JP2812672B2 - Manufacturing method of flame retardant fiber composite - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite of a halogen-containing fiber highly reinforced with a flame retardant and another fiber.
The present invention relates to a method for producing a flame-retardant fiber composite having excellent feel and moisture absorption and having flame retardancy. More specifically, it is a flame retardant
The present invention relates to a method for producing a flame-retardant fiber composite in which a halogen-containing fiber containing a large amount of an Sb compound and at least one kind of fiber selected from the group consisting of natural fiber and chemical fiber. In recent years, there has been a strong demand for flame retardancy not only in interiors, but also in textiles for clothing and bedding, and in addition to the flame retardancy, visual sensation, feeling, moisture absorption, washing resistance, and the like. Demands for performance such as durability are also increasing. [0003] Conventionally, research on flame retardancy of fibers has been carried out on single fibers of specific fibers such as polyester fibers and viscose rayon fibers, mainly on modacrylic fibers and polychloral fibers. Some of the products alone have excellent flame retardant performance, but at present they hardly meet the diversifying and sophisticated demands of consumers. Therefore, blending, blending, weaving, and the like of the flame-retardant fiber and other fibers are inevitably required. However, there are few studies on flame-retardation of composite fibers in which two or more kinds of different fibers are mixed. [0004] For example, a composite fiber obtained by mixing a phosphorus-containing polyester fiber and an acrylonitrile fiber (Japanese Patent Publication No. 52-2)
No. 1612) and a composite fiber obtained by mixing stannic acid and antimonic acid-containing polychloral fiber with polyester fiber, acrylic fiber, cotton, etc. (JP-A-53-6617) is effective. It is not enough in terms of flame retardancy, feeling, hygroscopicity, etc. [0005] The present invention addresses the increasingly diversified and sophisticated demands of consumers for flame retardancy, visual sensation, feeling, moisture absorption, washing resistance, durability and the like. This was done to solve the problem of no fibers being produced. Means for Solving the Problems The inventors of the present invention have made intensive studies in view of the above circumstances and as a result, have found that a fiber comprising a halogen-containing polymer containing a large amount of an Sb compound is different from other combustible fibers. It has been found that when mixed, a flame-retardant fiber composite is obtained in which the degree of decrease in flame retardancy is extremely small as compared with conventional flame-retardant fibers, and the present invention has been completed. That is, the present invention relates to acrylonitrile 30
To 70% (% by weight, hereinafter the same), a copolymer comprising 70 to 30% of a halogen-containing vinyl monomer and 0 to 10% of a vinyl monomer copolymerizable therewith, provided that the halogen is 19.9 to
A polymer containing 43.9%, and acrylonitrile 40 to
65% and vinylidene chloride and vinyl chloride in total
Excluding consisting 60-35% polymer, (hereinafter also referred to as halogen-containing copolymer), a of 12 to 50% relative to the copolymer
Incorporating Sb compound with particle size of 2μm or less, melt spinning
For 85 to 15 parts (parts by weight, hereinafter the same) of the obtained fiber (hereinafter, also referred to as halogen Sb-containing fiber), at least one fiber selected from the group consisting of natural fibers and chemical fibers ( hereinafter also referred to as other fiber) 15 to 85 parts including Maseru the
The present invention relates to a method for producing a flame-retardant fiber composite, which has a desired flame retardancy and diversifies consumers such as luminosity, feeling, moisture absorption, washing resistance and durability. To manufacture flame-retardant fiber composites that meet advanced requirements
Regarding that. [0008] The flame-retardant fiber composite is obtained by blending or blending a halogen-containing Sb-containing fiber with another fiber.
Sb-containing fibers and other fibers intertwisted, yarns produced using the blended or blended yarns, or interwoven or interwoven knitted fabrics produced using the intertwisted yarns, and combinations thereof. It is a concept that includes what is obtained by In the present invention, acrylonitrile 30-70
%, 70 to 30% of a halogen-containing vinyl monomer and 0 to 10% of a vinyl monomer copolymerizable therewith, provided that the polymer contains 19.9 to 43.9% of halogen.
And acrylonitrile 40-65% and vinyl chloride
Polymer consisting of 60-35% of den and vinyl chloride in total
Except, the (halogen-containing copolymer), fibers which contains a copolymerization Sb compound 12 to 50% of the particle size aligned to 2μm or less with respect to body is used. Examples of the halogen-containing copolymer used in the present invention include acrylonitrile-vinylidene chloride, acrylonitrile-vinyl chloride, acrylonitrile-vinyl chloride-vinylidene chloride, acrylonitrile-vinyl bromide, acrylonitrile-vinylidene chloride-vinyl bromide,
A copolymer of a halogen-containing vinyl monomer such as acrylonitrile-vinyl chloride-vinyl bromide and acrylonitrile, and one kind of a halogen-containing vinyl monomer such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinylidene bromide. Examples thereof include, but are not limited to, acrylonitrile and a copolymer of a vinyl monomer copolymerizable therewith. Further, the above copolymers may be appropriately mixed and used. The halogen-containing copolymer referred to in the present specification does not contain a partially acetalized polyvinyl alcohol in any form. The copolymerizable vinyl monomers include, for example, acrylic acid, esters thereof, methacrylic acid, esters thereof, acrylamide, methacrylamide, vinyl acetate, vinylsulfonic acid, salts thereof, methacrylsulfonic acid, salts thereof , Styrene sulfonic acid, salts thereof, and the like, and one or a mixture of two or more thereof can be used. The halogen-containing copolymer is a polymer comprising 30 to 70% of acrylonitrile, 70 to 30% of a halogen-containing vinyl monomer and 0 to 10% of a vinyl monomer copolymerizable therewith , provided that halogen is used. Containing 19.9 to 43.9%
And 40 to 65% of acrylonitrile and chloride
Vinylidene and vinyl chloride consist of 60-35% in total
Excluding the polymer , the obtained fiber is preferable because it has a desired fibrous property and a feeling of an acrylic fiber. When at least one of the copolymerizable vinyl monomers is a sulfonic acid group-containing vinyl monomer, the dyeability is improved, which is preferable. If the halogen-containing vinyl monomer in the halogen-containing copolymer is less than 30%, there may be a case where the flame retardancy of the fiber becomes insufficient, and if it exceeds 70%,
In some cases, the properties of the produced fibers such as the physical properties (strength, elongation, heat resistance, etc.), dyeing properties, and feeling are not sufficient. 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 and the} like), antimonic acid, antimony oxychloride. And the like, but not limited thereto. These may be used alone or in combination of two or more. The ratio of the Sb compound to the halogen-containing copolymer is 6 to 50%. If the amount is less than 6%, it is necessary to increase the mixing ratio of the halogen Sb-containing fiber in the flame retardant fiber composite in order to obtain the flame retardancy required for the flame retardant fiber composite. When the mixing ratio of the halogen-containing Sb-containing fiber is increased in this way, it becomes difficult to obtain performances other than the flame retardancy of the flame-retardant fiber composite, such as sight, feeling, moisture absorption, washing resistance, and durability. . On the other hand, if the amount exceeds 50%, nozzle clogging during fiber production and fiber physical properties (strength, elongation, etc.) are reduced, and problems arise in the production and quality of highly flame-retardant reinforced fibers. Is not preferred. In addition, when strong strength or the like for the flame-retardant fiber or good knitting property is required for the flame-retardant fiber composite, the ratio of the Sb compound is preferably 6% or more and less than 12%, and 6% or more and less than 8%. Is more preferred. When the flame retardant fiber composite is required to have a high degree of flame retardancy and spinning properties, the ratio of the Sb compound is preferably 12 to 40%, and more preferably 12 to 30%.
Is more preferred. In the present invention, 12 to 50% is employed. In the present invention, the amount of the Sb compound relative to the halogen-containing copolymer is 12 to 50% , and as long as this amount is maintained, it may be used in combination with other flame retardants. Other flame retardants which can be used in combination with the Sb compound include, for example, aromatic halides such as hexabromobenzene, aliphatic halides such as paraffin chloride, and tris (2,3-dichloropropyl). halogen-containing phosphorus compounds such as phosphates, organic phosphorus compounds such as dibutyl amino phosphate, inorganic phosphorus compounds such as ammonium polyphosphate, MgO, Mg (OH) _2, inorganic magnesium compound such as MgCO _3, stannic oxide, metastannic acid,
Examples thereof include inorganic tin compounds such as stannous oxyhalide, stannic oxyhalide, and stannous hydroxide. The use amount of the other flame retardant is preferably 0 to 10%. In the present invention, the halogen Sb-containing fiber
15 parts, preferably 60 to 15 parts, more preferably 60 to 20
Parts, particularly preferably 50 to 20 parts, and at least one fiber 15 to at least one selected from the group consisting of natural fibers and chemical fibers.
85 parts, preferably 40 to 85 parts, more preferably 40 to 80 parts
From parts, particularly preferably from 50 to 80 parts, the flame-retardant fiber composite according to the invention is produced. In the present invention, the proportion of the halogen Sb-containing fiber and at least one selected from the group consisting of natural fibers and chemical fibers depends on the flame retardancy, visual feeling, feeling, and moisture absorption required for the final product. It is determined by performance such as washing resistance and durability. The usage ratio is determined by the type and composition ratio of the halogen-containing Sb-containing fiber, and when another flame retardant is used, the type and amount of the flame retardant, the type and combination of the fibers to be mixed, and the like. When the content of the halogen Sb-containing fiber is less than 15 parts, that is, when the ratio of the natural fiber or the chemical fiber to be mixed exceeds 85 parts, the flame retardancy of the flame-retardant fiber composite is insufficient.
When the ratio of the natural fiber and the chemical fiber to be mixed is more than 85 parts and the ratio of the natural fiber and the chemical fiber to be mixed is more than 85 parts, other flame sensation, feeling, feeling, moisture absorption, Performances such as washability and durability are not sufficient, and neither is preferable. In order for the flame-retardant fiber composite according to the present invention to have the desired flame retardancy and to clarify the characteristics of the natural fiber and the chemical fiber to be mixed, the fiber containing halogen Sb should have a content of 60 to 60%.
It is preferable that the ratio of the natural fiber and the chemical fiber to be mixed is 40 to 85 parts in 15 parts. When the other fiber is a natural fiber, it is preferable to mix 40 to 85 parts of the natural fiber with respect to 60 to 15 parts of the halogen-containing Sb fiber, and when the other fiber is a chemical fiber, it is particularly preferable. It is preferable to mix 50 to 80 parts of the halogen Sb-containing fiber with 50 to 80 parts of the chemical fiber. The reason why the flame-retardant fiber composite according to the present invention has excellent flame retardancy is that the halogen-containing Sb-containing fiber contains a large amount of an Sb compound which produces a gas-type flame-retardant effect. It is presumed that gases such as hydrogen hydride, halogen, and antimony halide are generated at a relatively low temperature, and the incombustible decomposition products cover combustible fibers. Further, flame retardancy blend of flame retardant fiber composite according to the present invention, without depending交撚, cotton mixing, union, the composite method such as mixed knitting, show substantially the same performance, flameproofing test It is considered that the texture is very dense and uniform not only in blending, twisting, and blending but also in weaving and knitting, as compared with the size of the flame that comes into contact with the flame. Specific examples of the natural fibers include plant fibers such as cotton and hemp, and animal fibers such as wool, camel, goat wool, and silk. Specific examples of the chemical fibers include:
Examples include, but are not limited to, regenerated fibers such as viscose rayon fibers and cupra fibers, 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 singly combined with a halogen-containing Sb-containing fiber.
It may be combined with the contained fiber. The halogen Sb-containing fiber used in the present invention contains a large amount of a flame retardant such as an inorganic metal compound.
At the time of production, a flame retardant such as an inorganic metal compound is sufficiently pulverized with a vibration mill or the like, and the particle size is adjusted to 2 μm or less, so that there is little or no trouble in spinning such as nozzle clogging and thread breakage. Can be produced by a usual spinning method. As a method for producing a flame-retardant fiber composite,
It may be blended or blended in the state of a single fiber, may be twisted, may be twisted, and may be cross-woven or cross-knitted after each yarn is manufactured. Or may be wrapped. The fiber composite in the present invention is a concept including not only so-called fibers such as long fibers and short fibers, but also fiber products such as yarn, woven fabric, knitted fabric and non-woven fabric. [0029] Optionally the flame retardant fiber composite according to the present invention, an antistatic agent, a thermal coloring preventing agent, light resistance improver, whiteness enhancers, it may be contained and devitrification inhibitor Is a matter of course. The flame-retardant fiber composite according to the present invention thus obtained has the desired flame retardancy, and furthermore, the sensation, feeling, moisture absorption, washing resistance and durability of other fibers to be mixed. Etc. Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to only these Examples. The flame retardancy of the fibers in the examples was measured by the oxygen index method (LOI method) as follows. In general, the flame retardancy of fibers is measured and evaluated in the state of a woven fabric, but in woven fabrics, the combustibility differs depending on the number of twists, thickness, number of threads, etc. Is not able to be evaluated correctly. (Flammability) Take 2 g of cotton mixed at a predetermined ratio, divide it into eight equal parts, make eight koyori of about 6 cm, make them stand upright in the holder of the oxygen index tester, and keep the sample burning 5 cm. The minimum oxygen concentration required for the measurement was measured, and this was defined as the LOI value. The higher the LOI value, the less it burns and the higher the flame retardancy. Production Examples 1-2 Copolymers consisting of 49.0% of acrylonitrile and 51.0% of vinyl chloride were dissolved in acetone to a resin concentration of 27.0%. Antimony trioxide was added to a liquid obtained by diluting a part of the obtained resin solution with acetone three times so that the solid content concentration became 50%, and dispersed using a vibration mill. This dispersion was added to and mixed with the resin solution so that antimony trioxide was 20% of the resin to prepare a spinning stock solution. The obtained spinning stock solution was extruded into a 30% acetone aqueous solution using a nozzle having a nozzle hole diameter of 0.08 mm and a number of holes of 300, washed with water, dried at 120 ° C., and then dried.
This was heat-stretched twice and further heat-treated at 140 ° C. for 5 minutes to obtain a halogen Sb-containing modacrylic fiber (Production Example 1). In place of antimony trioxide, a resin obtained by adding 10% of magnesium oxide to a resin was spun similarly to obtain a modacrylic fiber (Production Example 2). Examples 1-4 and Comparative Examples 1-9 Each of the halogen Sb-containing modacrylic fiber obtained in Production Example 1 and the modaacryl fiber obtained in Production Example 2 was mixed with cotton in the ratio shown in Table 1, Samples for flammability test were prepared and LOI values were measured. The results are shown in Table 1 and FIG. The characteristics of the fiber composite as cotton (visual feeling,
Organoleptic test was conducted to determine whether or not it had a feeling. Table 1 shows the results. In Table 1, ○ indicates that it has the characteristics (hygroscopicity) of cotton, and X indicates that it does not. [Table 1] As is evident from the results shown in Table 1 and FIG. 1, the halogen-Sb-containing modacrylic fiber of Production Example 1 and the modaacrylic fiber of Production Example 2 alone have superior flame retardancy to the fiber of Production Example 2. However, when these are mixed with cotton to form a fiber composite, on the contrary, the use of halogen Sb-containing modacrylic fiber has a lower flame retardancy than that using the modacrylic fiber of Production Example 2. Very low, a high LOI value when the mixing ratio of cotton is more than 15 parts,
It can be seen that the flame retardancy is excellent. Examples 5-6 and Comparative Examples 10-11 Each of the modacrylic fibers obtained in Production Examples 1 and 2 was 70
Yarn of fiber composite with 30 parts of cotton and 30 parts of cotton (30/2)
As a result of a flameproof test of a plain weave test cloth (Example 5 and Comparative Example 10) having a length of 50 pieces / inch × 30, 40, 50 pieces / inch, respectively, by the method specified in the Fire Service Law, the production example was obtained. The one using the fiber of No. 1 passed, and the one using the fiber of Production Example 2 failed. The spun yarn (20/1) of 100% modaacrylic fiber obtained in Production Examples 1 and 2 was used as weft yarn at a rate of 130 yarns / inch, and the spun yarn of 100% cotton (30/1). To 85
A cross-woven plain woven fabric (Example 6 and Comparative Example 11, respectively) having a weight ratio of modacrylic fiber / cotton of 50/50 (each Example 6 and Comparative Example 11) was used as a warp so as to give a book / inch. As a result, those using the fiber of Production Example 1 passed,
Those using the fibers of Production Example 2 were rejected. From the above, it can be seen that the same effect is obtained in both the mixed spinning and the weaving. Production Examples 3 to 12 A copolymer comprising 50% of acrylonitrile, 34% of vinyl chloride, 15% of vinylidene chloride and 1.0% of sodium methacrylsulfonate was dissolved in dimethylformamide so that the resin concentration became 25%. Into the obtained solution, the vibration mill dispersion of antimony trioxide obtained in the same manner as in Production Example 1 was added.
0%, 2%, 6%, 8% of antimony trioxide to resin
%, 10%, 12%, 15%, 20%, 50%, and 70% were added and mixed (Production Examples 3 to 12, respectively) to prepare spinning stock solutions. The obtained stock solution was spun in the same manner as in Production Example 1 except that the solution was extruded into a 60% aqueous dimethylformamide solution to obtain a modacrylic fiber. In this case, the spinnability was good except that in the case of Production Example 12, the nozzle was clogged and the yarn was broken. Examples 7 to 10, Reference Examples 1 to 3, and Comparative Examples
12-14 Each of 50 parts of the modacrylic fiber obtained in Production Examples 3-12 and 50 parts of cotton were mixed to obtain a fiber composite. The LOI value of the obtained fiber composite was measured, and the difference from the LOI value of the non-cottonized modacrylic fiber alone was determined. Table 2 shows the results. [Table 2] From the results in Table 2, it can be seen that when the amount of antimony trioxide added is 6% or more (when those obtained in Production Examples 5 to 12 are used), the decrease in LOI value is clearly reduced. It turns out that is recognized. However, as described in Production Examples 3 to 12, when the addition amount of antimony trioxide reaches 70%,
Spinning problems such as nozzle clogging and yarn breakage occur. Example 11 60 parts of modacrylic fiber containing 20% of antimony trioxide obtained in Production Example 10 and various fibers 40 shown in Table 3 other than cotton
And a fiber composite. The difference between the LOI value of the obtained fiber composite and the LOI value of the non-cottonized modacrylic fiber alone was measured. Table 3 shows the results. Comparative Example 15 The procedure of Preparation Example 10 was repeated, except that metastannic acid was added to the resin in an amount of 20% in place of the antimony trioxide used in Preparation Example 10.
The fiber was spun in the same manner as in Example 10 to obtain a modacrylic fiber. Using the obtained modacrylic fiber, cotton was mixed in the same manner as in Example 11 to obtain a fiber composite. The difference between the LOI value of the obtained fiber composite and the LOI value of the non-cottonized modacrylic fiber alone was measured. Table 3 shows the results. [Table 3] From the results in Table 3, it can be seen that the fiber composite using the modacrylic fiber obtained in Production Example 10 (Example 11 ) has a smaller decrease in LOI value as compared with the fiber composite of Comparative Example 15. Recognize. When the flame-retardant fiber composite according to the present invention is used, it has a desired flame retardancy and is hardly evident from only a single flame-retardant fiber, and has a sensation of feeling, feeling, Textile products for interiors, clothing and bedding having characteristics such as moisture absorption, washing resistance, and durability can be obtained, and the effect of meeting the increasingly diverse and sophisticated demands of consumers can be obtained.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows the relationship between the blended cotton ratio and the LOI value when measuring the LOI value by blending the modacrylic fiber obtained in Production Examples 1 and 2 with cotton. It is a graph.

──────────────────────────────────────────────────の Continuation of the front page (51) Int. Cl. ⁶ Identification symbol FI // D03D 15/00 D03D 15/00 E 15/12 15/12 Z (56) References JP-A-53-6617 (JP, A) JP-A-49-118940 (JP, A) JP-A-51-82023 (JP, A) JP-B-57-17964 (JP, B2) (58) Fields investigated (Int. Cl. ⁶ , DB name) ) D02G 3/04 D01F 1/00-6/96

Claims (1)

(57) [Claims] 1. Copolymer comprising 30 to 70% by weight of acrylonitrile, 70 to 30% by weight of a halogen-containing vinyl monomer and 0 to 10% by weight of a vinyl monomer copolymerizable therewith. Coalescing , but c
A polymer containing 19.9 to 43.9% by weight of
40-65% by weight of acrylonitrile and vinylidene chloride
And a total of 60 to 35% by weight of vinyl chloride
Except, the 2μ particle size 12 to 50 wt% relative to the copolymer
melt spinning containing Sb compound aligned to less than m
Respect fibers 85-15 parts by weight of at least one fiber selected from the group consisting of natural fibers and chemical fibers 15-85
Made in the flame retardant fiber composite, characterized in that Maseru containing the parts
Law . 2. The method for producing a flame-retardant fiber composite according to claim 1, wherein at least one of the copolymerizable vinyl monomers is a sulfonic acid group-containing vinyl monomer. 3. A patent wherein the copolymer contains 40 to 85 parts by weight of at least one fiber selected from the group consisting of natural fibers and chemical fibers with respect to 60 to 15 parts by weight of fibers containing an Sb compound. A flame-retardant fiber composite according to claim 1 .
Law . (4 ) Patents containing 50 to 20 parts by weight of at least one kind of fiber selected from the group consisting of natural fibers and chemical fibers with respect to 50 to 20 parts by weight of fibers containing the Sb compound in the copolymer. A flame-retardant fiber composite according to claim 3 .
Law . 5. The method for producing a flame-retardant fiber composite according to claim 3, wherein 40 to 85 parts by weight of a natural fiber is contained with respect to 60 to 15 parts by weight of a fiber containing an Sb compound in the copolymer. . 6. The method for producing a flame-retardant fiber composite according to claim 4, wherein 50 to 80 parts by weight of a chemical fiber is contained with respect to 50 to 20 parts by weight of a fiber containing an Sb compound in the copolymer. .