JPH05239728A - Production of flame-retardant composite fiber - Google Patents

Abstract

PURPOSE:To provide the subject flame-retardant composite fiber having a desired flame retardancy and exhibiting satisfactory performances such as visual appearance, touch, moisture absorption, washing resistance and durability. CONSTITUTION:This invention is related to a method for characteristically producing a flame-retardant composite fiber by adding 8 to 50wt.% Sb compound to a polymer mixture composed of a halogen-containing polymer and a partially acetalized polyvinyl alcohol in a weight ratio of (the halogen-containing polymer)/(the partially acetalized polyvinyl alcohol)=(6/4) to (4/6), spinning the resultant mixture into a fiber and compounding 85 to 15 pts.wt. of the resultant fiber with 15 to 85 pts.wt. one or more kinds of fibers selected from natural fibers and chemical fibers so that the total amount may be 100 pts.wt.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention is a composite flame retardant having excellent flame feeling and hygroscopicity and having flame retardancy by mixing polyclar fiber highly flame retarded with a flame retardant and other fibers. Regarding the manufacturing method of fiber.

[0002]

2. Description of the Related Art In recent years, there has been a strong demand for flame retardancy not only in interiors but also in textile products for clothing. In addition to flame retardancy, performances such as visual sensation, texture, moisture absorption, washing resistance, durability, etc. Demand is growing.

[0003] Conventionally, research on flame retardation of fibers has been conducted mainly on modacrylic fibers and polyclar fibers, and single fibers such as polyester fibers and viscose rayon fibers have been studied. Although some fibers have excellent flame-retardant performance as a single substance, the present 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 phosphorus-containing polyester fiber and acrylonitrile fiber (Japanese Patent Publication No. 52-2).
1612) and composite fibers made by mixing polyclar fibers containing stannic acid and antimonic acid with polyester fibers, acrylic fibers, cotton, etc. (JP-A-53-6617) are effective. It is hard to say that it has sufficient flame retardancy, texture, and hygroscopicity.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a fiber that can meet consumers' increasingly diverse and sophisticated requirements for flame retardancy, visual feeling, texture, moisture absorption, washing resistance, durability, etc. It was made to solve the problem of not having it.

[0006]

Means for Solving the Problems The inventors of the present invention have made extensive studies in view of the above-mentioned circumstances, and as a result, have made a polyclar fiber containing a large amount of Sb compound and highly flame-retarded,
It has been found that, when mixed with other combustible fibers to form a composite fiber, the degree of reduction in flame retardancy is extremely small as compared with the conventional flame retardant fiber, and the present invention has been completed.

That is, the present invention relates to a polymer mixture having a halogen-containing polymer / partially acetalized polyvinyl alcohol (hereinafter referred to as partially acetalized PVA) in a weight ratio of 6/4 to 4/6. To 8 to 50% (wt%, the same below) of Sb compound produced at 85 to 15 parts (wt part, the same below) and at least one selected from the group consisting of natural fibers and chemical fibers Fiber 15 ~
The present invention relates to a method for producing a composite flame-retardant fiber, which is characterized by compounding 85 parts with a total amount of 100 parts, and having desired flame retardancy, visual feeling, texture, moisture absorption, resistance to A composite flame-retardant fiber that satisfies performance such as washability and durability can be obtained.

[0008]

Examples Halogen-containing polymers used in the present invention include, for example, 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 preferably 20% or more in order to maintain 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 can be used.

In the present invention, a polymer mixture having a halogen-containing polymer / partially acetalized PVA in a weight ratio of 6/4 to 4/6 (hereinafter referred to as a halogen-containing polymer / partially acetalized PVA mixture) is Fibers made from compositions containing 8-50% Sb compound to halogen-containing polymer / partially acetalized PVA mixture (hereinafter 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 partial acetalized PVA of If the ratio is less than the above range, 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 deterioration of general fiber performance such as strength and heat resistance occurs. 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 , Sb ₂ O ₄ , Sb ₂ O _5, etc.), antimonic acid, antimony oxychloride. Examples of the inorganic antimony compound include, but are not limited to. These may be used alone or in combination of two or more.

Halogen-containing polymer / partially acetalized P
The ratio of Sb compound to the VA mixture is 8-50%, preferably 8-40%. 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 physical properties (strength, elongation, etc.) occur, and Sb-containing polyclar fiber which is highly flame-retardant. This is not preferable because it causes problems in terms of manufacturing and quality.

In the present invention, the amount of the flame retardant based on the halogen-containing polymer / partially acetalized PVA mixture is 8 to.
50%, which may be used in combination with other flame retardants.

Examples of the flame retardant that can be used in combination with the Sb compound include inorganic materials such as stannic oxide, metastannic acid, stannous oxyhalide, stannic oxyhalide, stannous hydroxide and the like. Tin compounds, aromatic halides such as hexabromobenzene, aliphatic halides such as chloroparaffin, halogen-containing phosphorus compounds such as tris (2,3-dichloropropyl) phosphate, organic phosphorus compounds such as dibutylaminophosphate, polyphosphoric acid Examples thereof include inorganic phosphorus compounds such as ammonium.

In the present invention, 100 parts of the composite flame-retardant fiber of the present invention comprises 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. Is manufactured.

The proportion of the Sb-containing polyclar fiber used in the present invention and at least one fiber selected from the group consisting of natural fibers and chemical fibers depends on the flame retardancy, visual sensation, texture and moisture absorption required for the final product. It is determined by performance such as durability, washing resistance and durability. In addition, the above-mentioned use ratio is determined depending on the kind and composition ratio of the halogen-containing polymer used for producing the Sb-containing polyclar fiber, the kind and addition amount of the flame retardant, the kind and combination of fibers mixed in the composite flame-retardant fiber, etc. Can be decided.

Less than 15 parts of the Sb-containing polyclar fiber, that is, the ratio of natural fiber and chemical fiber to be mixed is
When the mixing ratio exceeds 85 parts, the composite fiber has poor flame retardancy, while the Sb-containing polyclar fiber exceeds 85 parts,
When the mixing ratio of the natural fiber and the chemical fiber to be mixed is less than 15 parts, other visual feeling, texture, although excellent in flame retardancy,
Performance such as hygroscopicity, washing resistance, durability is not sufficient,
Neither is preferable.

The reason why the composite flame-retardant fiber according to the present invention has excellent flame retardancy is that the Sb-containing polyclar fiber is mixed with a large amount of the Sb compound having a gas-type flame-retardant effect, and thus it comes into contact with the fire source. At this time, it is presumed that gases such as incombustible hydrogen halide, halogen, and antimony halide are generated at a relatively low temperature, and the incombustible decomposition product covers the combustible fiber.

Specific examples of the natural fibers include vegetable fibers such as cotton and hemp, animal fibers such as wool and silk, and specific examples of the chemical fibers include regenerated fibers such as rayon fibers and cupra fibers. Examples thereof include, but are not limited to, semi-synthetic fibers such as acetate fibers, and synthetic fibers such as nylon fibers, polyester fibers, and acrylic fibers. 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. During production, the flame retardant such as an inorganic metal compound is sufficiently crushed by a vibration mill or the like to have a particle size of By adjusting the thickness to 2 μm or less, it is possible to carry out the production by a normal spinning method without causing a trouble in spinning such as nozzle clogging or yarn breakage. In addition, colloidal Sb fine powder or a colloidal aqueous solution of Sb may be added to the spinning dope, or an aqueous solution of a water-soluble Sb compound may be added immediately before the nozzle in order to change the dullness of the Sb-containing polyclar fiber and the smoothness of the fiber surface. After mixing with the spinning dope of (1) and then spinning, it may be contained in the fiber in the form of a substantially water-insoluble Sb compound.

As a method for producing the composite flame-retardant fiber, it is possible to mix cotton in the state of a single fiber, mix-spin it, or twist it. Of course, it may be lumped into a slab, a nep, or wound during spinning.

The term "fiber" in the present specification 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.

If desired, the composite flame-retardant fiber according to the present invention may contain an antistatic agent, a heat discoloration preventing agent, a light resistance improving agent, a whiteness improving agent, a devitrification preventing agent and the like. Of course.

Thus, the composite flame-retardant fiber obtained by the production method of the present invention has desired flame-retardant properties, and the visual feeling, feel, hygroscopicity, washing resistance and durability of other fibers to be mixed. It also has characteristics such as sex.

Hereinafter, the production method of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to such Examples. The flame retardancy of the fibers in the examples was measured by 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.

(Combustibility) 2 g of cotton mixed in a predetermined ratio
Take this, divide it into 8 equal pieces, and make 8 pieces of 6 cm-long twist, stand upright on the holder of the oxygen index tester, measure the minimum oxygen concentration required for this sample to continue burning for 5 cm, and use this LO
The I value was used. The larger the LOI value, the harder it is to burn and the higher the flame resistance.

Production Examples 1 and 2 PVA having an average degree of polymerization of 1700 and a saponification degree of 99 mol% was dissolved in water at 70 ° C. to prepare a 16% PVA aqueous solution.
% Polyvinyl chloride (hereinafter referred to as PVC) emulsion, and a separately prepared 50% concentration antimony trioxide (average particle size 1.1 μm) aqueous dispersion is added and well stirred, and the weight ratio of PVC: PVA: Antimony trioxide = 50:
A spinning stock solution with a resin concentration of 21.0% was prepared at 50:15.

This spinning solution was discharged into a saturated Glauber's salt aqueous solution (350 g / liter) 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, stretched and heat treated. I did.

The obtained fiber is further acetalized in an acetalization bath at 70 ° C., neutralized with an aqueous sodium carbonate solution, washed with water and dried, and the weight ratio of PVC: partially acetalized PVA: antimony trioxide = 49. : 51:15 2d
The Sb-containing polyclar fiber with high flame retardancy was obtained (Production Example 1).

On the other hand, in the same manner, 15% metastannic acid was added to the above resin instead of antimony trioxide, and the same spinning was performed, and the weight ratio of PVC: partially acetalized PVA: metastannic acid = 50: 50: 15 was 2d. Polyclar fiber 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 and cotton were mixed at a ratio shown in Table 1 to form a composite fiber. I got it.

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

The characteristics of the composite fiber as cotton (visual feeling,
A sensory test was conducted to determine whether or not the product had a texture). The results are shown in Table 1.

In Table 1, ◯ means that cotton has characteristics, and x means that it does not.

[0036]

[Table 1]

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

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 form a composite fiber. (Corresponding to the composite fiber of Example 2 for cotton).

The LOI value of each of the obtained composite fiber and Sb-containing polyclar fiber itself was determined,
I calculated the difference. The results are shown in Table 2.

Comparative Example 10 Using the polyclar fiber containing 15% of metastannic acid obtained in Production Example 2 and mixing in the same manner as in Example 5, a composite fiber was obtained.

The LOI value of each of the obtained conjugate fiber and polyclar fiber itself was determined, and the difference between them was determined. The results are shown in Table 2.

[0042]

[Table 2]

From the results of Table 2, Sb obtained in Production Example 1
It can be seen that the conjugate fiber of the present invention using the contained polyclar fiber (Example 5) has less decrease in LOI value as compared with the conjugate fiber using metastannic acid obtained in Production Example 2 (Comparative Example 10). .

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

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

Examples 6-8 and Comparative Examples 11-14 50 parts of cotton and 50 parts of cotton, respectively, of the polyclar fiber obtained in Production Examples 3-9, the Sb-containing polyclar fiber and the comparative Sb-containing polyclar fiber were mixed. , A composite fiber was obtained.

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

[0048]

[Table 3]

From the results shown in Table 3, when polyclar fiber containing 10 to 50% of antimony trioxide (Sb-containing polyclar fiber) is used, the flame retardancy of a composite fiber of 50 parts of Sb-containing polyclar fiber and 50 parts of cotton is shown. It turns out that sex can be advanced. Moreover, these Sb-containing polyclar fibers can be produced without problems in spinning such as nozzle clogging and yarn breakage.

[0050]

When the composite flame-retardant fiber of the present invention is used, it has desired flame-retardant properties, and it is difficult to obtain 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 a composite fiber obtained by mixing cotton with each of the Sb-containing polyclar fiber obtained in Production Example 1 and the comparative polyclar fiber obtained in Production Example 2; It is a graph which shows the relationship between a mixed cotton ratio.

Claims (1)

[Claims] 1. Fiber produced by adding 8 to 50% by weight of Sb compound to a polymer mixture having a halogen-containing polymer / partially acetalized polyvinyl alcohol weight ratio of 6/4 to 4/6 85 to 15 parts by weight of fibers and 15 to 85 parts by weight of at least one fiber selected from the group consisting of natural fibers and chemical fibers are combined so that the total amount becomes 100 parts by weight. Fiber manufacturing method.