shrinkage in the temperature range of 5 (TC to 300 ° C) The difference is necessary to be a value above 〇. If it is expressed in the diagram of the present invention, for example, it corresponds to the circle shown in the arrows in Figs. 9 to 丨5. The following: For example, as shown in FIG. 9 or FIG. 11, when the temperature is monotonously contracted as the temperature rises, the contraction fluctuation becomes the contraction rate of the point 乂^(10)^^. As shown in the figure, when it is stretched once after shrinking and contracted again, according to the elongation at the time of one-degree elongation, in Fig. 12, the contraction fluctuation becomes the contraction rate of point c, and in Fig. 13, the contraction fluctuation becomes a contraction of 1 point. In FIGS. 14 and 15, the shrinkage fluctuation is the difference between the shrinkage ratio of the point 1) and the shrinkage ratio of b and the point. 3. As shown in Fig. 10, when it is monotonously stretched or stretched after shrinking and is broken midway, the shrinkage fluctuation becomes the shrinkage ratio indicated by the arrow (when the elongation is interrupted, the shrinkage fluctuation is 〇〇). 4. Point a in the figure is the softening start point. Between 3 o'clock and b o'clock, shrinkage caused by stress relaxation, shrinkage caused by decogging, and "stretching" caused by softening are superior to elongation. In the future, the shrinkage caused by the de-salt, the shrinkage due to carbonization (shape retention), and the "elongation" caused by softening form the following pattern: (1) When the carbonization ability is excellent, the shrinkage (or shape retention) is won. Over-extension 'forms a shrink pattern as shown in Figure 9 or Figure 11; elongation is superior at point b, at a certain point (b' point in the figure) and (2) when the stone reversal ability is still poor, the potential 'follows The temperature rises and the carbonization is in the dominance and begins to shrink (Fig. 12, 13, 14, 15); 152753.doc 201134992 (3) In the case of no carbonization ability _, after b point, the elongation is in an advantage, forming the shrink pattern of Fig. 10. . 5. There are four types of shrinkage patterns of the above halogen-containing fibers (Fig. 9, Fig. 12, Fig. 13, Fig. 14). The shrinkage pattern of the above halogen-containing fiber is preferably as shown in Fig. 9, followed by Fig. 12, and then Fig. 13 and Fig. 14. It can be a shrinkage caused by stress relaxation as shown in FIG. 9 and a shrinkage caused by the decoupling, and the carbonization ability is $, and the shrinkage pattern of the monotonic shrinkage is optimal, and the carbonization ability can be as shown in FIGS. 12, 13, and 14. Poor, even if it is stretched by softening before carbonization, it will shrink and shrink (shape maintain) at a certain temperature. More preferably, in the figure, b, the shrinkage ratio of the dots is G%, and the above-mentioned (four) fibers are carbonized at a load of 0.0054 mN/dtex from a temperature of 5 〇 β (: 3 〇 η: In the present invention, the above-mentioned element-containing fiber is increased in temperature from 5 〇〇 c to 3 〇〇 β under a load of 0.0054 mN/dtex (when it is carbonized, and remains without being cut, The above-mentioned dentate-containing fiber is used when the temperature is reduced from 5 (TC to 30 (rc) under the load of 〇〇〇54 mN/dtex, and the fiber shrinkage ratio is measured by the following method for measuring the fiber shrinkage ratio. 6. It is not cut off. 6. In contrast, 'Fig. 1 〇, Fig. ! i, Fig. j 5 shows the contraction fluctuation when the contraction fluctuation exceeds the %. In Fig. 10, if the temperature is increased, the elasticity is lost or cut off. In Fig. 11, 'the carbonization ability is excellent, (4) the temperature rises and monotonously shrinks, but the shrinkage caused by the stress relaxation (a to b points in the figure) is too large, and the shrinkage fluctuation of the temperature from 50 C to 300 ° C is exceeded. 65%. Figure 15 is the same shrinking pattern as Figures 12 and 13, but the carbonization ability is weak and the elongation is excellent. , shrinkage variation (difference between shrinkage rate at point b and shrinkage at b' point) exceeds 152753.doc •14·201134992 65% 〇The above halogen-containing fiber preferably has a single fiber strength of 〇5 to 16 cN/dtex, Preferably, it is 0.5M.1 cN/dtex. Among the above-mentioned dentate fibers, the load τ of 二54 2 N/dtex increases the temperature from thief to Cao c, and the shrinkage change easily becomes 65% or less, which is higher. In the present invention, the strength of the single fiber is measured in accordance with JIS L 1 015. The above-mentioned i-containing fiber may be a short fiber or a long fiber, and may be appropriately selected in a method of use. Suitablely selected according to the use of the flame-retardant fiber assembly and the fiber product, preferably W~5, for example, more preferably 15~3〇dtex', and even more preferably L7~15 dtexe cutting length can be based on the flame-retardant fiber assembly and The use of the fibrous product is appropriately selected, for example, a chopped fiber (fiber length of 0.1 to 5 mm) or a short fiber (fiber length "~丨" claw (4), or a completely uncut long fiber (filament). It is preferably a short fiber of about 3 (four) sides of the fiber length ... which can be used in combination with The fiber has the same fineness and may be finer or wider. The flame retardant mechanism of the above halogen-containing fiber will be described. (1) Regarding the metal compound (2-1) as the metal compound (2-1) 'For example, zinc oxide is generally used. It is considered that zinc oxide has an effect of promoting the de-toothing reaction of the dentate-containing fibers. Further, the inventors of the present invention believe that the zinc hydride formed by dehydrogenation and (10) hydrogenation of hydrogen (in the case of gas, gasification) (ZnCl2)) not only promotes carbonization by exerting a catalytic action on a multi-thin structure (the residue at the time of combustion becomes a form-retaining component), but also contributes to the formation of a three-till ring of acrylonitrile (the fiber shrinks by cyclization) The effect can be exhibited not only by zinc oxide, but also by other organic chemicals such as zinc, zinc octylate or zinc octoate, or a part of metal oxides such as tin oxide or copper oxide. Further, the carbide generated as a result of the carbonization and cyclization promoting action by the metal compound (2·1) is strong, and the residue, particularly the residue which retains the fiber form, can be present. When the fire is brought into contact with a composite such as cloth or non-woven fabric in which the residue at the time of heating, particularly the fiber remaining in the form of fibers, remains, the flame can be blocked by the residue. (2) The shrinkage fluctuation when the temperature is increased from 5 〇t to 300 °C under a load of 0.0054 mN/dtex is 65% or less. Normally, the halogen-containing fiber temporarily shrinks upon heating (combustion), and thereafter exhibits Extended behavior. As a factor of shrinkage during heating (combustion), two factors are considered: a. shrinkage caused by carbonization, b. shrinkage caused by residual residual stress. Its t, a. shrinkage caused by carbonization is caused by the decoupling reaction from the copolymer and the formation of the three-pill ring of acrylonitrile. It is derived from a chemical reaction of a copolymer composition, and it is difficult to suppress shrinkage caused by the reaction. On the other hand, the shrinkage caused by the residual shrinkage stress of the spinning is caused by the residual strain imparted to the fiber during the solidification or stretching operation in the fiber manufacturing process', by appropriately selecting the manufacturing conditions of the fiber, particularly the heat treatment in the fiber manufacturing process. Conditional inhibition. Examples of the heat treatment method include a relaxation heat treatment, a moist heat of 15 Torr or more, and a dry heat 180.紧张 The above heat treatment. Among them, as a heat treatment method for sufficiently suppressing the spinning residual stress, it is preferred to heat-treat. By performing these heat treatments, the spinning residual shrinkage stress can be suppressed, and the shrinkage during heating (combustion) can be varied, that is, the shrinkage fluctuation when the temperature is raised from 50 C to 300 ° C under a load of 0.0054 mN/dtex. For 152753.doc -16· 201134992, the temperature from 50 °C is higher than 65%. If the load is at 0.0054 mN/dtex and the shrinkage variation is less than 35% at 300 °C, the flame retardance of the flammability 'height. For example, in the United States bed burning test 16CFR1633 'because there is no such failure in the test, the fiber shrinkage is suppressed, the hole is exposed in the flame exposed portion, or the strain is generated. Cracked, the flame enters from there, and the internal flammable structure catches fire. In terms of exhibiting higher flame retardancy, the higher the flame barrier property, the temperature is increased from 50 ° C to 30 under the load of 0.0054 mN / dtex (the change in I at TC is preferably 6 〇). % or less, more preferably 50% or less, and particularly preferably 45% or less. Further, the above-mentioned shrinkage fluctuation from 5 (rc to 3〇〇r) is preferably as much as possible under a load of 0.0054 mN/dtex. Smaller, the closer to 〇%, the better. Further, it is preferable to increase the temperature from 5 (rc to 3 〇 under a load of 0.0054 mN/dtex (Γ: when carbonized, it remains without being cut off. In the present invention, the softening temperature of the above-mentioned element-containing fiber is close to the dehalogenation starting temperature (decomposition point). Therefore, if the heat treatment temperature is increased, the fiber is colored due to the occurrence of the de-reaction, or it is difficult to impart sufficient heat treatment. As a countermeasure against this, there is a method of lowering the softening point by lowering the acrylonitrile content of the dentate-containing fibers, whereby the heat treatment temperature can be set to be lower than the decomposition temperature, and at the softening point under the conditions of pressurized hot and humid heat. A sufficient heat treatment can be performed below the temperature. (3) About The shrinkage inhibition mechanism of the epoxy group-containing polymer (for example, polyglycidyl methacrylate (pGMA)) causes pGMA to react in the spinning process, and introduces a polymer crosslinked structure into the fiber, thereby suppressing shrinkage. The present inventors believe that the pGMA system 152753.doc •17·201134992 is crosslinked by heat of drying or heat treatment, and further crosslinking can be carried out as long as an acid catalyst is present. The inventors believe that the above The metal oxide (sb2〇3, zinc oxide (Zn〇)) contained in the dentate fiber captures the i element in the polymer contained in the fiber to form an autograft (in the case of gas) Forming SbClrZnCl2), which acts as an acid catalyst to promote cross-linking of {)(}1^8. The above-mentioned element-containing fiber can be obtained by containing acrylonitrile containing 3〇7〇% by mass of alizarin-containing vinylene. The base monomer and/or the dentate-containing vinyl monomer 7〇3 to 3% by mass, and the polymer (1) which can be copolymerized with the ethylene-based monomer 〇~1〇% by mass and promote At least one metal compound (2) of the carbonization reaction during the combustion and the carbonization reaction at the time of combustion The compound is produced by heat treatment after being spun, and specifically, it can be produced by a known method such as a wet spinning method, a dry spinning method, or a semi-dry semi-wet method. For example, in a wet spinning method. By dissolving the above polymer in a mixture of dimethyl dimethyl carbamide, n, n dimethyl acetamide, propyl hydrazine, aqueous thiocyanate, dimethyl sulfite, aqueous solution of succinic acid, etc. After the solvent is passed through a nozzle, it is extruded into a coagulation bath to be solidified, and then subjected to stretching, water washing, drying, heat treatment, and if necessary, a crimping and cutting is performed to obtain a product. The solvent is preferably two. Methylformamide, N,N-dimethyletheneamine, acetone', n,n-dimethylformamide, and acetone are preferred because they can be industrially handled. In addition, if the load τ at 0·0054 mN/dtex increases the temperature from scratch to a range of 65% or less at 3 〇〇C, it can be extended after spinning and before heat treatment. That is, the production of the above-mentioned N-containing fiber can be carried out by extruding (spun) a spinning solution containing the above composition, performing a 152753.doc 201134992 2 water washing, followed by drying, and performing secondary stretching, and Implementation of the implementation of the order. In the present invention, the term "secondary extension" means elongation in the fiber production step (spinning step) after spinning and until drying, and the so-called secondary stretching means self-drying, and: operating. Further, the primary stretching may be carried out in any step as long as it is before the drying step. For example, it may be carried out before water washing, one side = one side, water purely, or continuously washed from a water washing towel. In the production of the above-mentioned element-containing fiber, the stretching ratio multiplied by the relaxation ratio is determined to be 5 times or less, more preferably 4.8 times or less, and particularly preferably 3.7 times or less. Thereby, the spinning residual shrinkage stress can be further suppressed to obtain higher flame retardancy. Further, the total stretching ratio is preferably (M times ±, more preferably! 〇 times 1). In the present invention, the term "stretching magnification" means fibers in the fiber manufacturing step (spinning step) before heat treatment. The ratio of elongation is long. The spinning step before the above heat treatment includes, for example, a solidification step (extrusion of the spinning solution), a water washing step (including the case where the surface is extended while the surface is washed), a drying step, an extension step, and the like. For the treatment of the length of the fiber, for example, when the thread (fiber bundle) is moved between two parents, the stretching ratio is 1 () times if the speed of the human side roller is the same as the speed of the exit side. ^The treatment is performed when the length of the fiber is three times. For example, when the yarn (fiber bundle) is moved between the two rolls, the stretching ratio becomes 3 when the exit side roller speed is three times the speed of the inlet side roller. The above stretching ratio is not particularly limited, and the performance of the fiber and the fiber strength are exhibited, and the temperature of 152753.doc •19·201134992 is increased from 5〇C to 3〇〇 under a load of 0.0054 mN/dtex. Wide d* back to 3〇〇C The contraction variation is set to (10) in the following, preferably 1. 〇~10 〇 times 〇^ and as the above-mentioned extended 俾 夕 π π limit, more preferably 2.0 times... Under the evaluation of the sheep under the sheep | ·〇倍' as the upper limit value, more preferably 9.0 9.0 times, especially 8.0 times. For the middle Μ, early, f material a ”,, before the treatment, a plurality of spinning steps 2 are given plural: the situation of human extension When the stretching ratio of the present invention is multiplied by the stretching ratio of each extension 2, for example, as described above, in the case of Qiu Ben, 仃-person extension and secondary extension, the stretching ratio is the primary stretching ratio. Multiply _ ^ ^ one - the person who stretched the magnification. In this case

When the stretching ratio is the same, 贞彳&# A only J is better than the second extension, and the effect of one extension is larger. As a further aspect of the company, it is preferable to extend the aspect only by one extension. Further, the one-person extension ratio is preferably 8 times or less, more preferably 6 times or less, and particularly preferably A <; pull: ", σ. Further, the secondary stretching ratio is preferably 3 times or less', more preferably 1.5 times or less. Further, in the present invention, the relaxation ratio refers to the ratio of fiber shrinkage in the above heat treatment step. Specifically, it means a heat treatment step in the fiber manufacturing step (spinning step), for example, including a solidification step (extrusion of the spinning solution), a water washing step (including a case where one side is washed with one side), a drying step, and an extension. In the treatment step of the step material (4), the ratio of the fiber length shrinkage in the step of reducing the material row. For example, in the case of heat treatment for imparting a fiber length, the relaxation ratio is Κ0 times, and when the fiber length is changed to a heat treatment, the relaxation ratio is 〇·5 times. The above-mentioned relaxation ratio is particularly limited, and the temperature is increased from 5 〇 ° C to 30 under the load of 〇 〇 m 54 mN/dtex (the shrinkage variation at TC is 65% or less). Preferably, it is G.3~1.〇 times, and 'as the lower limit of the above relaxation ratio, more 152753.doc •20·201134992 is preferably 0.4 times, especially preferably 〇·5 times, as the upper limit value, More preferably, it is 9 times and preferably 0.8 times. The heat treatment of the present invention has a relaxation heat treatment and a tension heat treatment. The relaxation heat treatment in the present invention refers to heat treatment in the following state: for example, if a yarn (fiber bundle) is assumed When heat treatment is applied between the two rolls, the state of the wire when moving between the rolls (fixed length state) or the moving wire phase when the two rolls are set to the same rotational speed under the temperature condition in which the fibers are not shrunk In a state where it is more slack than this (relaxed state). Further, when the fiber is shrunk between the two rolls by heat treatment, the tension applied to the fiber is the same level as the above state, and the heat treatment is also relaxed. Also known as the present invention The intense heat treatment refers to a heat treatment in a state other than the state of the yarn in the relaxation heat treatment, for example, when the two rolls are set to the same rotation speed under the temperature condition in which the fibers are not shrunk, the movement between the rolls is exceeded. The state of the wire (the fixed length state) is applied to the state in which the tension of the fiber is greater (tension state). Further, when the fiber is shrunk between the two rolls by heat treatment, it is applied to the fiber as long as it is applied to the fiber. When the tension is the same as the above-mentioned state, the heat treatment is also intense. Further, when the roll is not used, if the heat treatment is the same as the state of the yarn in the relaxation heat treatment, the heat treatment is also performed. The heat treatment in the tension state equivalent to the state of the thread in the heat treatment is a stress heat treatment. The heat treatment method may be any one of a dry heat treatment method and a wet heat treatment method as a general heat treatment method. The wet heat treatment in the present invention is defined as heating in an environment containing water vapor (wet air). 152753.doc -21· 201134992 State treatment. The above environment is phase # is relative humidity of 30% or more, preferably relative humidity (four) or more, and further preferably relative humidity of 7〇% or more, preferably relative humidity surface (saturated water) The vapor content is higher. The higher the relative humidity, the better the shrinkage rate, the fiber whiteness, etc. Further, the wet heat treatment method includes a heating steam treatment method and a full heat pressure steam treatment method, but is not limited thereto. In the case of the thirst irritated >, ...the pressure-steaming treatment method, as the aspect of imparting the heat of the fish, and the special irp 6 ..., it is not limited to, for example, it can be exemplified in the presence of a thread. A method of introducing steam into a device, a method of introducing steam into a device having a wire to form a saturated steam condition, and a device for inserting a wire into a device equipped with a wire to generate a hot air generator (heater) provided outside the wire Hot air and put steaming, methods, etc. As a fiber during heat treatment. The tension state of the thread can be loose or tight. Furthermore, here is the so-called (four) two places = long state. As such a combination, a dry heat stress heat treatment method, a dry heat relaxation rail heat relaxation heat treatment method, a heating water vapor tension heat treatment method, a heating water vapor relaxation heat treatment method, a wet heat pressure steam tension heat treatment method, and a damp heat may be mentioned. Pressurized steam relaxation heat treatment method, preferably dry heat pine treatment method, heating water vapor relaxation heat treatment method, damp heat plus factory steaming heat treatment = further preferably dry heat relaxation heat treatment method, wet heat pressure steam Songta heat method. Further, the method or the tension state of the fibers (filaments) of the fibers may be combined to form a heat treatment step. Generally, in the heat treatment of dentate-containing fibers, the higher the treatment temperature, the lower the residual shrinkage stress of the invisible wire, especially in the case of wet heat treatment, and then in the case of heat treatment plus steam, even if heat required for heat treatment It can also be transferred to the inside of the fiber 152753.doc -22· 201134992 for the softening temperature or decomposition temperature of the fiber containing the element, so that the coloring or strength can be reduced without treatment. The above-mentioned enthalpy treatment can be used as a heat (1) continuation or batch processing. Especially when using acrylonitrile exceeds 5 〇 mass%; > p old octamer, it is preferred to add hydrazine steam treatment, moist heat addition steam... ^ -i- 〇 / LV -r - V xx . Use acrylonitrile for 50. In the case of a polymer, a dry heat treatment method or a thirst pressure steam treatment method is preferred. j:k is due to the force........ Because the color of any of the fibers is higher than the heat treatment temperature, and the heat treatment method for the heat treatment is (10) to preferably (10) to (10). C' and then the car t is preferably 150 to 170 ° C, very good, private 丄 r- right is wet heat pressure steam treatment, then 8 〇 ~ (10). c, preferably 90 to 15 〇t, and more preferably _~ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ In the case of the intense heat treatment, 'if dry heat treatment method' is 18 〇 to 26 〇. . Preferably, it is 180 to 24 () t: if it is a wet heat pressurized steam treatment, it is 150 to 23 (TC, preferably 160 to 210 C, and 160 to 250 C for heating steam treatment, It is preferably 17 〇 22 22 ( rc. The upper limit of the heat treatment temperature is not particularly limited, and is 300 C, preferably 250 ° C, and more preferably 22 in terms of the color of the above-mentioned element-containing fiber and industrial viewpoint.作为 ° C. The heat treatment is preferably a relaxation heat treatment, a dry heat stress heat treatment of 18 CTC or more, or a damp heat stress heat treatment of 15 〇e C or more. It can be easily obtained at a load of 0.0054 mN/dtex and the temperature is from 5 〇〇 c. It is a halogen-containing fiber with a change of I® of 65% or less when it is increased to 3〇〇〇c. Further, as a heat treatment, it is preferably a relaxation heat treatment, and it is preferable to relax in a damp heat of 9〇~丨5〇艽. Heat treatment ❶ In addition, the heat treatment in the present invention means shrinking the fiber under heating 152753.doc •23·201134992 to reduce and remove the spinning shrinkage stress. (Polyester fiber) In the present invention, the so-called polyester Fiber, refers to the oxygen index test according to JIS L丨〇9丨Ε method The measured oxygen index (hereinafter referred to as L〇I value) is a polyester fiber of 23 or less. For example, it also includes: polyethylene terephthalate, polybutylene dibutylate, polynaphthalene a fiber such as ethylene formate, polybutylene naphthalate or propylene terephthalate; or a component different from a melting point such as polypropylene by a composite spinning method or the like; a low-melting adhesive which is mixed with polyethylene and the like and is fiberized into one. Polyester-based fiber or the like (a flame-retardant fiber other than a halogen fiber). In the present invention, it is a flame-retardant fiber other than a halogen-containing fiber. As long as it is a fiber having flame retardancy other than the above-mentioned dentate-containing fiber, for example, an aromatic polyamide fiber, a benzoate fiber, a polyphenylene sulfide fiber, a polyetheretherketone fiber, or a polyfluorene fiber can be used. Amine fiber, polyamidoximine fiber, flame retardant polybenzazole fiber, melamine fiber, acrylate fiber, polyphenylene oxide (P〇lybenzoxide) fiber, polystyrene fiber, poly(ethylene diacetate) fiber, poly Gas vinyl alcohol fiber, polytetrafluoroethylene fiber, including Regenerated cellulose fiber such as regenerated cellulose fiber of inorganic compound or regenerated cellulose fiber containing phosphorus-based flame retardant, processed with flame retardant agent, processed with flame retardant cellulose fiber, oxidized acrylic fiber, carbon fiber, glass fiber, activated carbon fiber , 隹, etc. A fiber having an LOI value of 25 or more may be suitably used. The above-mentioned inorganic compound in the regenerated cellulose fiber containing an inorganic compound is preferably a bismuth component. Plain fiber I52753.doc -24· 201134992 'The content of the inorganic compound in the quasi-quantity, when the total amount is set to be just the mass binary value, preferably red 5% by mass, more preferably 3% by mass, and even more preferably 4: 罝. More preferably, it is 6 mass%, and the upper limit is preferably 32 mass%, more preferably 27 mass%. Further, it is more preferably 22% by mass, and particularly preferably "% by mass. In the above, the content of the inorganic compound is represented by the content of the inorganic compound (% by mass), and when the inorganic compound is a bismuth component, The content of the element of the stone eve, and the content of the element (4) of the regenerated cellulose fiber containing the (four) component, the lower limit is preferably 丨$% by mass, more preferably 3% by mass. More preferably, the mass % is particularly good, and the upper limit is preferably 32% by mass, more preferably 27% by mass, and even more preferably 22% by mass, and particularly preferably 16% by mass. The term "flammable polyester fiber" refers to a polyester fiber having a L0I value of 26 or more, and also includes a fiber containing a flame retardant or a polyarylate fiber, etc. Among them, flame retardancy or heat insulation, cost, and difficulty From the viewpoint of the texture of the fuel fiber assembly, etc., it is preferably a regenerated cellulose fiber containing a bismuth component or a phosphorus-based flame retardant, a processable flame retardant cellulose fiber, a melamine fiber, and a flame-retardant polyester fiber. Acrylate fiber, aromatic poly The amine fiber is more preferably a regenerated cellulose fiber containing a bismuth component or a phosphorus-based flame retardant, or a flame retardant cellulose fiber or an aromatic polyamide fiber coated with a flame retardant. For example, the product name "Kevlar" manufactured by Dup〇nt & Division, the trade name "Nomex" manufactured by Dupont Co., Ltd., the product name "RTechn〇ra" manufactured by Teijin Co., Ltd., the product name "Twaron" manufactured by Teijin Co., Ltd., and the Teijin company can be used. Trade name 152753.doc • 25· 201134992

Conex"', as the polyphenylene sulfide fiber, for example, a commercially available product manufactured by Toyobo Co., Ltd.; and, for example, the product name "p84" manufactured by Toyobo Co., Ltd.; For the amine fiber, for example, the product name "Kermel" manufactured by Kermel Co., Ltd., and the trade name "R Heim" manufactured by Toyobo Co., Ltd., and the trade name "Trevira CS" manufactured by Trevira Co., Ltd. can be used as the above-mentioned flame retardant polyester fiber; For the melamine fiber, for example, the product name "Bas〇fu" manufactured by Basofil Fiber Co., Ltd. can be used. For the acrylate fiber, for example, the product name "MoiSCarej" manufactured by Toyobo Co., Ltd. can be used as the above polyphenylene oxide fiber, for example, The product name "ZylGn" manufactured by the company; for the above-mentioned polyvinylidene-containing ethylene fiber, for example, the product name "Saran" manufactured by Asahi Kasei Fiber Co., Ltd.; and the regenerated cellulose fiber containing the bismuth component, for example, can be manufactured by Sated Co., Ltd. The trade name "(4)", D - the trade name "fr Corona" made by the company The product name "HOPE-FR" manufactured by Omikenshi Co., Ltd.; and the regenerated cellulose fiber containing the phosphorus-based flame retardant, for example, the product name "Lenzing FR" manufactured by Lenzing Co., Ltd., and the trade name "ΝΕχτ·" manufactured by Omikenshi Co., Ltd. FR", the product name "dfg" manufactured by Daiwabo Rayon Co., Ltd., etc. (Flame-resistant fiber aggregate) In the present invention, the term "c〇mp〇site" means a cotton, a nonwoven fabric, a woven fabric, a woven fabric, or the like which contains the above-mentioned filler-containing fiber. Mesh knits, braids, etc. In the present invention, the "flammable fiber composite" is an example of the above-mentioned flame-retardant fiber assembly, and is referred to as 152753.doc -26 - 201134992 ::: a dentate fiber and other fibers form a composite body. . In the present invention, the fiber assembly includes the above-mentioned ruthenium-containing fiber and the above-mentioned polyester fiber-containing fiber. When the total of 1 of the above-mentioned flame retardant and quasi-collector σ bodies is set to 〇〇 mass load/〇, the amount of the dentate-containing fibers is 3 to 30% by mass, preferably - sm. /. More preferably, it is 5 to 10 masses. If the range is 2, the desired properties can be obtained, especially for the incombustible fiber. When the aggregate is in the form of a non-woven fabric or a cloth, the flame is suppressed: the temperature of the face Rising 'to alleviate the effect of the heat of the internal structure that exists on the back side, and it can be smothered. Further, in the above-mentioned flame-retardant fiber, the content of the polyester-based fiber in the mouth-in-law is 2% to 3% by mass, preferably 20 to 40% by mass, and the flame retardancy of the flame-retardant fiber assembly can be simultaneously achieved. With fluffiness or f sensitivity. Further, the content of the flame retardant fiber other than the i-containing fiber in the flame-retardant fiber assembly is 30 to 77% by mass, preferably 35 to 75% by weight, and more preferably 4 to 65% by mass. . If the performance is within the range, it is easy to maintain the required fire-extinguishing property, and at the same time, it is difficult to obtain the above-mentioned fiber in the flame-retardant fiber assembly as long as it does not hinder the flame retardancy effect of the above-mentioned flame-retardant fiber assembly. Fibers other than the species. As natural fibers that can be contained, there are cotton (c〇tt〇n) fibers, kapok (kap〇k) fibers, flax fibers, hemp fibers, ramie fibers, jute fibers, and Manila hemp. Fiber, kenaf hemp) fiber, wool fiber, mohair hair, cashmere fiber, camel fiber, alpaca fiber, angora fiber, silk fiber, and the like. Recycled as a recycled fiber 152753.doc •27· 201134992 Cellulose fiber (poiynosic), trade name "Cupro" manufactured by Asahi Kasei Corporation, trade name "Tencel" manufactured by Lenzing, manufactured by Lenzing Trade name "Lenzing Modal"), regenerated collagen fiber, regenerated protein fiber, cellulose acetate fiber, promix fiber, and the like. Examples of the synthetic fibers that may be contained include nylon fibers, polylactic acid fibers, acrylic fibers, polyolefin fibers, polyvinyl alcohol fibers, polyethylene fibers (trade name "Dyneema" manufactured by Toyobo Co., Ltd.), and polyurethane fibers. Polyoxymethylene fiber, etc. The ratio in the above-mentioned flame-retardant fiber assembly is selected within the range of 〇3 to 3% by mass. When the dentate-containing fibers, the polyester fibers, and the flame-retardant fibers other than the dentate-containing fibers are contained in the above numerical range, the fibers may be contained in the flame-retardant fiber assembly. In the present invention, the above-mentioned flame-retardant fiber assembly can be produced by blending, blending, blending, and blending by interlacing, laminating, or the like. Also, there is a cotton material such as a filler or a braid. Cotton or the like as a filler or the like. As a non-woven fabric, right. How to weave, heat-bonded non-woven fabric, non-woven fabric, carded non-woven fabric, air-woven non-woven fabric, non-woven fabric, non-woven fabric, needle-punched non-woven fabric, water industry is relatively cheap. also,. Heat-bonded non-woven fabric, needle-punched non-woven fabric contains uniform surname on the top, non-woven fabric can be used in thickness, width, and long-sounding.", clear laminated structure, unclear laminated layer 152753.doc 颂 心 构 构 中 、 、 、 A composite yarn such as a sheath is a non-woven fabric, a woven fabric, a woven fabric, or a mesh knitted fabric of the above-mentioned flame-retardant fiber assembly, and is knitted with any of an open-fiber cotton, a cotton ball, a mesh, and a formed -28·201134992. There are plain weave, slanted fabric, satin fabric, variegated fabric, slanted woven fabric, woven satin fabric, fancy fabric, woven fabric, single layer fabric, double tissue, multiple tissues, vertical pile fabric, horizontal, A woven fabric, a woven fabric, a woven fabric, and a woven fabric are excellent in texture and strength as a product. The woven fabric includes a circular woven fabric, a weft knitted fabric, a warp knitted fabric, a piled woven fabric, etc. Jersey, plain weave, heavy weave, smooth stiteh, rib fabric, double reverse fabric, warp-knitted tissue, warp-knitted fabric, warp-knitted weave, tuck A woven fabric, a woven fabric, etc. The plain woven fabric and the heavy woven fabric are excellent in texture as a product. The fiber product (applicati〇n) of the invention of the present invention, which contains the above-mentioned fuel fiber aggregate, is as follows矣-. A general name for products such as the following: (υ Clothes and daily necessities materials (including outerwear, underwear, sweaters, vests, pants, etc.), gloves, scarves, hats, bedding, pillows, Um, cloth dolls, etc. U) special clothing protective clothing, fire service, overalls, winter clothes, etc. (3) interior decoration materials, chair covers, curtains, wallpapers, carpets, etc. (4) Industrial materials filter, refractory filler, lining material For example, a bed cushion, if the fiber product of the present invention is used to manufacture a bedding or furniture cushion pillow, a comforter, a bed cover, an early bed mattress, a bedding 152753.doc • 29-201134992, and other non-flammable fabric products, It is possible to obtain a fabric product which is flame retardant and has excellent properties such as texture, touch, color tone, moisture absorption, etc. As a mattress, for example, a bag spring in which a metal spring is used internally P〇cket coil mattress, frame spring mattress (b〇xc〇il mamess), or internal insulation for foaming styrene or amino phthalate resin or low repellency amine ruthenium citrate The mattress or the like of the mattress of the present invention can prevent the structure of the inside of the mattress from being burnt by the flame retardancy of the flame-retardant fiber assembly of the present invention, so that the mattress of any structure can be excellent in flame retardancy. At the same time, the mattress with excellent texture and touch is also used as a chair, which can be used as a stool, bench, single chair, armchair, recliner, sofa, seat device (combinable chair, separable chair) )), rocking chair, folding chair, packing chair, swivel chair, or seat for vehicles, etc., seat for cars, seats for ships, seats for airplanes, seats for trains, etc. It is also possible to obtain a flame-retardant product having the function of preventing the appearance and feel of the usual furniture as well as preventing the internal burning. As a time-making method for a flame-retardant cloth (four) product comprising a flame-retardant fiber of the present invention (hereinafter referred to as a raw material of the present invention), it may be: a fabric of a fabric or a knitted fabric, or a fabric, The pattern of knitted fabrics and non-woven fabrics is sandwiched between the fabric of the surface and internal structures such as amines, foams and filled cotton. In the case of a fabric for a surface: it is sufficient to replace the cloth of the previous surface with the raw material of the present invention. Further, in the case of being sandwiched between the surface material and the internal structure, the raw material of the present invention can be sandwiched between the two surface materials, and the internal structure can be covered with the raw material of the present invention. Further, in the case of the original invention of the invention (4) 152753.doc 201134992, it is preferred that at least part of the internal structure in contact with the fabric of the surface is covered by the raw material of the present invention. [Examples] Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto. Furthermore, in the following embodiments, "%" means "% by mass". (Evaluation method for decoupling reaction promotion) The evaluation method for the promotion of the detoxification reaction was carried out in the following manner using a thermogravimetric/thermal differential measurement meter (manufactured by Seiko Instrument Co., Ltd., trade name "TG/DTA220"). 50.1 parts by mass of acrylonitrile, 47 parts by mass of halogen-containing vinylidene monomer, and 5 parts by mass of sodium styrene sulfonate (1) 5 mg, under air conditions (gas flow rate: 200 ml/min, Heating rate: 2 (rc/min) When heating, the temperature at which the weight starts to decrease is measured. In the present invention, the temperature at which the weight starts to decrease is defined as the dehalogenation starting temperature. The measured dehalogenation starting temperature is 2 4 3 ° C. Then, 10 parts by mass of the metal compound shown in the following Table 1 was added to 100 parts by mass of the above polymer (1), and 5 mg of the sample which was sufficiently mixed was placed under air (gas flow rate: 200 ml). /min, heating rate: 2 (rc/min) heating. At this time, the starting temperature of the decoupling is less than 243^, which is determined to promote the dehalogenation reaction, and S is used as A. 243. above

If the shape is judged as not promoting the decoupling reaction, it is recorded as B. The results of the diced mussels of each metal compound are not shown in Table 1. (Evaluation method for carbonization reaction promotion) 152753.doc •31- 201134992 The evaluation method for carbonization reaction promotion is performed by using a thermogravimetric/thermal differential measurement meter (manufactured by Seiko Instrument Co., Ltd., trade name "TG/DTA220") in the following manner. Implementation. The polymer (1) 5 mg containing 51.5 parts by mass of acrylonitrile, 47.4 parts by mass of a halogen-containing vinylidene monomer, and 1.1 parts by mass of sodium styrene sulfonate is heated under air conditions (gas flow rate: 200 ml/min). Speed: 2 〇 t: / min) When heating, the residual weight ratio at 500 ° C was measured. As a result, the residual weight ratio was 52%, and then '100 parts by mass of the above polymer (1) was added, and 1 part by mass of the metal compound shown in the following Table 1 was added, and 5 mg of the sample which was sufficiently mixed was placed under air conditions. (Gas flow rate: 2 〇〇 ml/min, heating rate: 2 〇 ° C / min) Heating. At this time, the residual weight ratio at 5 ° C was 47 ° /. In the above case, it was judged that the carbonization reaction was promoted, and it was recorded that the residual weight ratio under 5〇〇t>c was less than 47%, and it was judged that the carbonization reaction was not promoted, and the evaluation of each metal compound was recorded as B^. The results are shown in Table 1 below. (the content of the inorganic compound and the content of the lanthanum element) The content of the inorganic compound or the sample (the flame retardant fiber in the flame retardant fiber other than the functional fiber in the flame retardant fiber aggregate) The content of the lanthanum element in the flame retardant fiber other than the dentate fiber in the aggregate is a fluorescent X-ray analyzer (sn., manufactured by Sn Nan〇Techn〇l〇gy, trade name "SEA221GA"). It is calculated by using a calibration curve for calculating the content of the element to be measured. 152753.doc -32· 201134992 [Table l]

Dechlorination onset temperature of metal compound (°c) (Evaluation method for dehalogenation reaction) 500°C residual weight (%) (Carbonation reaction evaluation method) Degassing reaction promotion performance Carbonization promotion performance No 243 52 - _ Zinc oxide 181 62 AA Carbonate 187 57 AA Zinc Sulfide 238 56 AA Tungsten Oxide 241 54 AA Oxidation Junction 238 54 AA Tin Oxide 200 56 AA Copper Oxide 222 62 AA Copper Phosphate 235 53 AA Indium Oxide 236 56 AA Barium Titanate 242 56 AA Boric Acid Zinc 237 49 AA zinc stannate 196 47 AA metastannic acid 234 51 AA antimony trioxide 220 42 AB five oxidation record 220 42 AB sodium citrate 220 42 AB iron oxide 233 11 AB iron phosphate 230 35 AB oxalate iron 227 28 AB vulcanization Iron 226 40 AB Oxidation _ 241 46 AB Antimony trioxide 197 43 AB Oxide 铋 191 39 AB Moth copper 203 41 AB Aluminium hydroxide 244 45. BB p-Toluene sulfonate 230 53 AA (Manufacture of _ fiber Example 1) A copolymer comprising 51% of acrylonitrile, 48% of vinylidene chloride and 1% of sodium p-styrenesulfonate was dissolved in acetone so that the resin of the obtained resin solution was 10 0 parts by mass, adding the amount of oxidation of the metal compound (2-1) (three types of zinc oxide JIS) and antimony trioxide as the metal compound (2-2) in the amount shown in the following Table 2 Silk stock solution. 152753.doc -33- 201134992 Using a nozzle with a nozzle hole diameter of 0·10 and a number of holes, the spinning dope is broadcasted to a 30% acetone aqueous solution and solidified while being 3.3 times. The stretching ratio was extended once, washed with water at 12 °t > c, and subjected to secondary stretching at a stretching ratio of 1.3 times at 140 ° C, and then heated under water vapor (saturated water vapor) at 17 ° C. The heat treatment was carried out for 20 seconds at a relaxation ratio of 0.85 times, and further cut, thereby obtaining a halogen-containing fiber. The resulting fiber had a fineness of 7.8 dtex and a short fiber length of 64 mm with a shrinkage variation of 58%. (Production Example 2 containing a ruthenium fiber) A copolymer containing 57% of acrylonitrile, 41% of ethylene diene oxide, and 2% hydrazine of allyl sulfonate was dissolved in dimethyl group at a resin concentration of 25%. In the formamide, zinc is added as a metal compound (2") as a metal compound (2-) in an amount of 1 part by mass based on the resin of the obtained resin solution, as shown in the following Table 2. 2) The ruthenium pentoxide is prepared into a spinning dope. The spinning dope is extruded into a 55% dimercaptoamine aqueous solution using a nozzle having a nozzle aperture of 0.06 mm and a number of holes of 1 boring. While solidifying, it was once stretched at a stretching ratio of 5.6 times, washed with water and dried under 12 liters, and further dried in a humidified pressurized vapor (saturated water vapor) 13 〇 c > Ct, and the relaxation ratio became Q. In the state of no tension of 85 times, the treatment was carried out for 5 minutes, and then cut, thereby obtaining the fiber containing the fiber. The obtained fiber has a fineness of 7.8 dtex, and the short fiber with a cutting length of 64 mm has a shrinkage change of 63. % 〇 (manufacturing example 3 containing spectrin fiber) is made to contain acrylonitrile 51. Diethylene carbamide and benzoate sulphate 152753.doc -34* 201134992 1 〇 / 〇 copolymer dissolved in acetone in a resin concentration of 30%, relative to the resin resin obtained i00 parts by mass The zinc oxide (three types of zinc oxide JIS) and the antimony trioxide as the metal compound (2_2) were added as a metal compound (2-1) in an amount shown in the following Table 2 to prepare a spinning dope. The spinning dope was extruded into a 30 〇/〇 acetone aqueous solution by a nozzle having a diameter of 1 〇 mm and a number of holes of 1 ,, and was solidified while being stretched at a stretching ratio of 3.3 times. After drying at 12 ° C, it was subjected to secondary stretching at a stretching ratio of 1.3 times at 140 ° C, and then heated under water vapor (saturated water vapor) * 17 〇〇 c at a relaxation ratio of 85 times for 20 seconds. The heat treatment was followed by heat treatment, and further, the halogen-containing fiber was obtained, and the obtained fiber had a fineness of 78 dtex and a short fiber length of 64 mm, and the shrinkage variation was 61%. (Manufacturing Example 4 of the tooth-containing fiber) Include acrylonitrile 51%, vinylidene chloride 48% and The copolymer of sodium sulfonate 1% was dissolved in acetone so that the resin concentration was 3% by weight, and the amount of the resin shown in the following Table 2 was added as a metal compound in an amount of 1 part by mass based on the resin of the obtained resin solution. The tin oxide is used as the metal compound (2_2) to form a spinning dope. The spinning dope is extruded to 3〇% using a nozzle having a nozzle diameter of 0.10 mm and a number of holes of 1 boring. In the aqueous acetone solution, while solidifying, the film was stretched once at a stretching ratio of 33 times, washed with water, dried under 12 Torr, and further expanded at a stretching ratio of Μ times at i4 〇t, and then heated in water. In a vapor (saturated water vapor), a ten-second tension heat treatment was carried out at a relaxation ratio of 0.85 times at a rate of 0.85 times, and further cut, thereby obtaining a tooth-containing fiber. The resulting fiber system 152753.doc •35- 201134992 has a fineness of 7.8 dtex' cut length of 64 _ and a short fiber shrinkage of 60%. (Production Example 5 of the element-containing fiber) A copolymer containing 51% of acrylonitrile, 48% of ethylene diene and 1% of sodium p-benzoate was dissolved in acetone so that the resin concentration became 3% by weight. 1 part by mass of the resin of the obtained resin solution was added with hydrazine as shown in the following Table 2, and zinc carbonate as a metal compound (2_丨) and trioxane (4) as a metal compound (2-2) were added. Into the spinning dope. The spinning dope was extruded using a nozzle having a nozzle aperture of m mm and a number of holes of 1000 holes. In the aqueous acetone solution, while solidifying, it was once stretched at a stretching ratio of 3.3 times, washed with water, dried at 12 (TC), and secondarily stretched at a stretching ratio of 13 times at 14 Torr, and then heated. In a water vapor (saturated water vapor), the ii-containing fiber was obtained by performing a two-second tension heat treatment at a relaxation ratio of 0.85 times at a relaxation ratio of 0.85 times, thereby obtaining a fiber-containing fineness of 7.8 dtex and a cutting length of 64. The short fiber of mm has a shrinkage variation of 60%. (Manufacturing Example 6 containing Nansu fiber) The surface is solidified to one side so that 51% of acrylonitrile, 48% of ethylene oxide and 1% of sodium p-styrenesulfonate are contained. The copolymer was dissolved in acetone so that the resin concentration was 3% by weight, and the amount of addition of the resin shown in Table 2 below was added as the metal compound (2-1) to 1 part by mass of the resin of the obtained resin solution. Zinc oxide (3 types of zinc oxide jIS) and antimony trioxide as the metal compound (2-2) are used to form a spinning dope. A nozzle having a nozzle aperture of 〇.1〇mm and a number of holes of 1 boring is used. The spinning dope is extruded into a 3 〇〇 /. acetone solution 152753.doc -36· 201134992 3·3 times the stretching ratio -: under-extension, after washing, drying at 12 (TC), after stretching at l4〇°C with a stretching ratio of 3 times : In the hot water vapor (saturated water vapor), the heat treatment is carried out at a relaxation rate of 85 times at a relaxation rate of 85 times, and further cut, thereby obtaining a fiber containing the fiber. The obtained fiber system has a fineness of 7 · 8 dtex, short fiber with a length of 64 mm, with a shrinkage change of 59%. (Manufacturing Example 7 of dentate fiber) 51% of acrylonitrile, 48% of ethylene dimerate and 1% of sodium p-styrenesulfonate The copolymer was dissolved in acetone so that the resin concentration was 3% by weight, and the amount of the resin represented by the following Table 2 was added as a metal compound (2_丨) with respect to 1 part by mass of the resin of the obtained resin solution. Zinc telluride (3 kinds of zinc oxide jis) and antimony trioxide as a metal compound (2·2) to prepare a spinning dope. Using a nozzle having a nozzle aperture of 〇.1 with a number of borings of 1 boring, The spinning dope is extruded into a 30% aqueous acetone solution and solidified while being stretched by 3.3 times. Perform an extension of 'washing, dry it under 12 〇, and perform a second extension at a stretching ratio of 1.3 times at 140 C, and then heat the water vapor (saturated water vapor) to $170 〇 CT, 缓 85 times the relaxation ratio. The heat treatment was carried out for 2 minutes, and further, the film was subjected to cutting to obtain a halogen-containing fiber. The fiber obtained having a fineness of 7.8 dtex and a short fiber having a length of 64 mm had a shrinkage variation of 52%. (Production Example of Halogen-Containing Fiber) 8) A copolymer containing 51% of acrylonitrile, 48% of ethylene dimerate, and 1% of sodium p-styrenesulfonate was dissolved in acetone so that the resin of the obtained resin solution was 10 〇. The mass fraction is 152753.doc •37·201134992 % as shown in Table 2 below, and is added as the oxidation word of the metal compound (2_!) (zinc oxide JIS $ species), and as the pentoxide of the metal compound (2_2). Make a spinning dope. The spinning dope is extruded into a 3〇% acetone water-reducing towel using a nozzle having a nozzle hole of 〇1〇mm and a number of holes of i-hole, and the surface is solidified, and the stretching is performed at a stretching ratio of 3β·3 times. - Sub-extension, after washing with water at 12 (drying at TC, sub-extension at a stretching ratio of 1 > 3 times at HOt, and then heating in water vapor (saturated water vapor) at 17 (rc, 〇.85 The tempering rate of the light into the lamp 20 private tension heat treatment 'and further cut, thereby obtaining the fiber containing the dentate fiber, the quasi-serving fiber has a fineness of 7.8 dtex, and the short fiber with a cutting length of 64 mm has a shrinkage of 60%. (Production Example 9 of dentate fiber) A copolymer containing 51% of acrylonitrile, 48% of ethylene dimerate, and 1% of sodium p-styrenesulfonate was dissolved in a polypropylene resin in such a manner that the resin has a moisture content of 30%. With respect to 100 parts by mass of the resin of the obtained resin solution, zinc oxide (three types of zinc oxide) as the metal compound (21) was added in an amount shown in the following Table 2 to prepare a spinning dope. 1〇 and a nozzle with a hole number of 1000 holes, and the spinning dope is extruded into a 3〇% acetone aqueous solution, While solidifying, it is stretched once at a stretching ratio of 33 times, washed with water at 12 〇t, and once extended at a stretching ratio of 3 times at 140 ° C, heated water vapor (saturated water) In the case of steam, it was subjected to a tension heat treatment for 2 minutes at a relaxation ratio of 0.85 times, and further cut, thereby obtaining a fiber containing a fiber having a fineness of 7.8 dtex and a cutting length of 64 mm. Short fiber, shrinkage change is 55 〇 / 〇. (Production Example 10 containing halogen fiber) 152753.doc -38- 201134992 Included propiononitrile 51%, vinylidene chloride 48% and sodium styrene sodium 1 The copolymer of % is dissolved in acetone so that the resin concentration is 30%, and zinc oxide is added as the metal compound (2-1) in an amount shown by the following Table 2 with respect to 100 parts by mass of the resin of the obtained resin solution. (3 kinds of zinc oxide JIS), and as a metal compound (2-2), antimony trioxide is used to prepare a spinning dope. The spinning is performed using a nozzle having a sniffer aperture of 〇mm and a number of holes of 1 boring. The stock solution is extruded into a 3〇〇/0 acetone aqueous solution and condensed on one side. One side was stretched at a stretching ratio of 3 to 3 times, and after drying, it was dried at 1 t to 140. (: The second extension was carried out at a stretching ratio of 1.3 times, and then at 182 C, the relaxation ratio was 85.85 times. The dry heat-strength heat treatment was carried out for 2 minutes, and the cutting was carried out to obtain a fiber containing the fiber. The obtained fiber had a fineness of 7.8 dtex and a short fiber length of 64 mm, and the shrinkage variation was 47%. Manufacture example of fiber η) A copolymer containing 51% of acrylonitrile, 48% of vinylidene chloride, and 1/? of sodium styrene sulfonate was dissolved in propionate at a resin concentration of 3% by weight. 1 part by mass of the resin of the resin solution, zinc oxide (zinc oxide jis ^ species) as the metal compound (2-1) and trioxide content as the metal compound (2_2) were added in the amounts shown in Table 2 below. , made into a spinning dope. Using a nozzle having a nozzle aperture of 〇.1 〇 mm and a number of holes of 1 boring, the spinning dope was extruded into a 30% aqueous solution of propylene and solidified while being subjected to a stretching ratio of 3.75 times. After stretching, the mixture was washed with water and then dried at 185 ° C for 2 minutes at a relaxation ratio of 8 times, and then cut, thereby obtaining a fiber containing the element. 152753.doc •39- 201134992 The fiber has a fineness of 7.8 dtex and a staple length of 64 mm. The shrinkage change is 41°/. . (Production Example 12 of Halogen-Containing Fiber) A copolymer containing 51% of acrylonitrile, 48% of ethylene dimerate, and 1% of sodium p-styrenesulfonate was dissolved in acetone so as to have a resin concentration of 30%. 1 part by mass of the resin of the obtained resin solution, zinc oxide (three types of zinc oxide jis) as a metal compound (2-1) and a metal compound (2-2) were added in an amount shown in the following Table 2. Antimony trioxide is made into a spinning dope. Using a nozzle having a nozzle aperture of 〇.〇6 mm and a number of holes of 1 boring, the spinning dope was extruded into a 30% acetone aqueous solution and solidified while extending at a magnification of 3·3 times. Perform one extension, dry after washing at 12 ° C. 'Secondary extension at 1.3 times extension at 140 ° C, and then heat the water vapor (saturated water vapor) at 17 ° C to 0.85. The tempering magnification was subjected to a ten-second intense heat treatment, and further cut, thereby obtaining a halogen-containing fiber. The obtained fiber system had a fineness of 丨·7 dtex and a short fiber of 64 mm in length had a shrinkage variation of 59%. (Production Example 13 of the element-containing fiber) The copolymer containing 51% of acrylonitrile, 48% of ethylene dimerate, and sodium p-styrenesulfonate was dissolved in acetone so as to have a resin concentration of 30%, relative to the obtained resin. 1 part by mass of the resin of the solution, zinc oxide (three kinds of zinc oxide JIS) as a metal compound (2-1), and trioxide as a metal compound (2·2) were added as an addition amount shown in the following Table 2锑, made into a spinning dope. Using a nozzle having a nozzle aperture of 0.14 mm and a number of holes of 1 boring, the spinning dope was extruded into a 30% aqueous acetone solution to solidify it, and a 152753.doc • 40-201134992 surface was 3.3. The stretching ratio is extended once, washed with water under i 2 〇艽, and then subjected to secondary stretching at a stretching ratio of 1.3 times at 140 ° C, and then heated under water vapor (saturated water vapor) at 17 Torr. The tensin-containing fiber was obtained by performing a ten-second intense heat treatment at a relaxation ratio of 0.85 times and further cutting. The obtained fiber had a fineness of 17 dte}i and a staple fiber length of 64 claws, and the shrinkage variation was 58%. (Production Example 14 of dentate-containing fibers) 51% of acrylonitrile, 48% of vinylidene chloride, and 1 of sodium p-styrenesulfonate were contained. The copolymer of the oxime is dissolved in acetone so that the resin concentration is 3% by weight, and is added as the metal compound (2-2) in an amount of addition shown in Table 2 below with respect to 100 parts by mass of the resin of the obtained resin solution. Antimony trioxide is made into a spinning dope. Using a nozzle having a nozzle aperture of 〇.1〇mm and a number of holes of 1000 holes, the spinning dope was broadcasted to a 30 〇/〇 acetone aqueous solution and solidified while performing an extension at a stretching ratio of 3.3 times. After washing with water, it was dried at 12 (TC), and then subjected to secondary stretching at a stretching ratio of 1.3 times at 140 ° C. After heating at a temperature of 17 ° C in saturated steam (saturated water vapor), a relaxation ratio of 0.8 times was used. After 20 seconds of intense heat treatment and further cutting, a halogen-containing fiber was obtained, and the obtained fiber had a fineness of 76 dtex and a short length of 64 mm. The shrinkage of the obtained fiber was cut during the measurement. It is impossible to measure. (Production Example 15 of the element containing fiber) The copolymer containing 51% of acrylonitrile, 48% of vinylidene chloride, and 1% of sodium p-styrenesulfonate was dissolved in such a manner that the resin concentration became 30%. In acetone, 1 part by mass of the resin of the obtained resin solution was added as 252753.doc -41 - 201134992 as shown in the following Table 2, and zinc oxide (zinc oxide jis ^ as a metal compound (2_1}) was added. Species) as a metal compound (2-2) Strontium trioxide is used to make a spinning dope. The spinning dope is extruded into a 3〇〇/0 acetone aqueous solution using a nozzle having a nozzle diameter of 010 mm and a number of holes of 1 boring, and is solidified while being solidified. The mixture was extended once at a stretching ratio of 5.9 times, washed with water at 120 ° C, and then subjected to dry heat stress treatment at a relaxation ratio of 0.85 times at 170 ° C for 2 minutes, and further cut, thereby obtaining The fiber obtained has a fiber denier of 7.8 dtex and a short fiber length of 64 mm, and the shrinkage variation is 67%. (Production Example 16 containing dentate fiber) 57% of acrylonitrile-containing ethylene oxide The copolymer of 4% by weight and 3% of allyl sulfonate was dissolved in dimethyl decylamine in such a manner that the resin concentration became 245%, and 1 part by mass of the resin of the obtained resin solution, as shown in the following table 2 Addition amount, adding antimony trioxide as the metal compound (2_2) to prepare a spinning dope. Using a nozzle having a nozzle aperture of 0.06 mm and a number of holes of 100,000, the spinning dope is extruded to 55%. In the aqueous solution of dimethyl hydrazine, one side is solidified, and one side is 5 6 times extension ratio, one extension, water washing, drying at 13 ° C, and further heat treatment at 115 ° C in a damp heat-pressurized vapor (saturated water vapor) at a relaxation ratio of 0 85 times for 15 minutes. Further, the yarn was cut to obtain a fiber containing γ. The obtained fiber had a fineness of 1.9 dtex and a short fiber having a length of 38 mm, and the shrinkage variation was 68%. (Production Example j of a halogen-containing fiber) Acetonitrile 57%, diethylene oxide 41% and allyl sulfonate 2〇/〇152753.doc •42· 201134992 /, the polymer is dissolved in the dimercapto by the resin concentration of 25% In the amine, with respect to 100 parts by mass of the resin of the obtained resin solution, zinc p-toluate as a metal compound (2·丨) and ruthenium pentoxide as a metal compound (2_2) are added as shown in Table 2 below. , made into a spinning dope. Using a nozzle having a nozzle aperture of 0.06 mm and a number of holes of 1 boring, the spinning dope was extruded into a 55% aqueous solution of dimethylguanamine to solidify it, and the surface was 5.6 times. The stretching ratio is extended once, and after washing with water, it is dried at 12 (TC, and then in a moist heat-pressurized vapor (saturated water vapor) 125 lt;), and the tempering ratio is 0.85 times in a state of no tension for 2 minutes. The relaxation treatment was further carried out to obtain a halogen-containing fiber. The obtained fiber had a fineness of 丨.7 dtex 'short fiber having a cut length of 64 mm, and the shrinkage variation was 85%. (Manufacturing Example 18 of a halogen-containing fiber) The copolymer containing 50% of acrylonitrile, 49% of ethylene, and 苯乙烯5〇/〇 of styrenesulfonate was dissolved in acetone so as to have a resin concentration of 30%, and 100 parts by mass or less of the resin of the obtained resin solution. Addition of 堇' added as a metal compound (2-1), zinc stannate, and polyglycidyl methacrylate containing an epoxy group (weight average molecular weight: 40,000) Raw liquid. Also, in the above spinning original "TINUVIN1577FF" (2-(4,6-diphenyl-1,3,5-tris-2-yl)), manufactured by Ciba Specialty Chemicals Co., Ltd., was added to the liquid, and the nozzle aperture was 〇. .1 nozzle with 12 pupils, the spinning dope is extruded into a 25% acetone aqueous solution, and is solidified while stretching once at a stretching ratio of 2.18 times. After washing, U5<;>c proceeded to 152753.doc •43·201134992, and dried at 145 ° C, then extended twice at a stretching ratio of 2.75 times 'and further at 170. (:, at a relaxation ratio of 0.92 times After 3 minutes of dry heat and heat treatment, and further cutting, the fiber containing the fiber was obtained. The obtained fiber has a fineness of 2.2 dtex and a short fiber length of 51 mm, and the shrinkage variation was 160% » (containing halogen fiber) Production Example 19) A copolymer comprising 52% of acrylonitrile, 46.8% of ethylene glycol and 1.2% of sodium styrene was dissolved in C-propane in a manner to have a resin concentration of 30%, relative to the obtained resin solution. 100 parts by mass of the resin, added as a metal in the amount shown in Table 2 below The zinc hydroxystannate of the compound (2-1) and the antimony trioxide of the metal compound (2-2) are used as a spinning dope. A nozzle having a nozzle aperture of 〇.〇8 mm and a number of holes of 15,000 holes is used. The spinning dope was extruded into a 38% aqueous acetone solution and solidified while being stretched once at a stretching ratio of 22 MPa. After washing with water, it was dried at 12 Torr and then at 15 ° C. The stretching was carried out at a stretching ratio of 3.0 times, and further, a dry heat treatment at a relaxation ratio of 0.80 times at a relaxation ratio of 0.80 times was carried out at 17 ° C to further perform cutting, thereby obtaining a fiber containing γ. The resulting fiber had a fineness of 3 dtex and a short fiber length of 38 mm and a shrinkage change of 73%. (Production Example 2 of Halogen-Containing Fiber) A copolymer containing 52% of acrylonitrile, 47% of ethylene diethylene oxide, and 1% of sodium methyldithioacetate was dissolved in dimethyl group at a resin concentration of 25%. In the formamide, the amount of the resin ruthenium of the obtained resin solution was added as the metal compound (η) in the amount of addition shown in Table 2 below, and 152753.doc 201134992 was used as the metal compound (2-2). ) pentoxide, made into a spinning dope, using a nozzle having a nozzle aperture of 0.07 mm and a number of holes of 30,000 holes. The spinning dope is extruded into a 50% aqueous solution of dimethylformamide to solidify it. One side was stretched at a stretching ratio of 8.0 times, washed with water at i3 (drying under rc), and then in a damp heat-pressurized vapor (saturated water vapor) at 120 〇C, and the relaxation ratio was 0.8 times in a state of no tension. The yarn was subjected to a relaxation treatment for 15 minutes to carry out cutting, thereby obtaining a fiber containing γ. The obtained fiber had a fineness of 7.8 dtex and a short fiber having a length of 64 mm, and the shrinkage variation was 72%. Production Example 21) Acrylonitrile was contained. The copolymer of 48% of gaseous ethylene and 2% of sodium decylallylsulfonate was dissolved in acetone so that the resin concentration became 30%, and the raw material of the spinning and bismuth was prepared. The nozzle aperture was 〇min and the number of holes was 30,000. The nozzle of the hole, the spinning dope was extruded into a 30% aqueous acetone solution, and the solidified surface was stretched once at a stretching ratio of 3.3 times, washed with water and dried at 135 ° C, and then at 145 ° > (:, the second extension is carried out at a stretching ratio of 2 to 49 times, and further, i5 minutes of relaxation is performed in a state where the relaxation ratio becomes 〇·7 times in a state of no tension in the wet heat-pressurized vapor (saturated water vapor) U5t. After the treatment and the relaxation treatment, it is dried for 1 minute in the crucible 5, and then stretched until the crimping is eliminated, and further cut, thereby obtaining the fiber containing the cellulose. The obtained fiber has a fineness of 7 8 I, cut into short fibers of 64 claws. The shrinkage fluctuation of the obtained fiber was not measured because it was cut at the time of measurement. (Production Example 22 containing _-fibers) 152753.doc •45- 201134992 Contains 51% acrylonitrile, 48% ethylene oxide and para-benzene The copolymer of 1% of sodium sulfonate was dissolved in acetone so that the resin concentration was 3% by weight, and 100 parts by mass of the resin of the obtained resin solution was added as a metal compound (2d) in an amount shown in Table 2 below. Zinc oxide (3 kinds of zinc oxide Jls) and antimony trioxide as the metal compound (2-2) are used as a spinning dope. The nozzle aperture is 〇·1〇mm and the number of holes is 1 boring. The nozzle was extruded into a 30 〇/〇 acetone aqueous solution and solidified while being stretched once at a stretching ratio of 3.3 times. After washing with water, it was dried to '140. (: After the second extension was carried out at a stretching ratio of 1.3 times, the dry heat-strength heat treatment was performed at a relaxation ratio of 0.85 times at 170 C for 2 minutes, and further cutting was performed, whereby the fibers containing the teeth were obtained. The short fiber with a fineness of 7.8 dtex and a length of 64 mm is cut, and the shrinkage variation is 70%. The shrinkage variation of the 'followed fiber' is measured as follows. (Method for measuring fiber shrinkage) The halogen-containing fiber produced in the example is 3333 dtex (after a taxi), using about 5 mm, using tma (thermal stress strain measuring device [manufactured by Seiko Instrument Co., Ltd., trade name ^ TMA/SS150C"], using gas: Nitrogen, gas flow rate: 3 〇 L / min 'heating rate: 2 〇 eC / min 'load 18 mN) is measured. If the initial sample length is set to X ' and the sample length at any temperature is set to γ, then the fiber The shrinkage ratio is represented by the following formula: The so-called functional fiber of the present invention has a temperature of from 50 〇 c to 3 〇〇 ° c under a load of 0.0054 mN/dtex, and is not cut and remains. 〇〇〇54 mN/dtex load When the temperature 152753.doc -46·201134992 degrees is increased from 50 ° C to 300 ° C ' while the fiber shrinkage ratio (also referred to as shrinkage ratio in the present specification) is measured by the above measurement method, the present invention contains The dentate fiber is not cut and remains: Fiber shrinkage ratio (°/.) = 1 00 - [(100 χΥ) / Χ]. (Method for calculating shrinkage fluctuation) The temperature is increased from 50 ° C to 300. (: The change in shrinkage at the time refers to the difference between the highest point (α%) and the lowest point (p%) of the fiber shrinkage rate in the temperature range of 5 (rc to 3 〇〇〇c) in the measurement of the fiber shrinkage rate. In the measurement of the shrinkage ratio of the fiber, the shrinkage variation is set to be infinite when the fiber is cut. One of the manufacturing examples 1 to 22 - female it # position, east, T of the person extension ratio, twice The spinning conditions such as the stretching ratio, the tempering ratio in the heat, and the total stretching ratio are also shown in the following Table 2, the extension ratio of the stretching extension H, the second extension ratio, and the relaxation ratio at the time of treatment. Value. 152753.doc -47. 201134992

(N 152753.doc S 塄00 ... mv〇s § 〇s <N »〇s V) Os V) 00 »〇5 00 v〇<n 00 P cs 〇卜墀S» ^ m rn ο W- ϊ ΓΛ om ro dmm 〇cn 〇CN mmo <N <N CN mmd cn ΡΊ d cn cn o CN W"1 (Ν fn ο in •«μ ^Τί ψ-^ (NW 峨揉temperature CC) ο 〇 Ooo 〇VMM oo (N 00 οο ooo 〇iT) CS ο VH ο 〇 s sg sg sg sg sm sg sg sg ϊ§ ϊ§ 狳铋红铋铋铋丝躲躲揉 · m 戚4i 癍揉揉- 戚4ί戚戚4ί 戚戚 暌 暌 eat mm 45? 佑mm 瘐m 佑 total extension ratio (times) \Τ) rn rn v〇— κη v〇rn Ό ΓΛ KTi v〇ΓΊ yn 〇r^ Μ-) VD r^i VO CO κη v〇ΓΛ vo ΓΛ ο cn Ό rn yn v〇rn cn S uS ^D — ν〇甘· <N i〇... η ο vd JO in ^> 热处理 Heat treatment relaxation ratio (times) 00 00 in 00 00 u-> 00 00 w-> 00 wo 00 00 00 οο 00 in 00 00 in oo 00 »0 00 (Ν On 〇〇00 卜 tn 00 ddo ο oo ο ο ο 〇〇 〇 - - - - 2 2 2 2 2 ρ 〇cn ο 寸 (N ΓΛ jn ro 1 time extension ratio (double) ro CO VO CO cn m ΓΛ m co m rn m rn cn ΓΛ ro mm cn CO CO m an Os VO ν〇... <N <Ν ο 00 m rn cn rn /*—S (Ν -3⁄4 〇H U"> o inch V) a 〇1 <η »r> yn Ο »-^ 1 Ο 1 <n 's-✓ 娥璜璜璜璜璜珑璜缋丄) *τ· -O Λ2 λΟ jJ jJ A3 jJ *τ- λ3 A3 JJ aJ a) 〇J XJ JJ irf jJ *t- <0 iisf J3 Η| 'Ί >Ί ,丨1 >Ί »1 ,丨1 >Ί '丨i , 'i 'Ί ,丨1 ,丨1 Η >Ί Η u| /—N φΐ ^ CN 〇s ο -3⁄4 φ! (N (N 〇<N (N CN 〇ov^ CS <N (Ν <Ν CN CN ο 1 T·^ ra 1 <N '·-^ *4〇/-S Compound name 竑 p-toluene sulfonate zinc dare to bully 4 竑 曱 曱 曱 j j j j j Jj 03 A3 JJ JJ JJ JJ JJ 03 1 1 5| 璨jD 1 -L) • x- « f iSif one iiSif two 4〇9 4 armored · by <n W"» in i〇^Τ) r^m yn mi〇in »〇(S vi (N age Vt *— <N m yn ^O 00 00 Ο (N m inch v 〇 00 ON < N CS · 48· 201134992 (single fiber strength) According to JIS L 10 1 5, the above manufacturing example 1, 丨丨, 1, 5, 16, 18 to 2 1 The fiber strength of the dentate fiber and Protex-M. The results are shown in Table 3 below. [Table 3] Halogen-containing fiber Production Example 1 11 15 16 18 19 20 21 Protex-M Single fiber strength (cN/dtex) 0.97 0.92 1.4 1.65 2.01 1.95 2.2 3 2.1 (Examples 1 to 15, 17 to 33) The fibers shown are mixed so as to have a predetermined mixing ratio as shown in the following Table 4, and after being opened by carding, a heat-bonded nonwoven fabric having a predetermined basis weight is produced by a usual heat-dissolving method. The halogen-containing fibers of Examples 1 to 13 are used as halogen-containing fibers, and the general-purpose fiber-reinforced fiber, that is, the product name "Tet〇ron" manufactured by Toray Co., Ltd. (denier 6 dtex, cutting length 51 mm, LOI value) is used. 21, hereinafter also referred to as reg.PET), and the hot-melt polyester fiber, manufactured by TORAY, under the trade name "Safmet" (denier of 4.4 dtex, cutting length of 51 mm, melting point of 110 °C) The LOI value is 20, and the following is sometimes referred to as meh PET. As the polyester fiber, the regenerated cellulose fiber containing the bismuth component, the product name "FR Corona" manufactured by Daiwabo Rayon Co., Ltd. (denier of 2.2 dtex, the cutting length is 5 1 mm, the LOI value is 25, and the content of the lanthanum element is 14% by mass. The following is also known as FR screw), a regenerated cellulose fiber containing a scale-based flame retardant, which is manufactured by Lenzing, under the trade name "Lenzing FR" (denier of 2.2 dtex 'cut length 51 mm, LOI value of 28), Jones Fiber 152753.doc • 49- 201134992

After the coating of the right chowder at the product, the processing of the flame retardant cellulose fiber after the processing of the flame retardant is processed (the fineness is 3 3 ^ Λ d u dtex, the cutting length is 64 mm, [〇1 value is 33) And Dupont Company manufactures Xi Long. "Appropriate quotient. The name "Nomex" (denier of 2.2 dtex, cut length of 50 mm, and bit dryness *a value of 30) is used as a flame retardant fiber other than halogen-containing fibers. (Example 16) A halogen-containing fiber produced by the above-described production method shown in the above-mentioned Production Example 1 was used as a general flat for the polyester fiber, and the ground B was made of __ GM S-fiber, Toray (T 〇RAY) The product name "Tetoron" manufactured by the company and the hard-to-scrape fiber TM purple other than the functional fiber are mixed in such a manner as to be the predetermined mixing ratio shown in Table 4 below. After that, the needle-punched non-woven fabric of the pre-twisted unit weight is produced by the usual acupuncture method. (Comparative Examples 1, 2, 4 to 20) The following fibers were mixed so as to have a predetermined mixing ratio as shown in the following Table 5, and after being opened by carding, they were produced by a usual hot melt method. A predetermined heat-bonding non-woven fabric per unit area weight. The halogen-containing fiber of Production Example 1 I4 to 22 and the trade name "IWex-M" (having a fineness of 2.2 dtex and a cut length of Μ _) manufactured by Kaneka Co., Ltd. were used as the dentate-containing fiber, and a general-purpose polyester fiber was used. The product name "Tet〇ron" manufactured by Toray (T〇Ray) Co., Ltd., and the hot-melt polyglycol fiber, the product name "Safmet" manufactured by Toray Co., Ltd., is used as a polyester fiber, and FR screw is used. It is a flame retardant fiber other than the fiber containing the element. (Comparative Example 3) After 100% by mass of iFR was opened by carding, a needle-punched nonwoven fabric having a basis weight of a predetermined amount was prepared by a conventional needle 152753.doc 201134992. Using the nonwoven fabrics of the examples and the comparative examples, the test bodies described below were produced, and the flammability was § f, and the results are shown in Tables 4 and 5 below. <Production Method of Mini Mattress Type Test Body> The structure of the mattress type test body is shown in Figs. First, use nylon, "糸" with a gap of 2 〇cm, two sheets of 45 cm long, 60 cm horizontal, 1.9 cm thick, and a density of 22 kg/m3 of polyurethane foam (Toyo Rubber) Produced by Industry, type 36〇s), polyurethane 45 cm, 60 cm horizontal, thickness i, 27 cm, density 22 kg/m3 polyurethane foam 2 (manufactured by Toyo Rubber Industry Co., Ltd. , type 360S) '1 piece of the non-woven fabric 3 of the embodiment or the comparative example, and the crepe sheet as the outer surface material 4 of the polyester/polypropylene woven fabric (weight per unit area ι 2 〇 g / m 2 ) quilted into the figure For the structure which is superimposed, a plate portion 6 as shown in Fig. 1B is produced. Then, a nylon yarn 5 is used, and the above-mentioned non-woven fabric 3 and 1 are used as the outer surface material 4 of the outer polyester 4 at a quilting interval of 5 em. A polypropylene woven fabric (having a weight per unit area of 120 g/m2) was quilted into a structure as shown in Fig. 2, and a length of 22 cm and a width 212 edge portion 7 as shown in Fig. 2B were produced. 5 'The polyester/polypropylene woven fabric of the surface material 4 of the outer layer is made of 3 pieces of the above non-woven fabrics at a quilting interval of 2 〇 cm. The weight of the surface area is 120 g/m2) quilted into a structure as shown in Fig. 2A. A bottom portion 8 of 45 cm in length and 60 cm in width as shown in Fig. 2C is produced. Further, '45 cm in length and 60 cm in width, The coil spring 16 with a height of 20 cm is equipped with two polyurethane foams of 45 cm in length, 60 cm in width, 1.27 cm in thickness and 22 kg/m3 in density (Manufactured by Toyo Rubber Industry Co., Ltd., 152753.doc) 201134992

In the manner of the belt (the weight per unit area is 2〇〇g/m2, the edge portion 7 is placed, and the bottom portion 10 is disposed on the bottom surface and sewn to be along the spiral pattern 3, and the width of the seam is made of polypropylene 36 Mm) 9 with a mini mattress shown in the 1st, 4th. <Manufacturing Method of Large Mattress Type Test Body> The plate portion 6 and the edge portion 7, the edge portion 7 and the bottom portion 8 are sewn together, and the structure of the large mattress type test body is shown in Figs. 5 to 8 as shown in the figure. . First, use nylon wire 5 to foam 2 pieces of 190 cm long and 97 kg/m3 of polyurethane at intervals of 20 cm, cm, 1.27 cm thick and 22 kg/m3. Body ll (T〇y〇Rubber Industry Co., Ltd., type 36〇s),

The structure is stacked as shown in Fig. 5A, and the plate portion 12 as shown in Fig. 5B is produced. Then, a nylon/polypropylene woven fabric (unit weight: 120 g/m2) of the surface material 4 of the outer layer was used as the outer layer of the nonwoven fabric 3 at a gap of 5 cm. The structure overlapped as shown in Fig. 6A, and the edge portion 13 having a length of 22 cm and a width of 576 cm as shown in Fig. 6B was produced. Then, using a nylon yarn 5' at a quilting interval of 20 cm, one piece of the above-mentioned non-woven fabric 3, 1 piece was used as the outer surface material 4 of the polyester/polypropylene woven fabric (weight per unit area: 120 g/m2). The structure was superposed as shown in Fig. 6A, and a bottom Η of 190 cm in length and 97 cm in width as shown in Fig. 6C was produced. Further, on a coil spring 17 of 19 cm in length, 97 cm in width, and 20 cm in height, a vinegar felt ls (unit weight) having a length of 19 cm, a width of 152753.doc -52 - 201134992 97 cm, and a thickness of 1 cm was placed. 12〇〇g/m2) 'The surface material 4 is provided on the upper surface, and the plate portion 12 is disposed on the upper surface thereof, and the edge portion 13 is disposed on the side surface, and the bottom portion 14 is disposed on the bottom surface, and the edge portion 13 is made of Kevlars 10 Sewing into a cylindrical shape along the side of the coil spring 17, as shown in Fig. 7, a side belt (a weight per unit area of 200 g/m2, a width of 40 mm) of 9 is used, and a Kevlar wire is used. The plate portion ^ and the edge portion 13, the edge portion 13 and the bottom portion 14 are sewn to form a large mattress as shown in FIG. (Inflammability evaluation method) &lt;Barrier back surface temperature at the time of burning false &&gt; A pearl having a thickness of 10 mm is prepared for a hole having a diameter of 55 mm and a hole having a diameter of 55 mm. The non-woven fabric of the example or the comparative example was prepared by fixing the four sides with a clip so that the non-woven fabric did not shrink when heated. The sample was vertically fixed, and the surface of the non-woven fabric of the example or the comparative example was from the β-type material to the level. In the direction of 42 mm, the American bed burning test method 16 (: 1^1633 bed side test τ type burner is used vertically. The combustion gas system uses propane gas at a gas pressure of ι 〇; kPa, the rolling body flow rate is Under the condition of 6 6 L/min, the flame is exposed for 9 seconds, and the non-contact infrared radiation thermometer (manufactured by Anritsu Meter Co., Ltd., the temperature of the flame side and the opposite side of the central portion of the non-woven fabric at this time (hereinafter, also The back surface temperature m obtained by the present measurement method is excellent in heat radiation resistance. The amine group A used for the mattress is usually formed in contact with the barrier fabric. Structure It is known that the thermal decomposition of the foam starts at about 220 to 300. (: At this time, 152753.doc • 53- 201134992 is released. The decomposition gas of the flammable gas is produced. Therefore, the urethane foam itself is inhibited. From the viewpoint of burning and suppressing the combustion of the mattress structure as a whole, it is more preferable that the temperature of the back surface of the barrier is low, that is, the temperature of the urethane foam which is in contact with the barrier is low, and it is more preferable that the temperature of the back surface of the barrier is lower than decomposition. In addition, the temperature at the back of the barrier is recorded by rounding off the maximum temperature. &lt;Mini mattress type test body evaluation method&gt; According to the United States bed burning test method 16 (: 1^1633 combustion test method) Implementation. If the method of burning the 16CFR1633 bed in the United States is simply described, the test method is as follows: a 1-shaped burner is placed horizontally from the upper surface of the bed to a vertical direction of 39 mm, and from the side The τ-shaped burner is placed vertically at a position of 42 mm in the horizontal direction, and the flame is started at the same time. The upper surface is flamed for 7 seconds, and the side is flamed for 5 sec. The combustion gas is made of a propane gas. In 1G1, the gas state of the upper surface is 12.9 L/min., and the gas flow of the burner on the side is 6·6 L/min. The evaluation of the flame retardancy is carried out as follows. : When the test is carried out by the above test method, the part which is exposed to the fire and which is exposed to the fire does not have cracks or holes. B grade combination #: When the same test is carried out, it is self-producing, but it is generated in the part exposed to the fire. C. No. 1 cm. Qualified for C grade: self-extinguishing when performing the same test, but cracking more than 1 cm in the part exposed to fire. ^Qualification of grade: Internal flammability when performing the same test The urethane is on fire, but it is extinguished immediately and eventually self-extinguishes. Failed: When the same test was carried out, the internal flammable amino phthalate was 152753.doc -54- 201134992 fire, mandatory fire extinguishing, suspension test. &lt;Evaluation of the area to be burned after 10 minutes of the plate portion of the mini mattress type test body&gt; According to the combustion test method of the bed test of the United States & 16 CFR 1633, the predetermined burner flame was performed for 70 seconds from the upper surface. A 50 second predetermined burner flame is applied from the side. The ratio of the area of the burned portion (the portion burned and carbonized) of the plate portion after the start of the test to the total area of the panel after 1 minute of the test is expressed as a percentage. The lower the value, the smaller the area to be burned, and the more excellent the fire extinguishing property and the flame retardancy. That is, when it is convenient to burn 1 〇〇% within 1 〇 minutes, it is also evaluated as 100. /〇. Further, when the internal flammable urethane was ignited and the fire was extinguished and the test was stopped, the evaluation was impossible. Furthermore, the area of the "expansion area" is recorded by rounding off one place. &lt;Total calorific value of 3 minutes of the large mattress type test body&gt; According to the combustion test method of the American bed burning test method 16CFR1633, a predetermined burner flame is applied for 70 seconds from the upper surface, and is implemented from the side. The 50 second predetermined burner is connected to the flame. At this time, the calorific value was measured by a cone calorimeter provided in the exhaust pipe, and the total calorific value after 30 minutes from the start of the test was calculated. When the value is low, it means that the calorific value, that is, the amount of the combustibles is small, and the flame retardancy is excellent. Furthermore, the 16CFR1633 eligibility standard does not exceed 15 MJ of total heat generation after 1 minute, and the maximum heating rate after 3 minutes has not exceeded 2 GG kW. In this evaluation, the test was aborted when the temperature exceeded 30 MJ within 3 G minutes. Furthermore, the total calorific value is recorded by rounding off the first place after the decimal point. 152753.doc •55- 201134992 [inch&lt;] m woven large mattress type test body Q w 璨〇〇 〇〇〇ο Cj (N 00 On 〇ο On m 〇Ο 〇ψ^· T—^ m 〇 Yn 00 00 〇〇 Mini Mattress Type Test Body Φν§ 53⁄4 § § S 〇〇§ g 〇S ο § S s % 〇§ % 〇§ S ο s SSS No evaluation&lt;&lt;&lt; 0D U υ Ο &lt ; &lt;&lt;&lt; UU &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt; 1 I 280 I ί 290 I 1 300 | I 330 1 ο 1 260 1 1 280 1 1 270 1 1 270 1 1 280 1 1 290 I 〇Os CS I 280 | 1 280 1 1 330 1 1 320 1 I 280 | 1 290 1 1 290 1 1 290 1 I 280 | 1 280 1 | 290 I 300 \ 300 1 270 1 260 1 320 I 350 I 280 I 270 雔 Unit weight! (g/m) 230 I 230 I 1 230 I 1 230 II 230 I 1 230 1 1 230 1 1_270 1 I 270 | 1 230 1 ο m &lt; N 1 230 1 1 230 I 〇 (N 〇1 230 1 1 230 1 1 230 1 〇 (N 1 230 1 〇 〇ΓΟ &lt;Ν I 230 | 1 230 1 〇1 230 I 1 230 1 1 230 1 I 230 | 1_230 1 230 1 〇〇μΛ &lt;3v U WW fiber type 鲅Uh 筚筚赜oi lx 鲅α; Uh 鲅鲅 鲅 tC tu cC 靼 ·UL· bi C *NS 1 Nomex | 鲅od ti- 鲅 i i i 鲅 鲅 鲅 鲅 鲅 鲅 鲅鲅οά 鲅Di U. 筚ct IX 鲅〇ί ti, paddle cd tu ex 鲅鲅鲅Pi (JU forged ot mass% »ri 〇m ίη Ό S 〇o 沄fe am «3 melt.PET |质量% 宕〇 1 Η UL) cu ώ mass % 宕o o 1 Ο 1 〇 halogen-containing weave quality % m υΊ 〇u~&gt; (N &lt;〇〇00 o 〇〇〇〇ο 〇〇〇〇〇〇〇〇〇 〇〇〇〇〇00 00 ^r\ 00 ΙΓ5 00 yr\ 00 00 00 κη 00 00 yn 00 V-) 00 m 00 00 〇〇00 00 V) 00 «η 00 vi 2 SS On ν*ϊ (N § V*&gt; ms ON l〇〇〇 Manufacturing example ψ-*· — *— »— — *—1 ·«· — &lt;N ΓΛ inch&lt;n 卜 Cn (N 〇r^· »·· ·—(N i (N m ¥ 1 vo 00 〇\ ο i marry SK CN 1 m 1 ► 1 1 ν〇i 卜 1 00 i province Os i |ϋ ¥ ¥- fS CN §; (N 13⁄4 00 (N 苳ON fS s®: 〇$ac : ϋκ (N co m 苳·56· 152753.doc 201134992 flammable large mattress type test body 30 minutes total calorific value (MJ) (N ( N over 30 over 30 over 30 over 30 over 30 over 30 over 30 over 30 (N over 30 over 30 1 over 30 over 30 over 30 over 30 over 30 over 30 over 30 over 30 mattress type test body « * Measurement 〇 Unable to measure Unable to measure Unable to measure Unable to measure 〇 Unable to measure Unable to measure 〇 Unable to measure Unable to measure Unable to measure Unable to measure Unable to measure Unable to measure Unable to measure Unable to measure Unable to measure Consolidated evaluation < Unqualified ^ &lt; | Unqualified | Unqualified | |Failed | |Failed | D Failed | Failed | &lt; |Failed | |Failed | Unqualified Unqualified Unqualified Unqualified Unqualified Unqualified 岔 "A Interesting B from m ^ 300 Measurement 360 410 380 380 330 330 350 340 320 330 350 380 330 340 330 370 370 330 Complex unit area weight (g/m2) 230 (N 230 j 270 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 $ € il Fiber type FR嫘萦1 FR嫘萦1 FR嫘萦| FR嫘萦| FR嫘萦FR嫘萦| FR嫘萦| | FR嫘萦| FR嫘萦FR嫘萦FR嫘萦FR嫘萦FR嫘萦FR嫘萦FR嫘萦FR嫘萦FR嫘萦FR嫘萦% by mass Ό 1 〇1 〇 polyester fiber melt.PET% by mass yn 〇1 〇reg.PET% by mass 1 1 1 〇1 〇 Halogen-containing fiber mass % 1 1 1 〇〇〇〇〇〇1 m 〇〇〇〇〇〇〇 shrinkage change (%) 1 1 1 00 yn 00 | Infinity | Infinity 00 00 1 00 00 V) 00 Unlimited Large (Ν Infinity 〇 Manufacturing Example 1 1 1 - 寸 VO ψ ψ -^ Protex-M 00 〇 \ Comparative Example 1 Comparative Example 2 Comparative Example 3 ! Comparative Example 4 | Comparative Example 5 1 Comparative Example 6 Comparative Example 7 Comparison Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 Comparative Example 14 Comparative Example 15 Comparative Example 16 Comparative Example 17 | Comparative Example 18 I Comparative Example 19 Comparative Example 20 -57- 152753.doc 201134992 From the above table The results of 4 and 5 show that the temperature is from 50 at a load of 0.0054 mN/dtex. (: In the combustion test of the mini-bed type test body containing the non-woven fabric of the embodiment of the predetermined configuration shown in Table 4, the shrinkage variation to 3 〇〇t is 65% or less, and 1 〇 After the minute, the area of the burnt surface was not met, and it was judged to be qualified. In addition, by suppressing the area of the burnt surface, it was compared with the shape of the smear-like non-woven fabric, and when the non-woven fabric was applied, the total calorific value of the large (four) type test body was 3 minutes. In the case of using FR rongrong as a flame retardant fiber other than the γ-containing fiber, and containing 3 to 10% by mass of the element-containing fiber, it is difficult to use the mini bed type test body. When the combustion test was carried out in the evaluation, the cracks or holes were not produced in the non-woven fabric, and it was qualified as the flame retardant fiber other than the dentate fiber, and the quality of the fiber containing the commercial fiber was 3 to 2 〇. In the case of %, the barrier back surface temperature (hereinafter referred to as the barrier back surface temperature) of the combustion assumption is lower than that of the comparative example, and the total calorific value of the large mattress type test body is also low for 3 minutes, so that it is good. Non-woven fabric The higher the content of the fiber, the lower the calcination area of the mini mattress type test body after 1 minute in the burning test, but the tendency of the test piece to be inferior in the evaluation of the flame retardancy is 'the content of the halogen-containing fiber is When it is 3 to 3 % by mass, it exhibits more excellent flame retardancy than the prior art. Further, from the comparison of Examples 3, 28 and 29, the load of the non-woven fabric containing the Nansu fiber at 0.0054 mN/dtex is known. The temperature is increased from 5〇.〇 to 300. The lower the shrinkage change at the time of the ,, the lower the temperature at the back of the barrier, and the lower the total calorific value of the large mattress type test body for 30 minutes, so the good 152753.doc • 58· 201134992. It is also clear from the comparison between Example 7 and Example 30 that it is difficult to ignite when the temperature changes from 50 〇 to 3 〇〇t when the temperature changes from 50 〇 to 3 〇〇t under the load of 0.0054 mN/dtex. The tendency of the evaluation results was good. Further, from the comparison between Example 8 and Comparative Example 5, it was found that when the temperature was changed from 50 ° C to 300 X at a load of 54 mN/dtex, the shrinkage variation was 41%. Even if the content of halogen-containing fibers contained in the non-woven fabric is super 3〇% by mass, the flame retardancy evaluation result is also good. On the other hand, from the results of Table 5, it can be clarified that the non-woven fabric does not contain the halogen-containing fiber Comparative Example 1 '3 and 11 in the mini mattress type test body burning test In the case where the non-woven fabric does not contain the γ-containing fiber, it is easy to be burned, and thus the flame retardancy is poor. Further, as in Comparative Example 2, only the polyester fiber is used. In the case of non-woven fabric, a carbonized film is not formed during combustion, so that the flame retardancy is poor. Further, as in the case of Comparative Example 3, when the nonwoven fabric is produced only by FR, in the combustion test of the mini mattress type test body, Within a few minutes, the area burned up to 1%.

Further, in the non-woven fabric under the load of 0.0054 mN/dtex, the temperature was changed from 50 ° C to 300 C, and the shrinkage variation exceeding 45% of the halogen-containing fibers exceeded 30% by mass of Comparative Examples 4 and 5 in the mini bed. In the burning test of the mat type test body, a hole was formed in the non-woven fabric during the test, and the internal flammable amino phthalate was ignited to extinguish the test, which was unsatisfactory. The reason for this is considered to be that since the content of the halogen-containing fibers in the nonwoven fabric is large, the shrinkage stress at the time of combustion cannot be sufficiently suppressed, or the amount of carbonized components at the time of combustion is insufficient. Moreover, the content of the polyester fiber in the non-woven fabric is not comparable to the quality. 152753.doc • 59· 201134992 Example 12 In the combustion test evaluation of the mini mattress type test body, the non-woven fabric is cracked during the burning test, and a hole is generated. The flammable amino phthalate ignited 'compulsory fire extinguishing and the test was terminated, so it was unqualified. The reason for this is presumed to be that the non-woven fabric has less polyester component which melts upon combustion and then acts. Further, in Comparative Example 13 in which the content of the polyester fiber in the nonwoven fabric exceeded 5 〇 mass 〇 / 于, in the combustion test evaluation of the mini mattress type test body, the nonwoven fabric was cracked during the combustion test, and voids were generated, and internal flammability was generated. The urethane fire was extinguished and forced to extinguish the fire and the test was terminated, so it was unqualified. The reason for this is considered to be that the amount of the carbonaceous component at the time of burning is insufficient because the amount of the polyester-based fiber in the nonwoven fabric is excessive. In addition, in Comparative Example 14 in which the content of the flame-retardant fiber other than the halogen-containing fiber in the nonwoven fabric was less than 30% by mass, in the combustion test evaluation of the mini mattress type test body, the nonwoven fabric was cracked during the burning test, and voids were generated and the inside was formed. The flammable amino phthalate ignited and forced to extinguish the fire and the test was terminated, so it was unqualified. The reason is considered to be that the flame retardant fiber other than the halogen-containing fiber in the nonwoven fabric is insufficient, and the amount of the carbonized component at the time of combustion is insufficient. The halogen-containing fiber contained in the nonwoven fabric has a temperature of 50 at a load of 0 0054 mN/dtex. (Comparative Examples 6, 7, 9, 10, and 20 in which the shrinkage variation at 300 ° C was increased to more than 65 ° C. In the combustion test of the mini mattress type test body, the nonwoven fabric was cracked during the burning test, and voids were generated. The internal flammable urethane fired 'compulsory fire extinguishing and stopped the test, so it was unqualified. Moreover, the halogen-containing fiber contained in the non-woven fabric will have a temperature from 50 at a load of 0.0054 mN/dtex. (: Increase to 300 In Comparative Example 8 in which the shrinkage variation at °C exceeded 65%, in the burning test of the mini mattress type test body, the product was 152753.doc -60·201134992 in less than 1 minute, and the product reached 100%. In any of 6 to i, the li-containing fiber in the non-woven fabric has a high shrinkage fluctuation, so that the structure of the non-woven fabric at the time of burning is weak, and the flame retardancy is poor. Further, in Comparative Example 9, an additional test was used. The halogen-containing fiber of Production Example 16 of the embodiment of the Japanese Patent Laid-Open No. Hei 6-287806. Further, when the temperature is increased from 5 至 to 300 ° C under an load of 0.0054 mN/dtex, the shrinkage variation is infinitely large. Protex_M" (made by Kaneka Co., Ltd.) as Comparative Example 15 of the halogen fiber In the combustion test evaluation of the mini mattress type test body, the non-woven fabric cracked during the burning test to generate a hole, and the internal flammable urethane was ignited, and the fire was extinguished to stop the test, so Qualified. It is considered that the reason is that pr〇tex_M increases the temperature from 50 ° C to 300 under the load of 0.0054 mN/dtex. (: When it is cut after shrinking, it is easy to produce voids in the non-woven fabric when the combustion test is performed. The addition test was carried out in Comparative Example 16. The halogen-containing fiber of Production Example 18 of the example of the present invention is disclosed in Japanese Patent Application Laid-Open No. 2004-197255. The Japanese Patent Application Publication No. 2004-197255 is a prior art related to the patent application filed by the present applicant. As can be seen from Table 2, the halogen-containing fiber of Production Example 18 increased the temperature from 5 ° C to 30 under a load of 0.0054 mN/dtex (the shrinkage variation at TC exceeded 65%. Therefore, the halogen containing the manufacturing example 18 was used. Comparative Example 16 of the fiber In the combustion test evaluation using the mini mattress type test body, a hole was formed in the nonwoven fabric during the combustion test, and the internal flammable amino phthalate was ignited to extinguish the fire. The test was tested and was therefore unsatisfactory. In Comparative Example 17, the halogen-containing fiber of Production Example 19 of the example of WO 01/32968 was additionally used. w〇01/32968 is related to the applicant's application 152753.doc • 6 201134992 The prior art related to the patent application. As can be seen from Table 2, the manufacturing example 19 has a shrinkage variation exceeding 65% when the temperature is raised from 50 ° C to 300 ° C under a load of 0.0054 mN/dtex. Therefore, in Comparative Example 17 using the halogen-containing fiber of Production Example 19, in the combustion test evaluation using the mini mattress type test body, cracks were generated in the nonwoven fabric during the combustion test, and fire was introduced from the crack. The internal flammable urethane was ignited, the fire was extinguished and the test was terminated, so it was unqualified. In the comparative example 18, the ii-containing fiber of Production Example 20 of the example of the Japanese Patent Laid-Open Publication No. 61-282420 was used. As is apparent from Table 2, the halogen-containing fiber of Production Example 20 exhibited a shrinkage variation of more than 65% from 5 〇 CI «c to 300 C under a load of 0.0054 mN/dtex. Therefore, in Comparative Example 18 using the halogen-containing fiber of Production Example 20, in the combustion test evaluation using the mini mattress type test body, voids were generated in the nonwoven fabric during the burning test, and the internal flammable urethane was ignited. In the case of the comparative example 19, the halogen-containing fiber of the production example 21 of the example of the Japanese Patent Laid-Open Publication No. SHO 53_186825 was used. Japanese Patent Laid-Open No. Sho 53-106825 is a prior art related to the patent application filed by the present applicant. As can be seen from Table 2, the shrinkage variation of the halogen-containing fiber of Production Example 2 under the load of 4. 〇 〇 $ 4 mN/dtex increased from 50 ° C to 3 〇 CTc exceeded 65%. Therefore, in Comparative Example 19 using the ?-containing fiber of Production Example 21, in the combustion test evaluation using the mini mattress type test body, a hole was formed in the nonwoven fabric during the burning test, and the internal flammable amine oleic acid vinegar was produced. Fired, forced to extinguish the fire and stopped the test, so it was unqualified. 152753.doc • 62· 201134992 [Brief Description of the Drawings] Fig. 1A is a side cross-sectional view of a plate portion of a mini bed type test body for evaluation of flame retardancy, and Fig. 1B is an overall view of the plate portion. Fig. 2 A is an edge portion and a bottom of a mini mattress type test body for evaluation of flame retardancy. A side cross-sectional view of the crucible, Fig. 2B is an overall view of the edge portion, and Fig. 2C is an overall view of the bottom portion. Fig. 3 is an explanatory view for explaining the assembly of a mini mattress type test body for evaluation of flame retardancy. Fig. 4 is an overall view of a mini mattress type test body for a flame retardant 5 parity. Fig. 5A is a side cross-sectional view of a plate portion of a large mattress type test body for evaluation of flame retardancy, and Fig. 5B is an overall view of the plate portion. Fig. 6A is a side sectional view showing the edge portion and the bottom cymbal of the large mattress type test body for evaluation of flame retardancy, Fig. 6B is an overall view of the edge portion, and Fig. 6C is an overall view of the bottom portion. Fig. 7 is an explanatory view for explaining the assembly of a large mattress type test body for evaluation of flame retardancy. Fig. 8 is an overall view of a large mattress type test body for evaluation of flame retardancy. Fig. 9 is a graph showing a shrinkage pattern of a fiber containing a fiber in an embodiment of the present invention. The figure shows a graph of the shrinkage pattern of the halogen-containing fiber of Comparative Example A. Figure U is a graph showing a shrink pattern of a halogen-containing fiber of a comparative example. Fig. 12 is a graph showing a shrinkage pattern of a dentate-containing fiber in the embodiment of the present invention. 152753.doc -63- 201134992 Figure 13 is a graph showing the shrinkage pattern of the γ-containing fiber in one of the embodiments of the present invention. Fig. 14 is a graph showing the shrinkage pattern of the element-containing fibers in the _眚&amp; + n embodiment of the present invention. Fig. 15 is a graph showing a shrinkage pattern of a dentate-containing fiber in a comparative example. [Description of main component symbols] 1 ' 2 &gt; 11 Polyurethane phthalate foam 3 Non-woven fabric 4 Surface material of outer layer 5 Nylon wire 6, 12 Plate part 7, 13 Edge part 8 &gt; 14 Bottom 9 Polypropylene Sewing side band 10 gram of fifteen 15 polyester felt 16 , 17 spiral spring 152753.doc 64·

Claims (1)

201134992 VII. Patent application scope: The body ' is characterized in that it contains a refractory fiber other than the dentate fiber and the dentate-containing fiber; and when the total amount of the aggregate is 100% by mass, the upper amount is 3 to 30 mass. /〇, the flame retardant fiber other than the i-containing fiber of the polyester fiber, the three-halogen fiber has a shrinkage fluctuation of 65% or less at a load of 0.0054 mN/dtex from 50C to 3〇〇. The above halogen-containing fiber comprises a polymer (1), and at least one metal compound (2) which promotes a denaturation reaction upon combustion of the above polymer (1) and a carbonization reaction upon combustion; and when the above polymer ( When the total amount of i) is 1% by mass, the above polymer (υ includes 30 to 70% by mass of acrylonitrile, halogen-containing vinylidene monomer, and/or 70% to 30% by mass of the monomer-containing vinyl monomer) And the unheated fiber aggregate of the above-mentioned dentate-containing fiber having a strength of 0.5 to 1.6 cN. /dtex 3. The flame-retardant fiber assembly of claim 1, wherein the dentate-containing fiber is increased in temperature from 50 ° C to 300 under a load of 0·0054 mN/dtex (::, not cut off) 4. Residue 4. The flame-retardant fiber assembly of claim 2, wherein the above-mentioned element-containing fiber is at 0.0054 The load of mN/dtex increases the temperature from 50 ° C to 300. (: When it is not cut off, it remains. 152753.doc 201134992 5. The flame-retardant fiber assembly according to any one of claims 1 to 4, The metal compound (2) contains a metal compound (2)) which promotes two reactions of the de-reaction and carbonization reaction, or a combination of the above-mentioned metal compound (5)) and a metal compound (2-2) which promotes a degumming reaction. The flame-retardant fiber assembly according to any one of claims 1 to 4, wherein the dentate-containing fiber is subjected to one-time stretching by extruding a spinning solution containing the polymer (1) and the metal compound (2) After washing with water, it is dried, subjected to secondary stretching, and subjected to heat treatment to be spun, and the stretching ratio at the time of the stretching is multiplied by the ratio of the fiber shrinkage at the time of the heat treatment, that is, the ratio of the relaxation is 5 times or less. 7. The flame-retardant fiber assembly according to any one of claims 1 to 4, wherein the dentate-containing fiber contains the above-mentioned metal compound (1) with respect to 1 〇〇 by mass of the polymer (1). ) 0.05 The non-flammable fiber assembly of claim 5, wherein the dentate fiber contains the metal compound Ρ-2) 5 to 30 parts by mass based on 100 parts by mass of the polymer (1). 9. The flame-retardant fiber assembly of claim 5, wherein the metal compound (2_D is selected from the group consisting of oxidized words, zinc carbonate, zinc sulfide, boric acid, tin stannate, tin oxide, oxidized erbium, tin oxide) At least one of a group consisting of copper oxide, copper silicate, indium trioxide, indium (tetra), and zinc p-toluene. The flame retardant fiber assembly of claim 5, wherein the metal compound (2-2) is selected from the group consisting of ruthenium compounds, iron oxide, iron phosphate, iron oxalate, sulfurization 152753.doc 201134992 iron, ruthenium oxide, trioxane (tetra) At least one of the group consisting of oxygen (four), and moth copper. 11. The flame-retardant fiber assembly according to claim 5, wherein the metal compound (7) comprises a metal compound (2_1) which promotes both the de-reaction and the carbonization reaction, or the metal compound (2·1) and promotes dehalogenation. A combination of metallization of the reaction (2-2). 12. The flame-retardant fiber assembly according to any one of claims 1 to 4, wherein the flame-retardant fiber other than the above-mentioned pixel-containing fiber is selected from the group consisting of an aromatic polyamide fiber, a benzoic acid fiber, and a polystyrene sulfide. Fiber, polyetheretherketone fiber, polyimine fiber, polyamidimide fiber, flame retardant polyester fiber, melamine fiber, acrylate fiber, polyphenylene oxide fiber, polyvinyl chloride fiber, polyethylene gas Ethylene fiber, polystyrene fiber, polytetrafluoroethylene fiber, regenerated cellulose fiber containing inorganic compound, regenerated cellulose fiber containing phosphorus-based flame retardant, processed flame retardant cellulose fiber after coating with flame retardant, oxidized acrylic acid At least one of a group consisting of fibers, carbon fibers, glass fibers, and activated carbon fibers. The flame-retardant fiber assembly according to claim 12, wherein the flame-retardant fiber other than the dentate-containing fiber is selected from the group consisting of regenerated cellulose fibers containing a bismuth component, regenerated cellulose fibers containing a refractory filler, and coated The fuel agent is then processed into at least one of a group consisting of a flame retardant cellulose fiber, a melamine fiber, a flame retardant polyester fiber, an acrylate fiber, and an aromatic polyamide fiber. 14. The flame-retardant fiber assembly according to claim π, wherein the flame-retardant fiber other than the above-mentioned element-containing fiber is selected from the group consisting of regenerated cellulose fiber containing diarrhea component, 152753.doc 201134992, containing a phosphorus-based flame retardant. At least one of a group consisting of regenerated cellulose fibers, a flame retardant-coated cellulose fiber, and an aromatic polyamide fiber coated with a flame retardant. A method for producing a flame-retardant fiber assembly, characterized in that the flame-retardant fiber assembly system comprises a tooth-containing fiber, a polyester fiber, and a flame-retardant fiber other than a halogen-containing fiber; When the total amount of the above-mentioned flame-retardant fiber aggregate is 1% by mass, 3 to 30% by mass of the halogen-containing fiber, 20 to 50% by mass of the polyester fiber, and 3〇 ～77 mass% of the flame retardant fibers other than the dentate fibers are mixed; and the shrinkage fluctuation of the halogen-containing fiber at a load of 0.0054 mN/dtex from 5 〇C to 300 °C is 65% or less The halogen-containing fiber is spun by a composition comprising at least one metal compound (2) comprising a polymer (1) and a carbonization reaction which promotes the refinement of the polymer (1) and (4) Thereafter, it is obtained by performing heat treatment; and when the total amount of the above polymer (1) is set to 1 〇〇 mass 〇 /. In the above, the polymer (1) contains 30 to 7 % by mass of acrylonitrile, a styrene-containing ethylene monomer, and/or a dentate-containing vinyl monomer of 7 〇 to 3 〇% by mass, and a mixed ethylene group. Is a monomer. ~1〇% by mass. The method for producing a flame-retardant fiber assembly according to claim 15, wherein the spinning of the dentate-containing fiber is carried out by extruding a spinning solution containing the polymer (1) and the metal compound (2) After performing one extension and water washing, drying, second stretching, and heat treatment are carried out, and the stretching ratio at the time of stretching is multiplied by the ratio of fiber shrinkage at the above heat treatment, that is, the relaxation ratio is obtained by the above-mentioned 152753.doc 201134992 The total stretch ratio is 5 times or less. 17. The method of producing a flame-retardant fiber assembly according to claim 15 or 16, wherein the heat treatment is dry heat of 140 ° C or more or 9 Torr.热处理 Heat treatment in the above moist heat. 8. The method for producing a flame-retardant fiber assembly according to the item 15 or 16, wherein the heat treatment is a dry heat of 180 ° C or more or a heat treatment of moist heat of 15 Torr or more. 19. The method for producing a flame-retardant fiber assembly according to claim 17, wherein the heat treatment is 90 to 15 (relaxation heat treatment in wet heat of TC. 20. 20. a flame-retardant fiber assembly such as Kiss 15 or 16) The manufacturing method, wherein the heat treatment is a relaxation heat treatment in a moist heat pressurized steam of 100 〇 C or more. 21. A fibrous product, characterized by comprising a flame-retardant fiber assembly according to any one of the claims 丨 to 丨々. The flame-retardant fiber assembly according to any one of claims 4 to 4, wherein the flame-retardant fiber other than the dentate-containing fiber is a fiber having a L〇I value of 25 or more. A flame-retardant fiber assembly, wherein the flame-retardant fiber other than the halogen-containing fiber has a fiber having an LOI value of 25 or more. The fiber product is characterized by comprising a flame-retardant fiber assembly as claimed or η. The method for producing a flame-retardant fiber assembly according to claim 15 or 16, wherein the flame-retardant fiber other than the above-mentioned element-containing fiber has a L0I value of 25 or more. 152753.doc 201134992 26. The flame retardant of claim 19 Fabric assembly The method wherein the flame-retardant fiber other than the halogen-containing fiber has a LOI value of 25 or more. 27. The method for producing a flame-retardant fiber assembly according to claim 20, wherein the flame-retardant fiber other than the halogen-containing fiber is Fibers with an LOI value of 25 or higher. 152753.doc