JPH0611930B2 - Composite flame retardant fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is a mixture of polyclar fiber highly flame-retarded and strengthened with a flame retardant and other fibers, and is excellent in feeling and hygroscopicity,
The present invention also relates to a composite flame-retardant fiber having flame retardancy.

[Prior Art] In recent years, there has been a strong demand for flame retardancy not only in interiors but also in textile products for clothing, and in addition to flame retardancy, performance such as visual feeling, texture, moisture absorption, washing resistance, durability, etc. Demand is growing.

BACKGROUND ART Conventionally, research on flame retardancy of fibers has been conducted on single fibers such as polyester fibers and viscose rayon fibers, centered on modacrylic fibers and polyclar fibers. Although some products have excellent flame-retardant performance, the current situation is that they have hardly met the increasingly diverse and sophisticated demands of consumers. Therefore, it is inevitably necessary to mix cotton, flame-spun fibers, and other fibers with each other, but there are few studies on flame-retardant composite fibers in which two or more different kinds of fibers are mixed.

For example, a composite fiber obtained by mixing a phosphorus-containing polyester fiber and an acrylonitrile fiber (Japanese Patent Publication No. 52-21612).
Also, there is a description that composite fibers obtained by mixing polyclar fibers containing stannic acid and antimonic acid with polyester fibers, acrylic fibers, cotton (JP-A-53-6617) are effective, but flame retardance, It is hard to say that it has sufficient feeling and hygroscopicity.

[Problems to be Solved by the Invention] The present invention is a fiber that can meet consumers' increasingly diverse and sophisticated requirements for flame retardancy, visibility, feeling, moisture absorption, washing resistance, durability, etc. It was made to solve the problem that there is no.

[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies in view of the above-mentioned circumstances, and as a result, have made a polyflame fiber containing a large amount of Sb compound and highly flame-retarded into another flammable material. The present invention has been completed by finding that the degree of reduction in flame retardancy is extremely small when mixed with a functional fiber to form a composite fiber, as compared with a conventional flame-retardant fiber.

That is, the present invention relates to a halogen-containing polymer / partially acetalized polyvinyl alcohol (hereinafter, partially acetalized PV
A) is a polymer mixture whose weight ratio is 6/4 to 4/6,
8 to 50% (wt%, the same applies hereinafter) of the polymer mixture
From 85 to 15 parts of fibers containing Sb compound (parts by weight, the same applies below) and 15 to 85 parts of at least one selected from the group consisting of natural fibers and chemical fibers, the total amount becomes 100 parts. The present invention relates to a composite flame-retardant fiber characterized by being compounded, having desired flame retardancy and satisfying performances such as visual feeling, texture, hygroscopicity, washing resistance and durability. .

Examples Examples of the halogen-containing polymer used in the present invention include homopolymers and copolymers of halogen-containing monomers such as vinyl chloride and vinylidene chloride, monomers copolymerizable with these halogen-containing monomers, such as acrylonitrile, Examples thereof include, but are not limited to, a copolymer with styrene, vinyl acetate, an acrylic ester, or a graft polymer in which a halogen-containing monomer is grafted on a PVA-based polymer. These halogen-containing polymers may be used alone or in combination. The chlorine content of the halogen-containing polymer is 20%
The above is preferable for maintaining flame retardancy.

The partially acetalized PVA used in the present invention is not particularly limited, and the partially acetalized PVA used for ordinary fiber production is used.
PVA can be used.

In the present invention, the halogen-containing polymer / partial acetalized PVA is a polymer mixture having a weight ratio of 6/4 to 4/6 (hereinafter,
Halogen-containing polymer / partially acetalized PVA mixture)
A fiber produced from a composition containing 8 to 50% of Sb compound with respect to the mixture (hereinafter referred to as Sb-containing polyclar fiber) is used.

When the ratio of the halogen-containing polymer in the halogen-containing polymer / partial acetalized PVA mixture is smaller than the above range, the desired high flame retardancy cannot be obtained, and conversely, the ratio of the partially acetalized PVA is the above. When the content is smaller than the range, the stability and spinnability of a spinning dope containing an aqueous emulsion of a halogen-containing polymer and a partially acetalized PVA aqueous solution mixture, or general fiber performance such as strength and heat resistance is deteriorated, which is not preferable.

The Sb compound used in the present invention is used as a flame retardant, and specific examples thereof include antimony oxide (Sb ₂ O ₃ ,
Examples thereof include inorganic antimony compounds such as Sb ₂ O ₄ , Sb ₂ O _5, etc.), antimonic acid, antimony oxychloride, etc., but are not limited thereto. These may be used alone or in combination of two or more.

The proportion of the Sb compound in the halogen-containing polymer / partially acetalized PVA mixture is 8 to 50%, preferably 8 to 40%. If the amount is less than 8%, it is necessary to increase the mixing ratio of the antimony-containing polyclar fiber in the composite flame-retardant fiber in order to obtain the flame-retardant property required as the composite flame-retardant fiber. , It becomes difficult to obtain performances such as visual feeling, feeling, hygroscopicity, washing resistance, and durability. On the other hand, when the amount exceeds 50%, nozzle clogging during production of Sb-containing polyclar fiber and deterioration of fiber properties (strength, elongation, etc.) occur, and Sb-containing polyclar fiber that is highly flame-retarded. Problems such as manufacturing and quality of
Not preferable.

Halogen-containing polymer / partial acetalization in the present invention
The amount of flame retardant relative to the PVA mixture is 8-50%, which may be combined with other flame retardants.

Examples of the flame retardant that can be used in combination with the Sb compound include inorganic tin compounds such as stannic oxide, metastannic acid, stannous oxyhalide, stannic oxyhalide, stannous hydroxide, and hexa. Aromatic halides such as bromobenzene, aliphatic halides such as chlorinated paraffins, halogen-containing phosphorus compounds such as tris (2,3-dichloropropyl) phosphate, organic phosphorus compounds such as dibutylaminophosphate, inorganics such as ammonium polyphosphate Examples include phosphorus compounds.

In the present invention, 100 parts of the composite flame-retardant fiber of the present invention is produced from 15 to 85 parts of Sb-containing polyclar fiber and 85 to 15 parts of at least one fiber selected from the group consisting of natural fibers and chemical fibers. It

The use ratio of the Sb-containing polyclar fiber and at least one fiber selected from the group consisting of natural fibers and chemical fibers in the present invention is such that the flame retardancy, visual feeling, feel, hygroscopicity required for the final product, It is determined by performance such as washing resistance and durability. The type and composition ratio of the halogen-containing polymer used to produce the Sb-containing polyclar fiber, the type and addition amount of the flame retardant, the type and combination of the fibers mixed in the composite flame-retardant fiber, the use ratio is Can be decided

The Sb-containing polyclar fiber is less than 15 parts, that is, the mixing ratio of the natural fiber and the chemical fiber to be mixed exceeds 85 parts, the composite fiber has poor flame retardance, while the Sb-containing polyclar fiber exceeds 85 parts and is mixed. With a mixing ratio of less than 15 parts of natural fibers or chemical fibers to be used, other visual properties such as flame retardancy, texture, hygroscopicity, washing resistance, durability and other performance are not sufficient, Neither is preferable.

The reason why the composite flame-retardant fiber of the present invention has excellent flame retardancy is
Sb with gas-type flame retardant effect on Sb-containing polyclar fiber
Since a large amount of the compound is mixed, when it comes into contact with a fire source, it produces incombustible hydrogen halide gas, halogen, antimony halide, and other gases at a relatively low temperature, and its incombustible decomposition products are flammable fibers. It is presumed that it will cover the.

Specific examples of the natural fibers include plant fibers such as cotton and hemp, and material fibers such as wool and silk. Specific examples of the chemical fibers include regenerated fibers such as rayon fibers and cupra fibers, and acetate fibers. Semi-synthetic fiber, such as
Alternatively, synthetic fibers such as nylon fibers, polyester fibers, and acrylic fibers may be used, but the present invention is not limited to these. These natural fibers and chemical fibers may be compounded with the Sb-containing polyclar fiber alone or in combination of two or more kinds with the Sb-containing polyclar fiber.

The Sb-containing polyclar fiber used in the present invention contains a large amount of a flame retardant such as an inorganic metal compound, but at the time of production, the flame retardant such as an inorganic metal compound is sufficiently pulverized by a vibration mill or the like to have a particle size of 2 μm or less. By aligning, it is possible to manufacture by a normal spinning method without causing troubles in spinning such as nozzle clogging and yarn breakage. If necessary, in order to change the dullness of Sb-containing polyclar fiber and the smoothness of the fiber surface, colloidal Sb fine powder or a colloidal solution of Sb is added to the spinning dope, or water-soluble.
The aqueous solution of the Sb compound may be mixed with the spinning stock solution facing the nozzle and then spun, so that it is contained in the fiber in the form of the substantially water-insoluble Sb compound.

As the method for producing the composite flame-retardant fiber, kneading in a single fiber state, kneading or spinning, or twisting may be performed. After each yarn is produced, it may be knitted and woven. At the time of, it may be lumped into a slab, a nep, or wrapped.

The term "fiber" as used herein is a concept including not only so-called fibers such as long fibers and short fibers but also fiber products such as yarns, woven fabrics, knitted fabrics, and non-woven fabrics.

The composite flame-retardant fiber of the present invention, if necessary, an antistatic agent,
As a matter of course, a heat discoloration preventing agent, a light resistance improving agent, a whiteness improving agent, a devitrification preventing agent and the like may be contained.

The thus obtained composite flame-retardant fiber of the present invention has desired flame-retardant properties, and has characteristics such as visual feeling, feeling, hygroscopicity, washing resistance and durability of other fibers to be mixed. I have both.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. The flame retardancy of the fibers in the examples is based on the oxygen index method (LOI
Method) as follows. This is because the flame retardancy of the fiber is generally measured and evaluated in the state of the woven fabric, but in the woven fabric, the flammability of the fiber itself changes due to the difference in the flammability depending on the number of twists, the thickness, and the number of threads. Because it cannot be evaluated correctly.

(Flammability) Take 2 g of cotton mixed in a predetermined ratio, divide it into 8 equal parts, and make 8 pieces of about 6 cm of twist to stand upright in the holder of the oxygen index tester, necessary for this sample to continue burning 5 cm. The minimum oxygen concentration was measured and used as the LOI value. The larger the LOI value, the less likely it is to burn and the higher the flame resistance.

Production Examples 1-2 PVA having an average degree of polymerization of 1700 and a degree of saponification of 99 mol% was dissolved in water at 70 ° C to prepare a 16% aqueous solution of PVA, in which a polyvinyl chloride (hereinafter referred to as PVC) having a concentration of 30% was prepared. ) Add the emulsion, and then add a separately prepared 50% concentration antimony trioxide (average particle size 1.1 μm) aqueous dispersion and stir well,
A spinning dope having a weight ratio of PVC: PVA: antimony trioxide = 50: 50: 15 and a resin concentration of 21.0% was prepared.

This spinning solution stock solution was discharged into a saturated Glauber's salt aqueous solution (350 g /) at 45 ° C. by a wet emulsion spinning method, then heat-treated in a saturated Glauber's salt aqueous solution at 95 ° C., washed with water, dried, and stretched.
Heat treatment was performed.

The obtained fibers are further acetalized in an acetalizing solution at 70 ° C, then neutralized with an aqueous sodium carbonate solution, washed with water,
After drying, a 2d highly flame-retarded Sb-containing polyclar fiber having a weight ratio of PVC: partially acetalized PVA: antimony trioxide = 49: 51: 15 was obtained (Production Example 1).

On the other hand, instead of antimony trioxide, 15% metastannic acid was added to the above resin, similarly spun, and the PV
C: Partial acetalization PVA: Metastannic acid = 50:50:15 2d
Polyclar fiber of was produced for comparison (Production Example 2).

Examples 1 to 4 and Comparative Examples 1 to 9 Each of the Sb-containing polyclar fiber obtained in Production Example 1 and the polyclar fiber for comparison was mixed with cotton at a ratio shown in Table 1 to obtain a composite fiber.

A sample for flammability test is prepared using the obtained composite fiber,
LOI value was measured. The results are shown in Table 1 and FIG.

In addition, a sensory test was conducted to determine whether or not the composite fiber has characteristics (visual feeling, texture, etc.) as cotton. The results are shown in Table 1.

In addition, ◯ in Table 1 has characteristics as cotton. X indicates that it does not have.

From the results shown in Table 1, the Sb-containing polyclar fiber (Production Example 1) used in the present invention, when mixed with cotton, was used in the present invention when the mixing ratio of cotton was 20 to 85 parts, as compared with the Polyclar fiber (Production Example 2). It can be seen that the use of the Sb-containing polyclar fiber used in Example 1 has a much smaller decrease in flame retardancy than the one using polyclar fiber, exhibits a high LOI value, and is excellent in flame retardancy.

Example 5 60 parts of polyclar fiber (Sb-containing polyclar fiber) containing 15% of antimony trioxide obtained in Production Example 1 and 40 parts of fibers such as cotton shown in Table 2 were mixed to obtain a composite fiber ( In the case of cotton, it corresponds to the composite fiber of Example 2).

The LOI values of the obtained composite fiber and Sb-containing polyclar fiber itself were calculated, and the difference between them was calculated.
The results are shown in Table 2.

Comparative Example 10 The polyclar fiber containing 15% of metastannic acid obtained in Production Example 2 was mixed in the same manner as in Example 5 to obtain a composite fiber.

LOI values were calculated using the obtained composite fiber and polyclar fiber itself, and the difference between them was calculated. The results are shown in Table 2.

From the results of Table 2, the composite fiber of the present invention using the Sb-containing polyclar fiber obtained in Production Example 1 (Example 5) is the composite fiber using methanestannic acid obtained in Production Example 2 (Comparative Example). It can be seen that the LOI value decreases less than that in 10).

Production Examples 3 to 9 PVC: partially acetalized PVA: antimony trioxide in weight ratio of 49: 51: 0, 49: 51: 2, 49: 51: 6, 49:
51:10, 49:51:20, 49:51:50, 49:51:70 (manufacturing examples 3 to 9), except that the polyclar fiber (manufacturing example 3) was prepared in the same manner as in manufacturing example 1. Sb-containing polyclar fibers (Production Examples 6 to 8) and Sb-containing polyclar fiber (Production Examples 4, 5, and 9) for comparison were obtained.

PVC: partially acetalized PVA: antimony trioxide
In the case of 49:51:70, the nozzle was clogged and thread breakage occurred.

Examples 6 to 8 and Comparative Examples 11 to 14 50 parts each of the polyclar fiber obtained in Production Examples 3 to 9, the Sb-containing polyclar fiber and the Sb-containing polyclar fiber for comparison were mixed and mixed to form a composite fiber. I got it.

The LOI value was measured using the obtained conjugate fiber. The results are shown in Table 3.

From the results in Table 3, the added amount of antimony trioxide is 10-50.
It can be seen that the flame retardancy of the composite fiber of 50 parts of Sb-containing polyclar fiber and 50 parts of cotton can be enhanced by using poly% Claral fiber (Sb-containing polyclar fiber). Moreover, these Sb-containing polyclar fibers can be produced without problems in spinning such as nozzle clogging and yarn breakage.

[Advantages of the Invention] When the composite flame-retardant fiber of the present invention is used, it has desired flame retardancy, and it is difficult to obtain it from a single flame-retardant fiber alone. Interior textiles and textiles for clothing, which have characteristics such as washability and durability, can be obtained, and can meet the increasingly diverse and sophisticated demands of consumers.

[Brief description of drawings]

FIG. 1 is a LOI value obtained by using the Sb-containing polyclar fiber obtained in Production Example 1 and the comparative polyclar fiber obtained in Production Example 2 and a composite fiber obtained by mixing cotton with each other. It is a graph which shows the relationship between a mixed cotton ratio.

Claims (1)

[Claims] 1. A polymer mixture having a halogen-containing polymer / partially acetalized polyvinyl alcohol in a weight ratio of 6/4 to 4/6 is allowed to contain 8 to 50% by weight of the Sb compound with respect to the polymer mixture. 85 to 15 parts by weight of fibers and at least one fiber selected from the group consisting of natural fibers and chemical fibers 15 to 15 parts by weight
Composite flame-retardant fiber characterized by being compounded so that the total amount becomes from 85 parts by weight to 100 parts by weight.