JP2593987B2 - 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 reinforced with a flame retardant, which is highly flame-retarded, and another fiber, which is excellent in feeling and hygroscopicity. And a method for producing a flame-retardant fiber composite having flame retardancy. More specifically, a halogen-containing fiber containing a large amount of an Sb compound as a flame retardant, and at least one selected from the group consisting of natural fibers and chemical fibers.
The present invention relates to a method for producing a flame-retardant fiber composite obtained by compounding a kind of 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
Up to 70% (% by weight, the same applies hereinafter), halogen-containing vinyl
70 to 30% and vinyl-based monomer copolymerizable with them
8% to the copolymer consisting of 0 to 10%
A fiber obtained by melt-spinning containing an Sb compound having a particle size of at least 12% and less than 2 μm (hereinafter, halogen Sb)
With respect to 85 to 15 parts (also referred to as “parts by weight”, hereinafter the same), at least one kind of fiber (hereinafter, also referred to as “other fibers”) selected from the group consisting of natural fibers and chemical fibers
85 parts A relates preparation <br/> flame retardant fiber composite, characterized in that Maseru contains, has desired flame retardancy, and luminous, texture, moisture absorption, resistance to washing, A flame-retardant fiber composite that satisfies diversified and sophisticated demands of consumers such as durability
It relates to a method of manufacturing . [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
%, Halogen-containing vinyl monomer 70 to 30% and these
And the copolymerizable vinyl monomer 0-10% than styrenesulfonate, a particle size of less than 12% more than 8% relative to the copolymer 2
A fiber containing an Sb compound having a size of not more than μm is used. Acrylonitrile 30-70 used in the present invention
%, Halogen-containing vinyl monomer 70 to 30% and these
And Examples of the copolymerizable vinyl consisting monomer 0-10% copolymer, A acrylonitrile - vinylidene chloride, acrylonitrile - vinyl chloride, acrylonitrile - vinyl chloride - vinylidene chloride, acrylonitrile - vinyl bromide , Acrylonitrile-vinylidene chloride-vinyl bromide, copolymers of acrylonitrile with halogen-containing vinyl monomers such as acrylonitrile-vinyl chloride-vinyl bromide, vinyl chloride, vinylidene chloride, vinyl bromide,
Halogen-containing vinyl monomers such as vinylidene bromide
Etc. copolymers of species or with acrylonitrile and copolymerizable with these vinyl monomer but is exemplified, but the invention is not limited thereto. Or it may be used by appropriately mixing prior Symbol copolymer. Note that the acrylic
Ronitrile 30-70%, halogen-containing vinyl monomer 70-
30% and vinyl monomers 0 to 10 copolymerizable therewith
% Does not contain 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. [0012] Before Kia acrylonitrile 30% to 70%, the fibers from the consisting co polymer of halogen-containing vinyl monomers from 70 to 30% and their co-polymerizable vinyl monomer 0-10%
Is preferred because it has the desired texture of acrylic fibers while having the desired flame retardancy. When at least one of the copolymerizable vinyl monomers is a sulfonic acid group-containing vinyl monomer, the dyeability is improved, which is preferable. The acrylonitrile 30-70%,
70-30% of a vinyl monomer containing a logene and co-weight with them
In case of a vinyl halide-containing organic vinyl monomer amount of the co-polymer in consisting monomer 0 to 10% is less than 30%, fiber becomes difficult to flame retarded, also more than 70% In addition, properties such as physical properties (strength, elongation, heat resistance, etc.), dyeing properties, feeling, etc. of the produced fibers become insufficient, and both are not preferred. The particle size used in the present invention is adjusted to 2 μm or less.
The Sb compound is used as a flame retardant, and specific examples thereof include antimony oxide (Sb ₂ O ₃ , Sb
Etc. _{2 O 4, Sb 2 O 5} ), antimony acid, inorganic antimony compounds such as antimony oxychloride and the like, but is not limited thereto. These may be used alone or in combination of two or more. Acrylonitrile 30-70%, containing halogen
70 to 30% of vinyl monomer and vinyl copolymerizable with them
The ratio of the Sb compound to the copolymer composed of 0 to 10% of the phenyl-based monomer is 8% or more and less than 12%. 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. . If the amount exceeds 50%, nozzle clogging during fiber production and fiber properties (strength, elongation, etc.)
This is undesirable because it causes problems in the production and quality of highly flame-retardant fibers. In particular, when the strength of the flame-retardant fiber and the good properties of the flame-retardant fiber composite and knitting properties are required, the ratio of the Sb compound is 6% or more.
%, More preferably 8% or more and less than 12%. When the flame retardant fiber composite is required to have a high degree of flame retardancy and yarn formability, the ratio of the Sb compound is preferably 12 to 40%, more preferably 12 to 30%. However, less than 8% and 12% or more are outside the scope of the present invention. In the present invention, acrylonitrile 30 to 70
%, Halogen-containing vinyl monomer 70 to 30% and these
It may be used in combination with another flame retardant as long as the amount of the Sb compound is maintained at 8% or more and less than 12% with respect to a copolymer composed of 0 to 10% of a vinyl monomer copolymerizable with the above. 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 of acrylonitrile (49.0%) and vinyl chloride (51.0%) (halogen content: 29%) 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.
A spinning stock solution was prepared. 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). Reference 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. Reference 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 woven test cloth of 50 / inch × 30, 40/50 / inch (Reference Example 5 and Comparative Example 10) formed 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 (Reference Example 6 and Comparative Example 11, respectively) in which the weight ratio of modacrylic fiber / cotton was 50/50 was used as a warp so as to give a book / inch, and a flameproof test was conducted by the method specified by the Fire Service Law. 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 (halogen content: 30.3%) consisting of 50% acrylonitrile, 34% vinyl chloride, 15% vinylidene chloride and 1.0% sodium methacrylsulfonate was added to dimethylformamide at a resin concentration of 25%. It dissolved so that it might become. Into the obtained solution, a vibration mill dispersion of antimony trioxide obtained in the same manner as in Production Example 1 was added, with antimony trioxide being 0%, 2%, 6%, 8%, 10%, 12% %, 15%, 20
%, 50%, and 70% (manufacturing 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 1-2, Reference Examples 7-11 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. Reference Example 12 60 parts of a 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 mixed fiber was obtained. 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 Reference Example 12 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 (Reference Example 12) 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.

   ────────────────────────────────────────────────── ─── Continuation of front page    (56) References JP-A-48-73521 (JP, A)                 JP-A-52-99399 (JP, A)                 JP-A-53-6617 (JP, A)                 Tokiko Sho 57-17964 (JP, B2)                 "Polymer" 22 (253) (1973) p. 218               −223

Claims (1)

(57) [Claims] 1 Acrylonitrile 30-70% by weight, halogen-containing vinyl
70 to 30% by weight of vinyl monomers and copolymerizable copolymers
A copolymer comprising 0 to 10% by weight of a phenyl-based monomer, having a particle size of 8% by weight or more and less than 12% by weight based on the
With respect to 85 to 15 parts by weight of the fiber obtained by melt spinning containing the Sb compound arranged below, 15 to 85 parts by weight of at least one kind of fiber selected from the group consisting of natural fibers and chemical fibers is used. preparation of the flame retardant fiber composite, characterized by containing Maseru. 2. The method according to claim 1, wherein at least one of the copolymerizable vinyl monomers is a sulfonic acid group-containing vinyl monomer.
The method according to claim 1 . (3 ) At least one fiber selected from the group consisting of natural fibers and chemical fibers is contained in an amount of 40 to 85 parts by weight with respect to 60 to 15 parts by weight of the fiber containing the Sb compound in the polymer. 2. The method according to claim 1, wherein (4) The polymer containing the Sb compound in an amount of 50 to 20 parts by weight, wherein 50 to 80 parts by weight of at least one kind of fiber selected from the group consisting of natural fibers and chemical fibers is contained. 4. The method according to claim 3, wherein 5. The method according to claim 3 , wherein natural fibers are contained in an amount of 40 to 85 parts by weight based on 60 to 15 parts by weight of the fiber containing the Sb compound in the polymer. 6. The method 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 polymer.