WO2010010639A1

WO2010010639A1 - Flame-retardant synthetic fiber, process for production of the same, flame-retarddant fiber composites and textile products

Info

Publication number: WO2010010639A1
Application number: PCT/JP2008/065832
Authority: WO
Inventors: 田中健; 羽木裕康; 戎敏明
Original assignee: 株式会社カネカ
Priority date: 2008-07-24
Filing date: 2008-09-03
Publication date: 2010-01-28

Abstract

The invention provides a flame-retardant synthetic fiber having high flame retardance and high flame barrier properties, a process for the production of the fiber, and flame-retardant fiber composites. A flame-retardant synthetic fiber which comprises 100 parts by mass of a polymer (1) comprising 30 to 70 parts by mass of acrylonitrile, 70 to 30 parts by mass of a halogen-containing vinylidene monomer, and 0 to 10 parts by mass of a vinyl monomer copolymerizable with both and at least one metal compound (2) capable of accelerating the dehalogenation and carbonization in the combustion of the polymer (1) and which exhibits a shrinkage variation of 45% or below as determined by raising the temperature from 50°C to 300°C under a load of 0.0054mN/dtex.

Description

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

The present invention expresses an extremely high degree of carbonization, shape retention, and self-extinguishing properties at the time of combustion, so that it can be suitably used for textile products that require high flame retardancy, such as bedding and furniture. The present invention relates to a flame retardant synthetic fiber having flame retardancy, a method for producing the same, and a flame retardant fiber composite.

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

In these upholstered products such as bedding and furniture, flammable materials such as cotton, polyester and urethane foam are often used for the interior and surface for comfort and design at the time of use. In order to ensure the flame retardancy, by using appropriate flame retardant materials in these products, it is necessary to have advanced flame retardancy that prevents the flame retardant materials from flaming for a long time. is important. In addition, the flame-retardant material needs to maintain the comfort and design of products such as bedding and furniture.

As this flame retardant material, various flame retardant fibers and flame retardants have been studied in the past as a flame retardant fiber material using fiber. This high flame retardant and demand for products such as bedding and furniture. Nothing has yet emerged that fully combines requirements such as comfort and design.

For example, there is a technique called so-called post-processing flame proofing that applies a flame retardant to cotton fabric, but there are problems such as uniform adhesion of the flame retardant, hardening of the fabric due to adhesion, detachment due to washing, and safety. It was.

In addition, since polyester fiber, which is an inexpensive material, melts when burned, when it is made only with polyester fiber, a hole is formed and the structure cannot be maintained, and it is used for the bedding and furniture described above. Cotton and urethane foam flared, and the performance was insufficient. Although there are flame retardant polyester fibers containing phosphorus atoms and the like, the behavior at the time of combustion was finally melted as described above, and the performance was insufficient.

In addition, the method of obtaining highly flame-retardant modacrylic fiber by adding antimony trioxide, antimony pentoxide, magnesium oxide, etc. to the spinning dope can provide flame retardancy, but has a shielding property against flame and heat. There was a problem that was not satisfactory. One of these performances, that is, flame retardancy and satisfying flame and heat barrier properties, is a crosslinked highly flame retardant acrylic fiber to which a polymer containing glycidyl methacrylate is added (patent) Document 1) When exposed to a strong flame such as a burner flame, the fiber itself may decompose and eventually pass through the flame.

Moreover, although there exists a highly flame-retardant modacrylic fiber added with a solid phase flame retardant represented by water glass or zinc oxide (Patent Document 2), these fibers are excellent in fire extinguishing performance and flame blocking performance. The carbonized film formed during combustion is hard, and depending on the type of furniture and bedding and the shape of the burning part, the shrinkage of the fiber is large, so stress is applied to the carbonized film during combustion, cracking occurs in the carbonized film, and a little In some cases, the carbonized film was perforated by a load of. As a means for solving this problem, a modacrylic fiber has been proposed in which zinc oxide and a condensed phosphate compound are added and the carbonization rate at the time of shrinkage is controlled so that cracks are hardly generated (Patent Document 3). When these fibers are used, there is a problem that a high degree of flame retardancy cannot be obtained with a plurality of and limited types of fibers and a more limited fiber mixture ratio.

Also, a manufacturing method for obtaining acrylic synthetic fibers having good heat shrinkage resistance by performing wet heat tension heat treatment has been proposed (Patent Document 4). However, the residual shrinkage stress cannot be removed sufficiently to apply heat treatment in a tension state, and the shrinkage can be suppressed at a relatively low temperature of 160 ° C., but it shrinks significantly at a high temperature of 200 ° C. or more like a flame. As a result, there existed a problem that a flame retardance was inferior. Further, since it is not considered at all to be mixed with other fibers necessary as a practical fiber product, it cannot be used as a practical flame retardant material.

A flame retardant fiber composite comprising a highly flame retardant halogen-containing fiber and a non-flame retardant fiber to which a large amount of a flame retardant is added (Patent Document 5), and an essentially flame-retardant fiber and a halogen-containing fiber A flame-retardant nonwoven fabric (Patent Document 6) having a bulky structure composed of, for example, has been proposed.

However, in these methods, the form before combustion such as a fabric or a woven fabric cannot be maintained at the time of combustion, and a desired flame retardancy, in particular, a flame shielding property cannot be ensured, and a plurality of limited types of fibers are further limited. If the fiber content is not high, high flame retardancy cannot be obtained, which may hinder the product design and manufacturing process. Generally, heat-resistant fibers and inherently flame-retardant fibers have the desired flame retardancy. Easy, but the fibers themselves are often hard and brittle, and handling is extremely difficult and costly. In addition, high flame retardancy cannot be obtained unless the fiber mixing ratio is limited, and in terms of product design and manufacturing. There is a problem in the process.

JP 2005-179876 A JP 2006-225805 A JP 2007-291570 A JP 58-156014 A JP 61-89339 A US Pat. No. 7,259,117

In order to solve the above-mentioned conventional problems, the present invention provides a flame retardant synthetic fiber that satisfies high flame retardancy and high flame shielding properties, a method for producing the same, a flame retardant fiber composite, and a fiber product.

The flame-retardant synthetic fiber of the present invention comprises 30 to 70 parts by mass of acrylonitrile, 70 to 30 parts by mass of a halogen-containing vinylidene monomer and / or a halogen-containing vinyl monomer, and a copolymer thereof with 100 parts by mass of the polymer. Polymer (1) containing 0 to 10 parts by mass of vinyl-based monomer, and at least one metal compound that promotes dehalogenation reaction during combustion and carbonization reaction during combustion of said polymer (1) (2), and the shrinkage variation when the temperature is increased from 50 ° C. to 300 ° C. under a load of 0.0054 mN / dtex is 45% or less.

The method for producing a flame-retardant synthetic fiber according to the present invention comprises 30 to 70 parts by mass of acrylonitrile, 70 to 30 parts by mass of a halogen-containing vinylidene monomer and / or a halogen-containing vinyl monomer, and 100 parts by mass of a polymer. A polymer (1) containing 0 to 10 parts by mass of a vinyl monomer copolymerizable with the polymer, and at least one kind of promoting the dehalogenation reaction during combustion and the carbonization reaction during combustion of the polymer (1) After spinning a composition containing the metal compound (2), the shrinkage variation when the temperature was raised from 50 ° C. to 300 ° C. under a load of 0.0054 mN / dtex was 45% or less. It is characterized by obtaining a certain flame-retardant synthetic fiber.

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

The fiber product of the present invention is characterized by containing the above-mentioned flame-retardant synthetic fiber.

According to the present invention, it is possible to obtain a textile product having high flame retardancy and high flame shielding properties.

FIG. 1 is an overall view showing the structure of a flame retardant evaluation specimen in one embodiment of the present invention. FIG. 2 is a side sectional view showing the structure of the flame retardant evaluation specimen of FIG. FIG. 3 is an overall view showing the structure of a flame retardant evaluation specimen in another example of the present invention. FIG. 4 is a side sectional view showing the structure of the flame retardant evaluation specimen of FIG. FIG. 5 is a graph showing the shrinkage behavior when the halogen-containing fiber obtained in Production Example 10 which is an example product of the present invention and the fiber of the comparative example product are heated. FIG. 6 is a graph showing a shrinkage pattern of the flame-retardant synthetic fiber in one example of the present invention. FIG. 7 is a graph showing the shrinkage pattern of the flame retardant synthetic fiber of the comparative example. FIG. 8 is a graph showing the shrinkage pattern of the flame retardant synthetic fiber of the comparative example. FIG. 9 is a graph showing a shrinkage pattern of a flame-retardant synthetic fiber in another example of the present invention. FIG. 10 is a graph showing a shrinkage pattern of a flame-retardant synthetic fiber in still another example of the present invention. FIG. 11 is a graph showing a shrinkage pattern of a flame-retardant synthetic fiber in still another example of the present invention. FIG. 12 is a graph showing the shrinkage pattern of the flame retardant synthetic fiber of the comparative example.

Explanation of symbols

1, 2, 6 Polyurethane foam 3 Non-woven fabric 4 Outer surface fabric 5 Nylon yarn

As a result of intensive studies to solve the above problems, the present inventors have promoted dehalogenation reaction and carbonization reaction on synthetic fibers containing acrylonitrile and halogen-containing vinylidene and / or halogen-containing vinyl monomer. Accommodating high flame retardance by containing a metal compound of various types and making the shrinkage variation less than 45% when the temperature is raised from 50 ° C to 300 ° C under a load of 0.0054mN / dtex. The present inventors have found that this can be done and have completed the present invention.

The polymer (1) of the present invention comprises 30 to 70 parts by mass of acrylonitrile, 70 to 30 parts by mass of a halogen-containing vinylidene monomer and / or halogen-containing vinyl monomer, and a copolymer thereof with 100 parts by mass of the polymer. Contains 0-10 parts by weight of possible vinylic monomers. In the polymer (1) of the present invention, “in 100 parts by mass of the polymer, 30 to 70 parts by mass of acrylonitrile, 70 to 30 parts by mass of the halogen-containing vinylidene monomer and / or halogen-containing vinyl monomer, and these The term “containing 0 to 10 parts by mass of a vinyl monomer copolymerizable with” means that 30 to 70% by mass of acrylonitrile, halogen-containing vinylidene monomer and / or halogen with respect to the total mass of the polymer (1). This means that it contains 70 to 30% by mass of the contained vinyl monomer and 0 to 10% by mass of the vinyl monomer copolymerizable therewith. When the acrylonitrile content is 30 to 70 parts by mass, heat resistance necessary for fiberization can be obtained and flame retardancy can be achieved. The acrylonitrile content is preferably 40 to 60 parts by mass, more preferably 40 to 46 parts by mass. When the acrylonitrile content is in the range of 40 to 60 parts by mass, the fiber is less colored.

In 100 parts by mass of such a polymer, 30 to 70 parts by mass of acrylonitrile, 70 to 30 parts by mass of a halogen-containing vinylidene monomer and / or a halogen-containing vinyl monomer, and a vinyl monomer copolymerizable therewith Examples of the polymer (1) containing 0 to 10 parts by mass include a copolymer of acrylonitrile and one or more halogen-containing vinylidene monomers such as acrylonitrile-vinylidene chloride and acrylonitrile-vinylidene chloride-vinylidene fluoride. A copolymer of at least one halogen-containing vinylidene monomer such as vinylidene chloride, vinylidene bromide, and vinylidene fluoride with acrylonitrile and a vinyl monomer copolymerizable therewith. It is not limited to. Further, one or more of the above copolymers may be appropriately mixed and used.

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

Specific examples of the polymer (1) containing 30 to 70 parts by mass of the acrylonitrile, 70 to 30 parts by mass of the halogen-containing vinylidene monomer, and 0 to 10 parts by mass of a vinyl monomer copolymerizable therewith For example, the following polymers may be mentioned.
(1) Copolymer containing 51 parts by weight of acrylonitrile, 48 parts by weight of vinylidene chloride and 1 part by weight of sodium styrenesulfonate (2) 43 parts by weight of acrylonitrile, 56.1 parts by weight of vinylidene chloride, 2-acrylamido-2-methyl Copolymer containing 0.9 part by weight of sodium propanesulfonate (3) 57 parts by weight of acrylonitrile, 41 parts by weight of vinylidene chloride, copolymer containing 2 parts by weight of sodium allyl sulfonate (4) 60 parts by weight of acrylonitrile, A copolymer containing 30 parts by weight of vinylidene chloride, 10 parts by weight of sodium 2-acrylamido-2-methylpropanesulfonate (5) 55 parts by weight of acrylonitrile, 43 parts by weight of vinylidene chloride, 2 parts by weight of sodium methallylsulfonate Copolymer (6) 69 parts by weight of acrylonitrile, salt A copolymer containing 16 parts by mass of vinylidene and 15 parts by mass of sodium 2-acrylamido-2-methylpropanesulfonate, and a copolymer containing 58 parts by mass of acrylonitrile and 42 parts by mass of vinylidene chloride in a mass ratio of 1/10. Mixed (59 parts by weight of acrylonitrile, 39.6 parts by weight of vinylidene chloride, 1.4 parts by weight of sodium 2-acrylamido-2-methylpropanesulfonate in the mixed system)
(7) A copolymer containing 56 parts by mass of acrylonitrile, 42 parts by mass of vinylidene chloride, and 2 parts by mass of sodium 2-acrylamido-2-methylpropanesulfonate.

The copolymer can be obtained by a known polymerization method. For example, the polymerization method includes bulk polymerization, suspension polymerization, emulsion polymerization, solution polymerization, and the like, and the polymerization form includes, but is not limited to, continuous, batch, and semi-batch. Among these, from an industrial point of view, emulsion polymerization and solution polymerization are preferable as polymerization methods, and continuous and semi-batch methods are preferable as polymerization forms.

The at least one metal compound (2) that promotes the dehalogenation reaction during combustion and the carbonization reaction during combustion of the polymer (1) of the present invention includes zinc oxide that promotes both the dehalogenation reaction and the carbonization reaction. , Zinc carbonate, zinc sulfide, zinc borate, zinc phosphate, zinc stannate, metastannic acid, tungsten oxide, zirconium oxide, tin oxide, copper oxide, copper phosphate, indium trioxide and barium titanate (2 -1) or an antimony compound that promotes a dehalogenation reaction with the metal compound (2-1), iron oxide, iron phosphate, iron oxalate, iron sulfide, metastannic acid, molybdenum oxide, bismuth trioxide, bismuth oxychloride A metal compound (2-2) selected from copper iodide can be used in combination.

The metal compound (2-1) promotes the dehalogenation reaction at the time of combustion of the polymer (1), promotes the production of a polyene that is a precursor of the carbonization reaction at the time of combustion, and further, a metal halogen produced by dehalogenation. It is believed that the chemical compound catalyzes the polyene structure to promote carbonization. As the metal compound (2-1), a compound that causes a dehalogenation reaction at 200 ° C. or lower is preferable from the viewpoint of the subsequent promotion of carbonization. In particular, at least one selected from zinc oxide, zinc stannate, zinc carbonate, and tin oxide is preferable.

The metal compound (2-1) may be used alone or in combination of one or more. Further, a polymer (1) selected from a metal compound (2-1) and an antimony compound, iron oxide, iron phosphate, iron oxalate, iron sulfide, molybdenum oxide, bismuth trioxide, bismuth oxychloride, and copper iodide. A metal compound (2-2) that promotes the dehalogenation reaction during combustion can also be used in combination. The metal compound (2-2) that promotes the dehalogenation reaction of the polymer (1) promotes the formation of a polyene that is a precursor of the carbonization reaction by promoting the dehalogenation reaction of the polymer (1). On the other hand, the single use of the metal compound (2-2) is not effective in the present invention because it does not have the ability to promote carbonization from the generated polyene structure.

As the metal compound (2-2), an antimony compound is particularly preferable. The antimony compound not only promotes the dehalogenation reaction during combustion of the polymer (1), but the antimony halide produced by dehalogenation becomes a gas in a wide temperature range during combustion, and this gas traps radicals. Works to suppress combustion, that is, exhibits fire extinguishing performance.

Examples of the antimony compounds include, but are not limited to, antimony oxide compounds such as antimony trioxide, antimony tetraoxide, and antimony pentoxide, inorganic antimony compounds such as antimonic acid and salts thereof, and antimony oxychloride. is not. These may be used in combination. Among these, antimony trioxide and antimony pentoxide are preferable from the viewpoints of performance and industrial availability.

The addition amount of the metal compound (2) is 30 to 70 parts by mass of acrylonitrile, 70 to 30 parts by mass of a halogen-containing vinylidene monomer and / or a halogen-containing vinyl monomer, and a vinyl monomer copolymerizable therewith. 0.05 to 50 parts by mass is preferable with respect to 100 parts by mass of the polymer (1) containing 0 to 10 parts by mass. About a lower limit, 0.1 mass part is more preferable, and 1 mass part is still more preferable. Moreover, about an upper limit, 40 mass parts is more preferable, and 30 mass parts is still more preferable. When the amount of the metal compound (2) used is 0.05 to 50 parts by mass, there is an effect of carbonizing the polymer at the time of combustion (carbonization effect), and the carbonization necessary for obtaining the desired high flame retardance performance. An effect can be obtained and a desired shrinkage rate can be obtained. In the preferred range, the above-mentioned effects are further increased.

The amount of the metal compound (2-1) added is 30 to 70 parts by mass of acrylonitrile, 70 to 30 parts by mass of a halogen-containing vinylidene monomer and / or a halogen-containing vinyl monomer, and a vinyl-based monomer copolymerizable therewith. 0.05 to 50 parts by mass is preferable with respect to 100 parts by mass of the polymer (1) containing 0 to 10 parts by mass of the monomer. About a lower limit, 0.1 mass part is more preferable, and 1 mass part is still more preferable. Moreover, about an upper limit, 40 mass parts is more preferable, and 30 mass parts is still more preferable. When the amount of the metal compound (2-1) used is 0.05 to 50 parts by mass, there is an effect of carbonizing the polymer at the time of combustion (carbonization effect), and the necessary carbonization to obtain the desired high flame resistance performance. An effect can be obtained and a desired shrinkage rate can be obtained. In the preferred range, the above-mentioned effects are further increased.

The addition amount of the metal compound (2-2) is 30 to 70 parts by mass of acrylonitrile, 70 to 30 parts by mass of a halogen-containing vinylidene monomer and / or a halogen-containing vinyl monomer, and a vinyl-based monomer copolymerizable therewith. 0 to 50 parts by weight, preferably 3 to 40 parts by weight, and more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the polymer (1) containing 0 to 10 parts by weight of the monomer. Even if it is 0 parts by mass, the desired flame retardant performance may be achieved, but since the self-extinguishing effect is small, it is 3 parts by mass or more when used for applications that require a higher level of self-extinguishing effect. It is preferable to add 40 parts by mass or less.

The average particle size of the metal compound (2) is preferably 3 μm or less, and more preferably 2 μm or less. When the average particle size of the metal compound (2) is 3 μm or less, troubles such as nozzle clogging in the production process of the fiber obtained by adding the metal compound component to the halogen-containing polymer, improvement of the fiber strength, From the viewpoint of dispersion of the metal compound component particles. Although the minimum in the average particle diameter of a metal compound (2) is not specifically limited, 0.01 micrometer or more is preferable from the point of handling property, and 0.05 micrometer or more is more preferable. Furthermore, the metal compound (2) may be subjected to chemical modification on the particle surface in order to improve blocking properties, or may be used in a state dispersed in water or an organic solvent. Here, the average particle diameter means a median diameter. As a method for measuring the median diameter, a light scattering method can be used.

The flame-retardant synthetic fiber of the present invention preferably further contains 0.1 to 20 parts by mass of an epoxy group-containing compound with respect to 100 parts by mass of the polymer (1). By including an epoxy group-containing compound, it is crosslinked by drying or heat treatment in the fiber production process, a polymer crosslinked structure is formed in the fiber, and fiber shrinkage can be further suppressed.

The epoxy group-containing compound may be a glycidyl ether type, a glycidyl amine type, a glycidyl ester type, a cyclic aliphatic type, or a copolymer containing these. Considering elution into the spinning bath and the number of reactive groups (epoxy groups) per unit weight, for example, polyglycidyl methacrylate (weight average molecular weight 3000 to 100,000) is preferably used as the glycidyl ester type.

The heat treatment of the present invention includes relaxation heat treatment and tension heat treatment. The relaxation heat treatment referred to in the present invention means that, for example, assuming that the heat treatment is applied when the yarn (fiber bundle) moves between the two rollers, the two rollers are identical under the temperature condition in which the fibers do not contract. This refers to heat treatment in the state of the yarn when moving between rollers when the rotation speed is set (constant length state), or in the state where the moving yarn is more slack (relaxed state). Even when the fiber contracts between the two rollers by heat treatment, if the tension applied to the fiber is at the same level as the above state, relaxation heat treatment is performed. The tension heat treatment referred to in the present invention is a state other than the state of the yarn in the relaxation heat treatment, for example, when the two rollers are moved at the same rotational speed under temperature conditions where the fibers do not contract. The heat treatment in the state (tensile state) where the tension applied to the fiber is larger than the yarn state (constant length state). Even when the fiber contracts between the two rollers by the heat treatment, if the tension applied to the fiber is at the same level as the above state, the tension heat treatment is performed. Even when no roller is used, if the heat treatment is in a tension state equivalent to the yarn state in the relaxation heat treatment, the heat treatment is a relaxation heat treatment, and if the heat treatment is in the tension state equivalent to the yarn state in the tension heat treatment, the tension is It becomes heat treatment.

As the heat treatment method for the flame-retardant synthetic fiber of the present invention, any of a general heat treatment method, a dry heat treatment method and a wet heat treatment method, is possible. Furthermore, examples of the wet heat treatment method include, but are not limited to, a heat steam treatment method and a wet heat pressure steam treatment method. The fiber state during the heat treatment may be either relaxed or tensioned. Here, the relaxed state includes a constant length state. These combinations include dry heat tension heat treatment, dry heat relaxation heat treatment, heated steam tension heat treatment, heated steam relaxation heat treatment, wet heat pressurized steam tension heat treatment, wet heat pressurized steam relaxation heat treatment, and dry heat. A relaxation heat treatment method, a heated steam relaxation heat treatment method, and a wet heat pressurized steam relaxation heat treatment method are preferred, and a dry heat relaxation heat treatment method and a wet heat pressurized steam relaxation heat treatment method are more preferred. Further, a heat treatment step may be formed by combining a plurality of these methods and fiber states.

In general, the heat treatment of the flame-retardant synthetic fiber can reduce the spinning residual shrinkage stress as the treatment temperature is higher. The heat necessary for heat transfer to the inside of the fiber even at a temperature lower than the softening temperature or decomposition temperature of the flame-retardant synthetic fiber enables sufficient heat treatment without coloring or strength reduction. The said heat processing can be performed by a continuous type or batch type process. In particular, when using a copolymer in which acrylonitrile exceeds 50 parts by mass, a heated steam treatment method and a wet heat pressurized steam treatment method are preferable, and when using a copolymer having acrylonitrile of 50 parts by mass or less, a dry heat treatment method, The wet heat pressurized steam treatment method is preferred. This is because all of them are less colored. In the case of the relaxation heat treatment, the heat treatment temperature is 120 to 200 ° C., preferably 140 to 180 ° C., more preferably 150 to 170 ° C. for the dry heat treatment method, and 80 to 160 ° C. for the wet heat pressurized steam treatment method. The temperature is preferably 90 to 150 ° C., more preferably 100 to 140 ° C., and 140 to 230 ° C., preferably 150 to 210 ° C., more preferably 160 to 190 ° C. in the case of the heat steam treatment method. In the case of the tension heat treatment, the dry heat treatment method is 180 to 260 ° C, preferably 180 to 240 ° C, and the wet heat pressure steam treatment method is 150 to 230 ° C, preferably 160 to 210 ° C. In the case of a treatment method, the temperature is 160 to 250 ° C, preferably 170 to 220 ° C. The upper limit of the heat treatment temperature is not particularly limited, but is 300 ° C., preferably 250 ° C., more preferably 220 ° C. from the viewpoint of coloring of the flame-retardant synthetic fiber and an industrial viewpoint.

In the present invention, the heat treatment is preferably a relaxation heat treatment, a dry heat tension heat treatment at 180 ° C. or higher, or a wet heat tension heat treatment at 150 ° C. or higher. A flame-retardant synthetic fiber having a shrinkage variation of 45% or less when the temperature is raised from 50 ° C. to 300 ° C. under a load of 0.0054 mN / dtex is easily obtained. As the heat treatment, a relaxation heat treatment is more preferable. The heat treatment referred to in the present invention refers to reducing or removing the spinning shrinkage stress by shrinking the fiber under heating.

In the present invention, after the spinning and before the heat treatment, the flame retardant synthetic fiber has a shrinkage variation of 45% or less when the temperature is increased from 50 ° C. to 300 ° C. under a load of 0.0054 mN / dtex. Stretching may be performed.

The shrinkage fluctuation when the temperature is raised from 50 ° C. to 300 ° C. means the difference between the highest point and the lowest point of the shrinkage rate in the temperature range of 50 ° C. to 300 ° C. For example, it is the difference indicated by the arrows in FIGS. Specifically, it is as follows.
1. For example, as shown in FIGS. 6 and 8, in the case of monotonous shrinkage as the temperature rises, the shrinkage variation = shrinkage rate at point c (ie 300 ° C.).
2. As shown in FIGS. 9 to 12, in the case of once expanding after contracting and contracting again, in FIG. 9, the contraction fluctuation = the contraction rate at the point c in FIG. Fluctuation = shrinkage rate at point b. In FIGS. 11 and 12, shrinkage fluctuation = shrinkage rate at point b−shrinkage rate at point b ′.
3. As shown in FIG. 7, when contracting monotonously after contracting, or extending and cutting in the middle, contraction fluctuation = shrinkage rate indicated by an arrow (shrinking fluctuation ∞ when extending and contracting).
4). Point a in the figure is the softening start point. Between points a and b, shrinkage due to stress relaxation, shrinkage due to dehalogenation, and “elongation” due to softening occur, but shrinkage prevails over elongation. From the point b onward, it becomes a competition of shrinkage due to dehalogenation, shrinkage due to carbonization (maintenance of shape), and “elongation” due to softening, but the following pattern is obtained.
(1) When carbonization ability is excellent, shrinkage (or shape maintenance) is superior to elongation, and a shrinkage pattern as shown in FIGS. 6 and 8 is obtained.
(2) When the carbonization ability is slightly inferior, the elongation is superior in the vicinity of the point b, but the carbonization is superior as the temperature rises and starts to contract again at a certain point (the point b ′ in the figure) (FIGS. 9, 10, 11, 12). .
(3) When there is no carbonization ability, after the point b, the elongation increases and the contraction pattern of FIG. 7 is obtained.
5). In the present invention, there are four shrinkage patterns of the flame-retardant synthetic fibers of the examples (FIGS. 6, 9, 10, and 11). In the present invention, the most preferable shrinkage pattern of the flame-retardant synthetic fiber of the example is FIG. 6, then FIG. 9, and then FIG. 10, FIG. The shrinkage due to stress relaxation and the shrinkage due to dehalogenation are small as shown in FIG. 6 and the carbonization ability is strong, and the most preferable shrinkage pattern is the monotonous shrinkage. However, as shown in FIGS. Inferior, even if stretched by softening before carbonization, the shrinkage pattern may be such that carbonization occurs again at a certain temperature or higher and shrinks (maintains the shape). However, the shrinkage rate at the point b ′ in the figure is more preferably 0% or more.
6). On the other hand, the contraction pattern of the fiber of the comparative example is shown in FIGS. In the shrinkage pattern of the fiber of the comparative example, FIG. 7 is not preferable because it will be stretched or cut when the temperature is raised. FIG. 8 shows excellent carbonization ability and monotonically shrinks with temperature, but the shrinkage due to stress relaxation (points a and b in the figure) is too large. Since it becomes above, it is not preferable. FIG. 12 shows the same shrinkage pattern as FIGS. 9 and 10, but is not preferable because the carbonization ability is weak, the elongation is excellent, and the shrinkage fluctuation (shrinkage rate at point b−shrinkage rate at point b ′) exceeds 45%.

The flame retardant synthetic fiber of the present invention may include other additives such as an antistatic agent, a thermal coloring inhibitor, a light resistance improver, a whiteness improver, a devitrification inhibitor, a colorant, and a flame retardant as necessary. May be included.

The flame-retardant synthetic fiber of the present invention comprises 30 to 70 parts by mass of acrylonitrile, 70 to 30 parts by mass of a halogen-containing vinylidene monomer and / or a halogen-containing vinyl monomer, and a copolymer thereof with 100 parts by mass of the polymer. A polymer containing 0 to 10 parts by mass of a vinyl-based monomer that can be used is produced by a known production method such as a wet spinning method, a dry spinning method, or a semi-dry semi-wet method. For example, in the wet spinning method, the above polymer is dissolved in a solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, acetone, rhodium salt aqueous solution, dimethyl sulfoxide, nitric acid aqueous solution, and then extruded into a coagulation bath through a nozzle. The product is obtained by coagulation with water, followed by washing with water, drying, stretching and heat treatment, and if necessary, crimping and cutting. The solvent is preferably N, N-dimethylformamide, N, N-dimethylacetamide, or acetone, and more preferably N, N-dimethylformamide or acetone because of industrial handling.

The flame-retardant synthetic fiber of the present invention may be a short fiber or a long fiber, and can be appropriately selected in the method of use. The fineness is appropriately selected depending on the use of the composite used and the fiber product, but is preferably 1 to 50 dtex, more preferably 1.5 to 30 dtex, and still more preferably 1.7 to 15 dtex. The cut length is appropriately selected depending on the use of the composite and the textile product. For example, a short-cut fiber (fiber length 0.1 to 5 mm), a short fiber (fiber length 38 to 128 mm), or a long fiber (filament) that is not cut at all can be mentioned. Among these, short fibers having a fiber length of about 38 to 76 mm are preferable. However, when combined with other fibers, the fineness of other fibers may be the same, and it may be thin or thick. The flame-retardant synthetic fiber of the present invention can be combined with other fibers, particularly polyester fibers.

The flame retardant mechanism in the flame retardant synthetic fiber of the present invention will be described.

(1) Metal compound (2-1) As the metal compound (2-1), for example, zinc oxide, zinc oxide is said to have a function of promoting the dehalogenation reaction of the flame-retardant synthetic fiber. . In addition, zinc halide produced by dehalogenation or dehydrohalogenation (in the case of chlorine, zinc chloride (ZnCl ₂ )) acts catalytically on the polyene structure to promote carbonization (the residue during combustion is a form-retaining component) In addition, it is thought to contribute to the triazine ring formation reaction of acrylonitrile (fibers shrink by cyclization). Such an effect is exhibited not only in zinc oxide but also in other zinc compounds, organic zinc compounds such as zinc carbamate and zinc octylate, or some metal oxides such as tin oxide and copper oxide. In addition, the carbide generated as a result of the carbonization and cyclization promoting action by the metal compound (2-1) is strong and allows the presence of a residue, particularly a residue retaining the fiber form. When a flame is applied to such a composite body such as a fabric or a nonwoven fabric using a fiber in which a residue remaining during heating, in particular, a residue retaining a fiber form remains, the flame can be blocked by the residue.

(2) About shrinkage fluctuation when the temperature is raised from 50 ° C. to 300 ° C. under a load of 0.0054 mN / dtex, 45% or less Generally, halogen-containing fibers are once shrunk during heating (combustion), and then Extensive behavior is shown. The shrinkage factors during heating (combustion) include: a. Shrinkage due to carbonization; b. There are two possible causes: shrinkage due to spinning residual stress. Of these, a. Shrinkage due to carbonization is caused by dehalogenation reaction from the copolymer and triazine ring formation of acrylonitrile. This is a chemical reaction derived from the copolymer composition, and it is difficult to suppress shrinkage due to this reaction. On the other hand, b. Shrinkage due to spinning residual shrinkage stress is due to residual strain applied to the fiber during solidification and drawing operations in the fiber manufacturing process, and the fiber manufacturing conditions, particularly the heat treatment conditions in the fiber manufacturing process, should be selected as appropriate. Can be suppressed. Examples of the heat treatment method include relaxation heat treatment, tension heat treatment at 150 ° C. or higher in wet heat, and tension heat treatment at 180 ° C. or higher in dry heat. Of these, relaxation heat treatment is preferred as a heat treatment method for sufficiently suppressing the spinning residual stress. By applying these heat treatments, the residual shrinkage stress in spinning can be suppressed, and the shrinkage fluctuation during heating (combustion), that is, when the temperature is raised from 50 ° C. to 300 ° C. under a load of 0.0054 mN / dtex. Shrinkage variation can be reduced to 45% or less. If the shrinkage variation when the temperature is raised from 50 ° C. to 300 ° C. under a load of 0.0054 mN / dtex is 45% or less, high flame retardancy and high flame shielding properties are exhibited. For example, in the combustion test 16CFR1633 in the United States, fiber shrinkage is suppressed during combustion, and there is a hole in the exposed part of the flame, a crack is generated due to distortion, and a flame enters from there to ignite the internal flammable structure. Therefore, it is preferable because it does not fail the test. Since the flame-retardant synthetic fiber of the present invention has a softening temperature and a dehalogenation start temperature (decomposition point) close to each other, the dehalogenation reaction occurs when the heat treatment temperature is raised, or the fiber is colored or given sufficient heat treatment. May be difficult. As a solution to this, there is a technique of lowering the softening point by lowering the acrylonitrile content of the flame-retardant synthetic fiber of the present invention, and according to this, the heat treatment temperature can be set to the decomposition temperature or lower. In addition, sufficient heat treatment can be performed even at a temperature equal to or lower than the softening point temperature under a pressurized moist heat condition.
In addition, if the range of shrinkage variation is 45% or less when the temperature is raised from 50 ° C. to 300 ° C. under a load of 0.0054 mN / dtex, the flame retardant synthesis of the present invention after spinning and before heat treatment. The fiber may be stretched. In this case, the total draw ratio (= stretch ratio (%) × (100−relaxation ratio (%)) × 0.01) obtained by multiplying the stretch ratio by the relaxation ratio (magnification), which is the ratio at which the fiber shrinks during heat treatment, It is preferably less than 4.8 times, and more preferably less than 4.2 times. Thereby, the spinning residual shrinkage stress can be further suppressed, and higher flame retardancy can be obtained.

(3) About shrinkage suppression mechanism of polymer containing epoxy group (for example, polyglycidyl methacrylate (pGMA)) Inhibition of shrinkage by reacting pGMA in spinning process and introducing polymer cross-linked structure into fiber . pGMA is cross-linked by the heat of drying or heat treatment, but if an acid catalyst is present, it is considered that cross-linking proceeds further. The metal oxide (antimony trioxide (Sb ₂ O ₃ ), zinc oxide (ZnO)) contained in the flame-retardant synthetic fiber of the present invention deprives the halogen in the polymer contained in the fiber (in the case of chlorine). SbCl ₃ , ZnCl ₂ ), which are believed to promote cross-linking of pGMA as an acid catalyst.

The flame-retardant synthetic fiber of the present invention can be used alone or in combination with natural fiber, recycled fiber, other synthetic fiber, or the like.

The flame retardant fiber composite of the present invention means a composite formed by combining the flame retardant synthetic fiber of the present invention and other fibers. In the present invention, the flame-retardant fiber composite is 10% by mass or more of the above-mentioned flame-retardant synthetic fiber and 90 masses of at least one kind of fiber selected from natural fibers, recycled fibers, and synthetic fibers other than the above-mentioned flame-retardant synthetic fibers. % Or less included. Further, the upper limit of the content of the flame retardant synthetic fiber in the flame retardant fiber composite is preferably 90% by mass or less, and at least one selected from natural fibers, recycled fibers, and synthetic fibers other than the flame retardant synthetic fibers. The lower limit of the fiber content is preferably 10% by mass or more.

Natural fibers include cotton fiber, kapok fiber, flax fiber, cannabis fiber, ramie fiber, jute fiber, manila fiber, kenaf fiber, wool fiber, mohair fiber, cashmere fiber, camel fiber, alpaca fiber, angora fiber, silk fiber, etc. There is. Examples of regenerated fibers include regenerated cellulose fibers (rayon, polynosic, trade name “Cupura” manufactured by Asahi Kasei Co., Ltd., product names “Tencel” and “lenting modal” manufactured by Asahi Kasei), regenerated collagen fibers, regenerated protein fibers, cellulose acetate fibers, There are promix fibers. Synthetic fibers include polyester fiber, polyamide fiber, polylactic acid fiber, acrylic fiber, polyolefin fiber, polyvinyl alcohol fiber, polyvinyl chloride fiber, polyvinylidene chloride fiber (trade name "Saran" manufactured by Asahi Kasei Fibers), polyclar fiber, polyethylene Fiber (trade name “Dyneema” manufactured by Toyobo Co., Ltd.), polyurethane fiber, polyoxymethylene fiber, polytetrafluoroethylene fiber, aramid fiber (trade names “Kevlar” manufactured by DuPont, “Nomex”), “Technola” manufactured by Teijin Limited ”,“ Twaron ”,“ Conex ”), benzoate fiber, polyphenylene sulfide fiber (trade name“ Procon ”manufactured by Toyobo Co., Ltd.), polyether ether ketone fiber, polybenzazole fiber, polyimide fiber (trade name, manufactured by Toyobo Co., Ltd.) “P84”), Riamidoimido fiber (Kerumeru trade name "Kerumeru"), and the like. Furthermore, specially regenerated cellulose fiber (rayon fiber containing water glass: trade name “Vigil” manufactured by Satellite, trade name “FR Corona” manufactured by Daiwabo Co., Ltd.), a fire retardant, and post-processed flame retardant cellulose fiber And flame retardant rayon fiber (trade name “Lentining FR” manufactured by Lenzing). Synthetic fibers include flame retardant polyester (trade name “Hheim” manufactured by Toyobo Co., Ltd., product name “Trevira CS” manufactured by Trevira), polyethylene naphthalate fiber (trade name “Teonex” manufactured by Teijin Limited), and melamine fiber (Vasofil Fibers). Product name “Vasofil”), acrylate fiber (trade name “MOISCARE” manufactured by Toyobo Co., Ltd.), and polybenzoxide fiber (trade name “Zyron” manufactured by Toyobo Co., Ltd.). In addition, there are oxidized acrylic fiber, carbon fiber, glass fiber, activated carbon fiber and the like.

Among these, cotton fiber, rayon fiber, water glass-containing rayon fiber, polyester fiber, and aramid fiber are preferable, polyester fiber is particularly preferable, the cost is low, and in the case of a nonwoven fabric, it is bulky. Moreover, cotton fiber, rayon fiber, water glass-containing rayon fiber, and aramid fiber are preferable in that they can further impart flame retardancy. It is preferable that the synthetic fiber other than the flame-retardant synthetic fiber is a polyester fiber, and the content in the flame-retardant fiber composite is 40% by mass or more. The upper limit is preferably 90% by mass or less.

In the present invention, the flame retardant fiber composite includes mixed cotton, mixed spinning, mixed fiber, aligned yarn, synthetic yarn, core sheath and other composite yarn, union, union, lamination, etc. Cotton, non-woven fabric, woven fabric, knitted fabric, lace knitted fabric, braided fabric, etc.

Examples of cotton for filling include open cotton, ball cotton, web, and molded cotton.

Nonwoven fabrics include wet papermaking nonwoven fabrics, carded nonwoven fabrics, airlaid nonwoven fabrics, thermal bond nonwoven fabrics, chemically bonded nonwoven fabrics, needle punched nonwoven fabrics, hydroentangled nonwoven fabrics, and stitch bond nonwoven fabrics. Thermal bond nonwoven fabric and needle punched nonwoven fabric are industrially inexpensive. The nonwoven fabric may have any of a uniform structure, a clear laminated structure, and an unclear laminated structure in the thickness, width, and length directions.

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

The knitting includes round knitting, weft knitting, warp knitting, pile knitting, etc., flat knitting, tengu knitting, rib knitting, smooth knitting (double-sided knitting), rubber knitting, pearl knitting, denby knitting, cord knitting, atlas knitting, There are chain structures, inserted tissues, and the like. Tengu and ribs are excellent in texture as products.

In the present invention, the textile product contains the flame retardant synthetic fiber. Examples of the textile products include the following.
(1) Clothing and daily necessities Clothing (including outerwear, underwear, sweaters, vests, trousers, etc.), gloves, socks, mufflers, hats, bedding, pillows, cushions, stuffed animals, etc. (2) Special clothing Protective clothing, fire fighting clothing (3) Interior materials Chair upholstery, curtains, wallpaper, carpets, etc. (4) Industrial materials Filters, flameproof stuffing, lining materials, etc.

For example, if a textile product of the present invention is used to produce bedding or furniture such as a bed mattress, pillow, comforter, bed spread, mattress pad, futon, cushion, chair, etc. A fabric upholstered product having excellent properties such as texture, touch, color tone, and hygroscopicity can be obtained. Examples of the bed mattress include a pocket coil mattress in which a metal coil is used, a box coil mattress, an insulator in which styrene or urethane resin is foamed, or a mattress in which low-rebound urethane is used. . Due to the flame retardancy of the flame retardant synthetic fiber of the present invention, it is possible to prevent the spread of fire to the internal structure of the mattress. Therefore, in any mattress of the structure, a mattress excellent in texture and touch as well as flame retardancy is obtained. be able to. As chairs, used indoors, tools, benches, side chairs, armchairs, lounge chairs / sofas, seat units (sectional chairs, separate chairs), rocking chairs, folding chairs, stacking chairs, swivel chairs, or outdoors Automotive seats, marine seats, aircraft seats, train seats, etc. used for vehicle seats, etc., but these also prevent the spread of internal fire as well as the appearance and feel required for normal furniture It is possible to obtain a flame retardant product having the function of

The use of the fabric containing the flame retardant synthetic fiber and / or the flame retardant fiber composite of the present invention (hereinafter referred to as the fabric of the present invention) for a flame retardant upholstered product is as follows. It may be used in a form, or may be sandwiched in the form of a woven fabric, a knitted fabric or a non-woven fabric between a fabric on the surface and an internal structure such as urethane foam or stuffed cotton. When used for the surface fabric, the fabric of the present invention may be used instead of the conventional surface fabric. Further, when a woven fabric or a knitted fabric is sandwiched between the surface fabric and the internal structure, the surface fabric may be sandwiched in a manner of overlapping two sheets, or the internal structure may be covered with the fabric of the present invention. When sandwiching the fabric of the present invention between the surface fabric and the internal structure, be sure to cover the entire internal structure with the fabric of the present invention on the outside of the internal structure at least for the part that contacts the surface fabric. Apply the surface fabric from above.

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

(Evaluation method for promoting dehalogenation reaction)
The evaluation method for promoting the dehalogenation reaction was carried out as follows using a differential heat / thermogravimetry (trade name “TG / DTA220” manufactured by Seiko Instruments Inc.).

5 mg of a polymer (1) consisting of 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 styrenesulfonate was added under air conditions (gas flow rate: 200 ml / min, temperature rise) When heating at a rate of 20 ° C./min), the temperature at which weight loss starts, that is, the dehalogenation start temperature was measured. As a result, the dehalogenation start temperature was 243 ° C.

Next, with respect to 100 parts by mass of the polymer (1), 10 parts by mass of the metal compound shown in Table 1 was added, and 5 mg of a sufficiently mixed sample was subjected to air conditions (gas flow rate: 200 ml / min, heating rate) : 20 ° C./min). At that time, when the temperature at which weight reduction starts, that is, the dehalogenation start temperature was less than 243 ° C., it was judged that the dehalogenation reaction was promoted, and was set to A. Further, when the dehalogenation start temperature was 243 ° C. or higher, it was determined that the dehalogenation reaction was not promoted, and was set to B. The evaluation results of each metal compound are shown in Table 1.

(Evaluation method for carbonization reaction promotion)
The evaluation method of carbonization reaction acceleration was carried out as follows using a differential heat / thermogravimetry (trade name “TG / DTA220” manufactured by Seiko Instruments Inc.).

5 mg of a polymer (1) consisting of 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 styrenesulfonate was added under air conditions (gas flow rate: 200 ml / min, temperature rise) When heated at a rate of 20 ° C./min), the residual weight ratio at 500 ° C. was measured. As a result, the remaining weight ratio was 52%.

Next, with respect to 100 parts by mass of the polymer (1), 10 parts by mass of the metal compound shown in Table 1 was added, and 5 mg of a sufficiently mixed sample was subjected to air conditions (gas flow rate: 200 ml / min, heating rate) : 20 ° C./min). At that time, when the remaining weight ratio at 500 ° C. was 47% or more, it was judged that the carbonization reaction was promoted, and was set to A. Moreover, when the remaining weight ratio in 500 degreeC was less than 47%, it judged that the carbonization reaction was not accelerated | stimulated and was set as B. The evaluation results of each metal compound are shown in Table 1 below.

[Table 1]

(Production Examples 1 to 9 of halogen-containing fiber)
A copolymer consisting of 51% acrylonitrile, 48% vinylidene chloride and 1% p-styrene sulfonic acid soda was dissolved in acetone to a resin concentration of 30%. 2, zinc oxide (3 types of zinc oxide JIS) as the metal compound (2-1), antimony trioxide as the metal compound (2-2), and polyglycidyl methacrylate (weight average molecular weight 40000) as the epoxy group-containing compound. Added to make a spinning dope. This spinning dope was extruded into a 30% acetone aqueous solution using a nozzle having a nozzle hole diameter of 0.10 mm and a hole number of 1000 holes, washed with water while being stretched, dried at 120 ° C., and further at 123 ° C. in wet heat and pressurized steam for 15 minutes. Then, a relaxation treatment was performed in a non-tensioned state, and a halogen-containing fiber was obtained by further cutting. At this time, the total draw ratio was 2.6 times. The obtained fiber was a fine fiber having a fineness of 7.8 dtex and a cut length of 64 mm.

(Production Examples 10 and 11 of halogen-containing fiber)
A copolymer consisting of 43% acrylonitrile, 56% vinylidene chloride and 1% sodium p-styrene sulfonate was dissolved in acetone so that the resin concentration was 30%. 2, zinc oxide (3 types of zinc oxide JIS) as the metal compound (2-1), antimony trioxide as the metal compound (2-2), and polyglycidyl methacrylate (weight average molecular weight 40000) as the epoxy group-containing compound. Added to make a spinning dope. This spinning dope is extruded into a 30% acetone aqueous solution using a nozzle having a nozzle hole diameter of 0.10 mm and a hole number of 1000 holes, washed with water while being stretched, dried at 120 ° C., and then at 170 ° C. for 2 minutes in a state of no tension. Was subjected to dry heat relaxation treatment and further cut to obtain a halogen-containing fiber. At this time, the total draw ratio was 3.0 times. The obtained fiber was a fine fiber having a fineness of 7.8 dtex and a cut length of 64 mm.

(Production Example 12 of halogen-containing fiber)
A copolymer consisting of 38% acrylonitrile, 61% vinylidene chloride and 1% p-styrene sulfonic acid soda was dissolved in acetone so that the resin concentration would be 30%. 2, zinc oxide (3 types of zinc oxide JIS) as the metal compound (2-1), antimony trioxide as the metal compound (2-2), and polyglycidyl methacrylate (weight average molecular weight 40000) as the epoxy group-containing compound. Added to make a spinning dope. This spinning dope is extruded into a 30% acetone aqueous solution using a nozzle having a nozzle hole diameter of 0.10 mm and a hole number of 1000 holes, washed with water while being stretched, dried at 120 ° C., and then at 170 ° C. for 2 minutes in a state of no tension. Was subjected to dry heat relaxation treatment and further cut to obtain a halogen-containing fiber. At this time, the total draw ratio was 3.0 times. The obtained fiber was a fine fiber having a fineness of 7.8 dtex and a cut length of 64 mm.

(Production Example 13 of halogen-containing fiber)
A copolymer consisting of 51% acrylonitrile, 48% vinylidene chloride and 1% p-styrene sulfonic acid soda was dissolved in acetone to a resin concentration of 30%. 2, zinc oxide (3 types of zinc oxide JIS) as the metal compound (2-1), antimony trioxide as the metal compound (2-2), and polyglycidyl methacrylate (weight average molecular weight 40000) as the epoxy group-containing compound. Added to make a spinning dope. This spinning stock solution was extruded into a 30% acetone aqueous solution using a nozzle having a nozzle hole diameter of 0.10 mm and a hole number of 1000 holes, washed with water while being stretched, dried at 120 ° C., and further dried at 185 ° C. for 2 minutes. The total draw ratio was 3.0 times. The obtained fiber was a fine fiber having a fineness of 7.8 dtex and a cut length of 64 mm.

(Production Example 14 of halogen-containing fiber)
A copolymer consisting of 51% acrylonitrile, 48% vinylidene chloride and 1% p-styrene sulfonic acid soda was dissolved in acetone to a resin concentration of 30%. 2, zinc oxide (3 types of zinc oxide JIS) as the metal compound (2-1), antimony trioxide as the metal compound (2-2), and polyglycidyl methacrylate (weight average molecular weight 40000) as the epoxy group-containing compound. Added to make a spinning dope. This spinning dope was extruded into a 30% acetone aqueous solution using a nozzle with a nozzle hole diameter of 0.10 mm and a hole number of 1000 holes, washed with water while being stretched, dried at 120 ° C., and further dried at 150 ° C. for 15 minutes in wet heat pressurized steam. The halogen-containing fiber was obtained by further heat-cutting and heat-treating. At this time, the total draw ratio was 4.5 times. The obtained fiber was a fine fiber having a fineness of 7.8 dtex and a cut length of 64 mm.

(Production Example 15 of halogen-containing fiber)
A copolymer consisting of 51% acrylonitrile, 48% vinylidene chloride and 1% p-styrene sulfonic acid soda was dissolved in acetone to a resin concentration of 30%. 2, zinc oxide (3 types of zinc oxide JIS) as the metal compound (2-1), antimony trioxide as the metal compound (2-2), and polyglycidyl methacrylate (weight average molecular weight 40000) as the epoxy group-containing compound. Added to make a spinning dope. This spinning dope is extruded into a 30% acetone aqueous solution using a nozzle with a nozzle hole diameter of 0.10 mm and a hole number of 1000 holes, washed with water while being stretched, dried at 120 ° C., and further cut without performing a relaxation treatment. To obtain a halogen-containing fiber. At this time, the total draw ratio was 3.0 times. The obtained fiber was a fine fiber having a fineness of 7.8 dtex and a cut length of 64 mm.

(Production Example 16 of halogen-containing fiber)
A copolymer consisting of 51% acrylonitrile, 48% vinylidene chloride and 1% p-styrene sulfonic acid soda was dissolved in acetone to a resin concentration of 30%. In addition amounts shown in 2, zinc oxide (3 types of zinc oxide JIS) as the metal compound (2-1), antimony trioxide as the metal compound (2-2), cresol novolac epoxy as the epoxy group-containing compound (product of Nippon Kayaku Co., Ltd.) The name “EOCN-104S”) was added to give a spinning dope. This spinning dope was extruded into a 30% acetone aqueous solution using a nozzle having a nozzle hole diameter of 0.10 mm and a hole number of 1000 holes, washed with water while being stretched, dried at 120 ° C., and further at 123 ° C. in wet heat and pressurized steam for 15 minutes. Then, a relaxation treatment was performed in a non-tensioned state, and a halogen-containing fiber was obtained by further cutting. At this time, the total draw ratio was 2.6 times. The obtained fiber was a fine fiber having a fineness of 7.8 dtex and a cut length of 64 mm.

(Production Example 17 of halogen-containing fiber)
A copolymer consisting of 51% acrylonitrile, 48% vinylidene chloride and 1% p-styrene sulfonic acid soda was dissolved in acetone to a resin concentration of 30%. 2, zinc oxide (3 types of zinc oxide JIS) as the metal compound (2-1), antimony pentoxide as the metal compound (2-2), and polyglycidyl methacrylate (weight average molecular weight 40000) as the epoxy group-containing compound. Added to make a spinning dope. This spinning dope was extruded into a 30% acetone aqueous solution using a nozzle having a nozzle hole diameter of 0.10 mm and a hole number of 1000 holes, washed with water while being stretched, dried at 120 ° C., and further at 123 ° C. in wet heat and pressurized steam for 15 minutes. Then, a relaxation treatment was performed in a non-tensioned state, and a halogen-containing fiber was obtained by further cutting. At this time, the total draw ratio was 2.6 times. The obtained fiber was a fine fiber having a fineness of 7.8 dtex and a cut length of 64 mm.

(Production Example 18 of halogen-containing fiber)
A copolymer consisting of 51% acrylonitrile, 48% vinylidene chloride and 1% p-styrene sulfonic acid soda was dissolved in acetone to a resin concentration of 30%. 2, zinc oxide (3 types of zinc oxide JIS) as metal compound (2-1), copper iodide as metal compound (2-2), and polyglycidyl methacrylate (weight average molecular weight 40000) as epoxy group-containing compound. Added to make a spinning dope. This spinning dope was extruded into a 30% acetone aqueous solution using a nozzle having a nozzle hole diameter of 0.10 mm and a hole number of 1000 holes, washed with water while being stretched, dried at 120 ° C., and further at 123 ° C. in wet heat and pressurized steam for 15 minutes. Then, a relaxation treatment was performed in a non-tensioned state, and further cut to obtain a halogen-containing fiber. At this time, the total draw ratio was 2.6 times. The obtained fiber was a fine fiber having a fineness of 7.8 dtex and a cut length of 64 mm.

(Production Example 19 of halogen-containing fiber)
A copolymer consisting of 51% acrylonitrile, 48% vinylidene chloride and 1% p-styrene sulfonic acid soda was dissolved in acetone to a resin concentration of 30%. 2, tin oxide as the metal compound (2-1), antimony trioxide as the metal compound (2-2), and polyglycidyl methacrylate (weight average molecular weight 40000) as the epoxy group-containing compound were added. did. This spinning dope was extruded into a 30% acetone aqueous solution using a nozzle with a nozzle hole diameter of 0.10 mm and a hole number of 1000 holes, washed with water while being stretched, dried at 120 ° C., and further dried at 15 ° C. at 123 ° C. A halogen-containing fiber was obtained by performing a relaxation treatment in a state of no tension for a minute and further cutting. At this time, the total draw ratio was 2.6 times. The obtained fiber was a fine fiber having a fineness of 7.8 dtex and a cut length of 64 mm.

(Production Example 20 of halogen-containing fiber)
A copolymer consisting of 51% acrylonitrile, 48% vinylidene chloride and 1% p-styrene sulfonic acid soda was dissolved in acetone to a resin concentration of 30%. 2, zinc carbonate as the metal compound (2-1), antimony trioxide as the metal compound (2-2), and polyglycidyl methacrylate (weight average molecular weight 40000) as the epoxy group-containing compound were added. did. This spinning dope was extruded into a 30% acetone aqueous solution using a nozzle having a nozzle hole diameter of 0.10 mm and a hole number of 1000 holes, washed with water while being stretched, dried at 120 ° C., and further at 123 ° C. in wet heat and pressurized steam for 15 minutes. Then, a relaxation treatment was performed in a non-tensioned state, and further cut to obtain a halogen-containing fiber. At this time, the total draw ratio was 2.6 times. The obtained fiber was a fine fiber having a fineness of 7.8 dtex and a cut length of 64 mm.

(Production Examples 21 and 22 of halogen-containing fibers)
A copolymer consisting of 51% acrylonitrile, 48% vinylidene chloride and 1% p-styrene sulfonic acid soda was dissolved in acetone to a resin concentration of 30%. In the addition amount shown in 2, antimony trioxide was added as the metal compound (2-2), and polyglycidyl methacrylate (weight average molecular weight 40000) was added as the epoxy group-containing compound to prepare a spinning dope. This spinning dope is extruded into a 30% acetone aqueous solution using a nozzle having a nozzle hole diameter of 0.10 mm and a hole number of 1000 holes, washed with water while being stretched, dried at 120 ° C., and then at 170 ° C. for 2 minutes in a state of no tension. Was subjected to dry heat relaxation treatment and further cut to obtain a halogen-containing fiber. At this time, the total draw ratio was 2.6 times. The obtained fiber was a fine fiber having a fineness of 7.8 dtex and a cut length of 64 mm.

(Production Example 23 of Halogen-Containing Fiber)
A copolymer consisting of 51% acrylonitrile, 48% vinylidene chloride and 1% p-styrene sulfonic acid soda was dissolved in acetone to a resin concentration of 30%. Zinc oxide (3 types of zinc oxide JIS) was added as the metal compound (2-1) in the addition amount shown in 2, and antimony trioxide was added as the metal compound (2-2) to obtain a spinning dope. This spinning stock solution was extruded into a 30% acetone aqueous solution using a nozzle having a nozzle hole diameter of 0.10 mm and a hole number of 1000 holes, washed with water while being stretched, dried at 120 ° C., and further dried at 170 ° C. for 2 minutes. The total draw ratio was 5.0 times. The obtained fiber was a fine fiber having a fineness of 7.8 dtex and a cut length of 64 mm.

(Production Example 24 of Halogen-Containing Fiber)
A copolymer consisting of 51% acrylonitrile, 48% vinylidene chloride and 1% sodium p-styrene sulfonate was dissolved in dimethylformamide so that the resin concentration was 23%. 2, zinc oxide (3 types of zinc oxide JIS) as the metal compound (2-1), antimony trioxide as the metal compound (2-2), and polyglycidyl methacrylate (weight average molecular weight 40000) as the epoxy group-containing compound. Added to make a spinning dope. This spinning dope was extruded into a 55% dimethylformamide aqueous solution using a nozzle having a nozzle hole diameter of 0.06 mm, washed with water while being stretched, dried at 130 ° C., stretched, and further subjected to wet heat tension treatment at 140 ° C. for 15 minutes. Further, a halogen-containing fiber was obtained by cutting. At this time, the total draw ratio was 4.8 times. Further, the obtained fiber was a short fiber having a fineness of 1.7 dtex and a cut length of 64 mm.

(Production Example 25 of halogen-containing fiber)
A copolymer consisting of 57% acrylonitrile, 41% vinylidene chloride and 2% sodium allyl sulfonate is dissolved in dimethylformamide so that the resin concentration is 25%. The resin mass of the resulting resin solution is as shown in Table 2 below. Antimony trioxide was added as a metal compound (2-2) in the addition amount shown to obtain a spinning dope. This spinning dope was extruded into a 55% dimethylformamide aqueous solution using a nozzle having a nozzle hole diameter of 0.06 mm, washed with water while being stretched, dried at 130 ° C., stretched, and further subjected to wet heat tension treatment at 130 ° C. for 15 minutes. Further, a halogen-containing fiber was obtained by cutting. At this time, the total draw ratio was 6.0 times. Further, the obtained fiber was a short fiber having a fineness of 1.7 dtex and a cut length of 64 mm.

(Production Example 26 of Halogen-Containing Fiber)
2 parts of a copolymer composed of 60% acrylonitrile, 30% vinyl chloride and 10% sodium allyl sulfonate, 22 parts of a copolymer composed of 42% acrylonitrile, 57% vinyl chloride and 1% sodium p-styrene sulfonate The resin stock solution was dissolved to a concentration of 23%, and metastannic acid was added as a metal compound (2-1) in the addition amount shown in Table 2 below with respect to the resin mass of the obtained resin solution to obtain a spinning stock solution. . This spinning dope is extruded into a 60% dimethylformamide aqueous solution using a nozzle having a nozzle hole diameter of 0.06 mm, washed with water while being stretched, dried at 130 ° C., further subjected to wet heat tension treatment at 130 ° C. for 15 minutes, and further cut. Thus, a halogen-containing fiber was obtained. At this time, the total draw ratio was 5.1 times. The obtained fiber was a fine fiber having a fineness of 2.2 dtex and a cut length of 64 mm.

(Production Example 27 of halogen-containing fiber)
A copolymer consisting of 55% acrylonitrile, 43% vinylidene chloride and 2% sodium allyl sulfonate was dissolved in dimethyl sulfoxide to a resin concentration of 23.5%. Antimony trioxide was added as a metal compound (2-2) in the addition amount shown in the following to obtain a spinning dope. This spinning dope is extruded into a 55% dimethyl sulfoxide aqueous solution using a nozzle having a nozzle hole diameter of 0.065 mm, washed with water while being stretched, dried at 130 ° C., further subjected to wet heat tension treatment at 160 ° C. for 15 minutes, and further cut. Thus, a halogen-containing fiber was obtained. At this time, the total draw ratio was 4.8 times. The obtained fiber was a fine fiber having a fineness of 2.2 dtex and a cut length of 64 mm.

(Production Example 28 of Halogen-Containing Fiber)
A copolymer consisting of 55% acrylonitrile, 43% vinylidene chloride and 2% sodium allyl sulfonate was dissolved in dimethyl sulfoxide to a resin concentration of 23.5%. Antimony trioxide was added as a metal compound (2-2) in the addition amount shown in the following to obtain a spinning dope. This spinning dope is extruded into a 55% dimethyl sulfoxide aqueous solution using a nozzle having a nozzle hole diameter of 0.065 mm, washed with water while being stretched, dried at 130 ° C., further subjected to wet heat tension treatment at 160 ° C. for 15 minutes, and further cut. Thus, a halogen-containing fiber was obtained. At this time, the total draw ratio was 4.2 times. The obtained fiber was a fine fiber having a fineness of 2.2 dtex and a cut length of 64 mm.

(Production example 29 of halogen-containing fiber)
A copolymer consisting of 55% acrylonitrile, 43% vinylidene chloride and 2% sodium allyl sulfonate was dissolved in dimethyl sulfoxide to a resin concentration of 23.5%. Zinc oxide (3 kinds of zinc oxide JIS) was added as a metal compound (2-1) in the addition amount shown in FIG. This spinning dope is extruded into a 55% dimethyl sulfoxide aqueous solution using a nozzle having a nozzle hole diameter of 0.065 mm, washed with water while being stretched, dried at 130 ° C., further subjected to wet heat tension treatment at 160 ° C. for 2 minutes, and further cut. Thus, a halogen-containing fiber was obtained. At this time, the total draw ratio was 4.8 times. The obtained fiber was a fine fiber having a fineness of 2.2 dtex and a cut length of 64 mm.

(Production Example 30 of Halogen-Containing Fiber)
A copolymer consisting of 51% acrylonitrile, 48% vinylidene chloride and 1% p-styrene sulfonic acid soda was dissolved in acetone to a resin concentration of 30%. In the addition amount shown in 2, antimony trioxide was added as the metal compound (2-2), and aluminum hydroxide was added as the other metal compound to prepare a spinning dope. This spinning dope was extruded into a 30% acetone aqueous solution using a nozzle having a nozzle hole diameter of 0.10 mm and a hole number of 1000 holes, washed with water while being stretched, dried at 120 ° C., and further at 123 ° C. in wet heat and pressurized steam for 15 minutes. Then, a relaxation treatment was performed in a non-tensioned state, and a halogen-containing fiber was obtained by further cutting. At this time, the total draw ratio was 2.6 times. The obtained fiber was a fine fiber having a fineness of 7.8 dtex and a cut length of 64 mm.

(Production method of flame retardant evaluation specimen)
The flame retardancy evaluation of the flame retardant synthetic fiber, the flame retardant composite, and the fiber product using the same was carried out by preparing a sample for flame retardancy evaluation using the following method.

1. Preparation Method of Thermal Bond Nonwoven for Flame Retardancy Evaluation Test After the fibers shown below are mixed so as to have the predetermined mixing ratios shown in Tables 2 and 3 below, the fibers are opened with a card, and then by a normal heat fusion method. A thermal bond nonwoven fabric with a predetermined basis weight was produced.
Halogen-containing fibers produced by the production methods shown in the above-mentioned halogen-containing fiber production examples 1 to 29, a product name “Tetron” (fineness 6 dtex, cut length 51 mm) manufactured by TORAY which is a general-purpose polyester fiber as a polyester fiber In the following, it is also referred to as “reg.PET”), a trade name “SAFMET” (a fineness of 4.4 dtex, a cut length of 51 mm, a melting point of 110 ° C.), which is a heat-bonded polyester fiber, and a melt PET. General purpose rayon and / or para-aramid fiber (trade name “Kevlar” manufactured by Dupont).

2. Method for producing needle punched nonwoven fabric for flame retardancy evaluation test The halogen-containing fibers produced by the production methods shown in Production Examples 5, 11, and 22 above and manufactured by Toray Co., Ltd. which is a general-purpose polyester fiber as a polyester fiber The product name “Tetron” (fineness: 6 dtex, cut length: 51 mm) was mixed so that the fibers had the predetermined mixing ratios shown in Tables 2 to 3 below, opened with a card, and then specified with a normal needle punch method. A needle punched nonwoven fabric with a basis weight of 1 was prepared.

3. Method for Producing Pillow Top Type Mattress Specimens The structure of a pillow top type mattress is shown in FIGS. Two polyurethane foams (type 360S manufactured by Toyo Rubber Industries Co., Ltd.) (1), 30 cm long x 45 cm wide x 1.9 cm thick x 1.9 cm thick, density 1.27 cm, density 30 cm long One 22 kg / m3 polyurethane foam (type 360S manufactured by Toyo Tire & Rubber Co., Ltd.) (2), one non-woven fabric (3) prepared by the method for preparing a non-flammability evaluation test non-woven fabric, and outer surface fabric ( 4) A structure in which one piece of fabric selected from polyester / polypropylene woven fabric, polyester woven fabric, rayon / polyester woven fabric, and cotton woven fabric (weighing 120 g / m ² ) is stacked as shown in FIG. A nylon thread (5) is used to quilt at a quilting interval of 20 cm, and the polyurethane foam having a thickness of 15 cm (type 360 manufactured by Toyo Tire & Rubber Co., Ltd.) S) (6) was laminated to produce a pillow top type mattress specimen.

4). Method for Producing Tight Top Type Mattress Specimen The structure of a tight top type mattress specimen is shown in FIGS. One nonwoven fabric (3) produced by the method for producing a flame retardant evaluation test nonwoven fabric, and polyester / polypropylene woven fabric, polyester woven fabric, rayon / polyester woven fabric, cotton woven as the outer surface fabric (4) One piece of fabric (weight per unit area: 120 g / m ² ) selected from cloth and a structure laminated as shown in FIG. 4 is quilted with a nylon thread (5) at a quilting interval of 20 cm, and this is polyurethane foam (Toyo A tight top type mattress test specimen was prepared by pasting onto a rubber industry type 360S) (6).

5). Pillow specimen preparation method (Manufacture of batting)
Product name “Tetron” (fineness 6 dtex, cut length 51 mm) manufactured by TORAY, which is a general-purpose polyester fiber as a halogen-containing fiber and a polyester-based fiber produced by the production methods shown in Production Examples 5, 11, and 22 above. )It was used. These fibers were opened with a card at a blending ratio shown in Table 3 below to form a web, and multilayered to produce batting.
(Production of side land)
A spun yarn with a metric count of 34 was obtained by blending 50% by weight of cotton fiber and 50% by weight of polyester fiber. A plain weave fabric having a basis weight of 120 g / m ² was produced from this spun yarn by a known method.
(Production method of the flame retardant cushion)
The produced batting is cut into a length of about 30.5 cm and a width of about 30.5 cm. The batting is sandwiched between fabrics (side ground) cut to about 38.1cm in length and 38.1cm in width, and a plate with a weight of 325g is placed on it, and the height of the cushion is 89mm (3.5inch) or more and 102mm (4.0inch) ) Was adjusted so as to be within the range, and the four sides were closed with a cut yarn to produce a flame retardant evaluation cushion.

6). Specimen preparation method assuming fabric The halogen-containing fibers and cotton prepared by the production methods shown in the above Production Examples 5, 11, and 22 are mixed so as to have a predetermined mixture ratio shown in Table 3 below, and opened by a card. After that, a needle punched nonwoven fabric with a predetermined basis weight was produced by a normal needle punch method. The prepared needle punched nonwoven fabric was thermally compressed at 150 ° C. for 300 seconds with a hot press machine to prepare a test specimen having a thickness of 2 mm, which was used as a specimen assuming a cloth.

7). Method for preparing test specimen of knit fabric A predetermined amount of the halogen-containing fiber and cotton fiber prepared in the production example are mixed to produce a spun yarn (meter count 34), and a predetermined circular knitting machine is used. A knit fabric having

(Flame retardance evaluation method)
For the flame retardancy performance of the flame retardant synthetic fiber in the examples, a test specimen prepared in the procedure for preparing a flame retardant evaluation specimen was used.

1. Panel test evaluation method The test was conducted according to the combustion test method for the upper surface of the bed of 16 CFR 1633 in the United States. Briefly explaining the combustion test method on the upper surface of the bed of US 16CFR1633, a T-shaped burner was set horizontally at 39 mm from the upper surface of the bed, propane gas was used as the combustion gas, the gas pressure was 101 KPa, The flow rate is 12.9 L / min, and it is a test method for flaming for 70 seconds. The evaluation of flame retardancy was as follows.
A rank pass: When tested by the above test method, self-extinguishing and no cracks or holes were found in the exposed part.
Rank B: Same as above, but self-extinguishing, but a crack of less than 1 cm occurred in the part exposed to flame.
C rank: Same as above, but self-extinguishing, but a crack of 1 cm or more occurred in the part exposed to the flame.
D rank pass: Same as above, once ignited the internal flammable urethane, but immediately disappeared and finally self-extinguished.
Fail: Same as above, the internal flammable urethane was ignited, the fire was forcibly extinguished, and the test was stopped.

2. Stove test evaluation method A pearlite plate with a length of 200 mm × width 200 mm × thickness 10 mm was prepared by making a hole with a diameter of 15 cm at the center, and was prepared based on a method for preparing a thermal bond nonwoven fabric for flame retardant evaluation test. A nonwoven fabric was placed, and four sides were fixed with clips so that the nonwoven fabric for flame retardancy evaluation test did not shrink during heating. The sample is placed on the gas stove (trade name “PA-10H-2”, manufactured by Paloma Kogyo Co., Ltd.) with the surface of the non-woven fabric for flame retardant evaluation test facing upward, and the center of the sample and the center of the burner are 40 mm from the burner surface. Set to fit. The fuel gas used was propane with a purity of 99% or more, the flame height was 25 mm, and the flame contact time was 180 seconds. At this time, the case where there was no through hole or crack in the carbonized layer of the non-woven fabric for flame retardancy evaluation test, or the case where there was no through hole but there was a crack, was accepted, and the case where there was a hole or crack was rejected.

3. TB604 Test Evaluation Method Flame retardancy was carried out based on a draft (TB604) Section 2 published in October 2004 by the combustion test method Technical Bulletin 604 in California, USA. The TB604 combustion test method in California, USA will be briefly described. In the test for pillows and cushions, the test piece is 3/4 inch below one corner of the flame retardant evaluation cushion that is leveled. A 35 mm flame is applied for 20 seconds. If the weight loss rate after 6 minutes is 25% by weight or less, it is acceptable. In Table 3 below, those having a weight reduction rate of 25% by weight or less were accepted, and those exceeding 25% by weight were rejected. The burner tube used has an inner diameter of 6.5 mm, an outer diameter of 8 mm, and a length of 200 mm. The fuel gas is butane gas with a purity of 99% or more, the butane gas flow rate is 45 ml / min, and the flame height is about 35 mm.

4). JIS L1091 A-4 Test Evaluation Method The evaluation of the fabric was performed based on the JIS L1091 A-4 method. Five test specimens (8.9 cm long × 25.4 cm wide) prepared by a test specimen preparation method assuming a cloth were prepared and set on a support frame. Next, the test body is vertically held in a vertical combustion tester compliant with the JIS L1091 A-4 test, and the distance from the tip of the Bunsen burner mounted at an angle of 25 ° to the center of the lower end of the test body is 17 mm. The positions of the burner and the specimen were adjusted so that A flame was contacted to the sample, and when the sample ignited, it was measured with a stopwatch. Next, a weight (0.25 lb) was hooked on one side of the carbonized part of the test specimen after the test, and the part torn when it was slowly pulled up with the opposite end was measured as the carbonized length, and the carbonized length was less than 254 mm at maximum The case where the average was 178 mm or less was determined to be acceptable, and the others were determined to be unacceptable.

(Measurement method of fiber shrinkage)
About 5 mm of halogen-containing fiber, 3333 dtex (decitex), prepared according to the above production example, is taken, and TMA (thermal stress strain measuring device (trade name “TMA / SS150C” manufactured by Seiko Instruments Inc.), gas used: nitrogen, gas flow rate: 30 L / Min, temperature increase rate: 20 ° C./min, load 18 mN) When the initial sample length is X and the sample length at an arbitrary temperature is Y, the fiber shrinkage is expressed by the following equation.
Fiber shrinkage (%) = 100 − [(100 × Y) / X]

(Examples 1 to 20)
According to Production Examples 1 to 20, a halogen-containing fiber was prepared by adding the metal compound (2-1), metal compound (2-2), and epoxy group compound in the amounts shown in Table 2 below, and a thermal bond for flame retardancy evaluation test A non-woven fabric is prepared with a predetermined mixing ratio (halogen-containing fiber: regular polyester fiber (reg. PET): melt polyester fiber (mPET) = 50: 30: 20, basis weight 280 g / m ² ), and a pillow top type using this nonwoven fabric. Flame retardant evaluation using a mattress specimen and fiber shrinkage measurement by thermal stress strain measurement were performed. The results are shown in Table 2 below.

In Examples 1 to 9, the halogen-containing fiber is 0.05 to 50 parts by weight of metal oxide (2), particularly 0.05 to 0.05 parts by weight of metal compound (2-1), relative to 100 parts by weight of polymer (1). The temperature was raised from 50 ° C. to 300 ° C. under a load of 0.0054 mN / dtex by containing 50 parts by mass and being subjected to relaxation treatment at 123 ° C. for 15 minutes in wet heat and pressurized steam under no tension. The shrinkage fluctuation was 45% or less, the combustion test result using the flame retardant test specimen was good, and the pass / fail judgment was acceptable.

In Examples 10 to 12, the halogen-containing fiber is 0.05 to 50 parts by mass of the metal oxide (2), particularly 0.05 to 0.05 parts by mass of the metal compound (2-1) with respect to 100 parts by mass of the polymer (1). It contains ~ 50 parts by mass and is subjected to dry heat treatment at 170 ° C for 2 minutes in a no-tension state, so that the shrinkage variation when the temperature is raised from 50 ° C to 300 ° C under a load of 0.0054 mN / dtex. It became 45% or less, the combustion test result using the flame retardant evaluation specimen was good, and the pass / fail judgment was acceptable.

In Example 12, as described above, the combustion test result using the flame retardant evaluation specimen was good and the pass / fail judgment was acceptable, but the halogen-containing fiber was acrylonitrile 38%, vinylidene chloride 61. Since a copolymer comprising 1% and p-styrene sulfonic acid soda 0.9% was used, the heat resistance was inferior to that of the other examples, and the fibers were fused to each other during spinning, particularly during the relaxation treatment. Since it became hard, when the nonwoven fabric for flame-retardant evaluation was produced, the opening property was bad, and the nonwoven fabric in which the halogen-containing fiber, the polyester fiber, and the heat-fused polyester fiber were uniformly mixed could not be produced.

In Example 13, the halogen-containing fiber is 0.05 to 50 parts by mass of the metal oxide (2), particularly 0.05 to 50 parts by mass of the metal compound (2-1) with respect to 100 parts by mass of the polymer (1). Contained in parts by mass and subjected to a dry heat treatment in tension at 185 ° C for 2 minutes, the shrinkage variation when the temperature is raised from 50 ° C to 300 ° C under a load of 0.0054 mN / dtex is 45% or less. The combustion test results using the flame retardant test specimen were good, and the pass / fail judgment was acceptable.

In Example 14, the halogen-containing fiber is 0.05 to 50 parts by mass of the metal oxide (2), particularly 0.05 to 50 parts by mass of the metal compound (2-1) with respect to 100 parts by mass of the polymer (1). Contained in parts by mass and subjected to wet heat treatment at 150 ° C. for 15 minutes in a tension state, the shrinkage variation when the temperature is raised from 50 ° C. to 300 ° C. under a load of 0.0054 mN / dtex is 45% or less. Thus, the result of the combustion test using the flame retardant evaluation specimen was good, and the pass / fail judgment was acceptable.

In Example 15, the halogen-containing fiber is 0.05 to 50 parts by mass of the metal oxide (2), particularly 0.05 to 50 parts by mass of the metal compound (2-1) with respect to 100 parts by mass of the polymer (1). Although contained by mass and not heat-treated, the halogen-containing fiber has a shrinkage variation of 45% or less when the temperature is raised from 50 ° C. to 300 ° C., and a combustion test using a flame retardant test specimen The result was good, the result of the combustion test using the flame retardant test specimen was good, and the pass / fail judgment was acceptable.

In Example 16, cresol novolac epoxy resin was used as the epoxy group compound instead of polyglycidyl methacrylate, but the shrinkage variation when the temperature was increased from 50 ° C. to 300 ° C. under a load of 0.0054 mN / dtex was 45%. The results of the combustion test using the flame retardant evaluation specimen were good, and the pass / fail judgment was acceptable.

In Examples 17 and 18, as the metal compound (2-2), antimony pentoxide and copper iodide were used in place of antimony trioxide, respectively. However, under a load of 0.0054 mN / dtex, 50 ° C. to 300 ° C. The shrinkage variation when the temperature was increased to 45% or less, the combustion test result using the flame retardant evaluation specimen was good, and the pass / fail judgment was acceptable.

In Examples 19 and 20, tin oxide and zinc carbonate were used instead of zinc oxide as the metal compound (2-1), respectively, but the temperature was increased from 50 ° C. to 300 ° C. under a load of 0.0054 mN / dtex. The shrinkage fluctuation when raised was 45% or less, the combustion test result using the flame retardant evaluation specimen was good, and the pass / fail judgment was acceptable.

(Comparative Examples 1 to 10)
In Comparative Example 1, relaxation heat treatment was applied. However, since the flame-retardant synthetic fiber does not contain the metal compound (2-1), the temperature was increased from 50 ° C. to 300 ° C. under a load of 0.0054 mN / dtex. The shrinkage fluctuation when it was raised was 47%, which was 45% or more. Therefore, in the combustion test evaluation using the flame retardant test specimen, a hole is formed in the flame retardant nonwoven fabric used in the flame retardant test specimen during the combustion test, and the internal flammable urethane is ignited. However, because the test was stopped by forcibly extinguishing the fire, it failed.

In Comparative Example 2, the flame-retardant synthetic fiber had a shrinkage variation of 28% and 45% or less, but does not contain the metal compound (2-1). In the combustion test evaluation used, at the time of the combustion test, there was a hole in the non-woven fabric for flame retardant evaluation used in the test specimen for flame retardant evaluation, the internal flammable urethane was ignited, the fire was forcibly extinguished, and the test was stopped. As a result, it was rejected.

In Comparative Example 3, the halogen-containing fiber contains zinc oxide as the metal compound (2-1). However, the halogen-containing fiber was subjected to a dry heat treatment at 170 ° C. for 2 minutes in a tension state, so that the load was 0.0054 mN / dtex. When the temperature was raised from 50 ° C. to 300 ° C., the shrinkage variation was 67%, which was 45% or more. Therefore, during the combustion test, a crack occurred in the test body, and fire started from there and ignited the internal flammable urethane.

In Comparative Example 4, the halogen-containing fiber contains zinc oxide as the metal compound (2-1), but under a load of 0.0054 mN / dtex by wet heat treatment at 140 ° C. for 15 minutes in a tension state. When the temperature was raised from 50 ° C. to 300 ° C., the shrinkage variation was 48%, which was 45% or more. Therefore, during the combustion test, a crack occurred in the test body, and fire started from there and ignited the internal flammable urethane.

In Comparative Examples 5 and 7, the halogen-containing fiber did not contain the metal compound (2-1), and was wet-heat treated in a tension state at 130 ° C. for 15 minutes. Therefore, under a load of 0.0054 mN / dtex, Shrinkage fluctuations when the temperature was raised from 50 ° C. to 300 ° C. were 93% and 68%, respectively, and were 45% or more. Therefore, in the combustion test evaluation using the flame retardant test specimen, a hole is formed in the flame retardant nonwoven fabric used in the flame retardant test specimen during the combustion test, and the internal flammable urethane is ignited. However, because the test was stopped by forcibly extinguishing the fire, it failed.

In Comparative Example 6, the halogen-containing fiber contains metastannic acid as the metal compound (2-1). However, the moisture-containing fiber was subjected to a wet heat treatment at 130 ° C. for 15 minutes to obtain a load of 0.0054 mN / dtex. The shrinkage variation when the temperature was raised from 50 ° C. to 300 ° C. was 62%, which was 45% or more. Therefore, during the combustion test, a crack occurred in the test body, and fire started from there, and the internal flammable urethane was ignited.

In Comparative Example 8, the halogen-containing fiber had a total draw ratio of less than 4.8 times during spinning, but was wet-heat treated under tension at 130 ° C. for 15 minutes and further contained a metal compound (2-1). Therefore, the shrinkage variation when the temperature was increased from 50 ° C. to 300 ° C. under a load of 0.0054 mN / dtex was 63%, which was 45% or more. Therefore, in the combustion test evaluation using the flame retardant test specimen, a hole is formed in the flame retardant nonwoven fabric used in the flame retardant test specimen during the combustion test, and the internal flammable urethane is ignited. However, the test was stopped because the fire was forcibly extinguished, so it failed.

In Comparative Example 9, zinc oxide was contained as the metal compound (2-1), but the halogen-containing fiber was wet-heat treated in a tension state at 130 ° C. for 2 minutes, so that under a load of 0.0054 mN / dtex, When the temperature was raised from 50 ° C. to 300 ° C., the shrinkage variation was 65%, which was 45% or more. Therefore, during the combustion test, a crack occurred in the test body, and fire started from there and ignited the internal flammable urethane.

Comparative Example 10 contains aluminum hydroxide as the metal compound but does not contain the metal compound (2-1), so the temperature was raised from 50 ° C. to 300 ° C. under a load of 0.0054 mN / dtex. The shrinkage fluctuation at that time was 46%, which was 45% or more. Therefore, in the combustion test evaluation using the flame retardant test specimen, a hole is formed in the flame retardant nonwoven fabric used in the flame retardant test specimen during the combustion test, and the internal flammable urethane is ignited. However, the test was stopped because the fire was forcibly extinguished, so it failed.

(Examples 21 to 47, Comparative Examples 11 to 26)
In Examples 21 to 47, the mixing ratio of the halogen-containing fiber produced in Production Example 5 or 11 which is the flame-retardant synthetic fiber of the present invention in the fiber composite is 10% or more, and other components included in the fiber composite are included. Regardless of the type of fiber and the structure of the product, in various tests, excellent flame retardancy was exhibited, and all passed. On the other hand, in Comparative Examples 11 to 20, since the halogen-containing fiber produced in Production Example 22 that does not contain the metal compound (2-1) that promotes carbonization during combustion of the polymer (1) is used, The exam also failed. In Comparative Examples 21 to 26, the halogen-containing fiber produced in Production Example 5 which is the flame-retardant synthetic fiber of the present invention is used, but the mixture ratio of the halogen-containing fiber in the fiber composite is less than 10%. Both tests failed.

Table 2 below summarizes the flame retardant combustion test results of Examples 1 to 20 and Comparative Examples 1 to 10. Table 3 below summarizes the results of flame retardant combustion tests of Examples 21 to 47 and Comparative Examples 11 to 26.

[Table 2]

[Table 3]

FIG. 5 shows the halogen-containing fiber (A) obtained in Production Example 10 which is a flame-retardant synthetic fiber of the present invention, the current product modacrylic fiber (trade name “Protex-M” manufactured by Kaneka Corporation) (B), Each of the halogen-containing fibers (C) obtained in Production Example 29, which is a comparative product in the present invention, takes about 3 mm of 3333 dtex (decitex), and is heated in the atmosphere at a rate of temperature increase of 20 ° C./min, 18 mN. The results of measuring the shrinkage behavior from 50 ° C. to 300 ° C. or higher under load (corresponding to the tension applied to a normal product) are shown. The current product (B) as a comparative product shrinks from around about 180 ° C., peaks at about 205 ° C., then turns into elongation and cuts at about 250 ° C. Further, the fiber (C) obtained in Production Example 29 as a comparative example product greatly shrinks to about 200 ° C. when it exceeds about 180 ° C. In contrast, the fiber (A) obtained in Production Example 10 which is a product of the present invention gradually shrinks from above about 170 ° C., but the shrinkage rate is lower than that of the fiber (C), and It remains without being carbonized and cut.

Claims

In 100 parts by mass of the polymer, 30 to 70 parts by mass of acrylonitrile, 70 to 30 parts by mass of the halogen-containing vinylidene monomer and / or halogen-containing vinyl monomer, and 0 to 10 vinyl monomers copolymerizable therewith A polymer (1) containing parts by weight;
Including at least one metal compound (2) that promotes dehalogenation reaction during combustion and carbonization reaction during combustion of the polymer (1),
A flame-retardant synthetic fiber having a shrinkage variation of 45% or less when the temperature is raised from 50 ° C to 300 ° C under a load of 0.0054 mN / dtex.
The flame-retardant synthetic fiber according to claim 1, comprising 0.05 to 50 parts by mass of the metal compound (2) with respect to 100 parts by mass of the polymer (1).
Metal compound (2-1) in which the metal compound (2) promotes both dehalogenation reaction and carbonization reaction, or metal compound (2-2) in which the metal compound (2-1) promotes dehalogenation reaction The flame-retardant synthetic fiber according to claim 1 or 2, comprising a combination of the following.
The flame-retardant synthetic fiber according to claim 3, comprising 5 to 30 parts by mass of the metal compound (2-2) with respect to 100 parts by mass of the polymer (1).
The metal compound (2-1) is zinc oxide, zinc carbonate, zinc sulfide, zinc borate, zinc phosphate, zinc stannate, metastannic acid, tungsten oxide, zirconium oxide, tin oxide, copper oxide, copper phosphate, trioxide. The flame-retardant synthetic fiber according to claim 3, which is at least one selected from the group consisting of indium and barium titanate.
The flame-retardant synthetic fiber according to claim 5, wherein the metal compound (2-1) is at least one selected from the group consisting of zinc oxide, zinc stannate, zinc carbonate, and tin oxide.
The metal compound (2-2) is at least one selected from the group consisting of an antimony compound, iron oxide, iron phosphate, iron oxalate, iron sulfide, molybdenum oxide, bismuth trioxide, bismuth oxychloride, and copper iodide. The flame-retardant synthetic fiber according to claim 3 or 4.
The flame-retardant synthetic fiber according to claim 7, wherein the metal compound (2-2) is an antimony compound.
The flame-retardant synthetic fiber according to claim 1, further comprising 0.1 to 20 parts by mass of an epoxy group-containing compound with respect to 100 parts by mass of the polymer (1).
The flame retardant synthetic fiber according to claim 9, wherein the epoxy group-containing compound is glycidyl methacrylate.
The polymer (1) comprises 40 to 60 parts by mass of acrylonitrile, 60 to 30 parts by mass of a halogen-containing vinylidene monomer and / or a halogen-containing vinyl monomer, and 0 to 30% of a vinyl monomer copolymerizable therewith. The flame-retardant synthetic fiber according to claim 1, containing 10 parts by mass.
In 100 parts by mass of the polymer, 30 to 70 parts by mass of acrylonitrile, 70 to 30 parts by mass of the halogen-containing vinylidene monomer and / or halogen-containing vinyl monomer, and 0 to 10 vinyl monomers copolymerizable therewith A polymer (1) containing parts by weight;
A composition containing at least one metal compound (2) that promotes the dehalogenation reaction during combustion and the carbonization reaction during combustion of the polymer (1) is spun and then heat-treated, whereby 0.0054 mN / A method for producing a flame-retardant synthetic fiber, comprising obtaining a flame-retardant synthetic fiber having a shrinkage variation of 45% or less when the temperature is increased from 50 ° C to 300 ° C under a load of dtex.
The method for producing a flame-retardant synthetic fiber according to claim 12, wherein the heat treatment is a relaxation heat treatment in a dry heat of 140 ° C or higher or a wet heat of 90 ° C or higher.
The method for producing a flame-retardant synthetic fiber according to claim 12, wherein the heat treatment is a tension heat treatment in a dry heat of 180 ° C or higher or a wet heat of 150 ° C or higher.
The method for producing a flame-retardant synthetic fiber according to claim 12 or 13, wherein the heat treatment is a relaxation heat treatment in a wet heat pressurized steam at 100 ° C or higher.
The method for producing a flame-retardant synthetic fiber according to any one of claims 12 to 15, comprising 0.05 to 50 parts by mass of the metal compound (2) with respect to 100 parts by mass of the polymer (1).
12. At least one selected from the group consisting of 10% by mass or more of the flame retardant synthetic fiber according to any one of claims 1 to 11, and natural fiber, regenerated fiber, and synthetic fiber other than the flame retardant synthetic fiber. A flame-retardant fiber composite comprising 90% by mass or less of fibers.
The flame retardant fiber composite according to claim 17, wherein the synthetic fiber other than the flame retardant synthetic fiber is a polyester fiber, and the content in the flame retardant fiber composite is 40% by mass or more.
A textile product comprising the flame-retardant synthetic fiber according to any one of claims 1 to 11.