JPH0418050B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention is a flame-retardant fiber that is a composite of halogen-containing fibers highly flame-retardantly reinforced with a flame retardant and other fibers, and has excellent texture, moisture absorption, etc., and flame retardancy. Concerning complexes. For more details, see Sb, a flame retardant.
The present invention relates to a flame-retardant fiber composite made of a halogen-containing fiber containing a large amount of a compound and at least one type of fiber selected from the group consisting of natural fibers and chemical fibers. [Conventional technology] In recent years, there has been a strong demand for flame retardancy not only for interior decorations, but also for clothing and bedding textile products. The demand for improved performance is also increasing. Research on flame retardancy in fibers has traditionally been conducted on specific fibers such as modacrylic fibers and polyclar fibers, as well as polyester fibers and viscose rayon fibers. Although products with excellent flame retardant properties are available, the current situation is that they hardly meet the increasingly diverse and sophisticated demands of consumers. Therefore, blending, blending, and weaving of flame-retardant fibers and other fibers is inevitably required, but there are only a few studies on flame-retardant composite fibers that are a mixture of two or more different types of fibers. few. For example, composite fibers made by mixing phosphorus polyester fibers and acrylonitrile fibers (Special Publications
-21612) and composite fibers made by mixing polyclar fibers containing stannic acid and antimonic acid with polyester fibers, acrylic fibers, cotton, etc. (Japanese Unexamined Patent Publication No. 1983-6617) are effective. However, it is difficult to say that it is sufficient in terms of flame retardancy, texture, moisture absorption, etc. [Problems to be solved by the invention] The present invention provides fibers that meet consumers' increasingly diverse and sophisticated demands for flame retardancy, visibility, texture, moisture absorption, wash resistance, durability, etc. This was done to solve the problem of not having one. [Means for Solving the Problems] In view of the above-mentioned circumstances, the present inventors have made extensive studies and found that when fibers made of a halogen-containing polymer containing a large amount of Sb compound are mixed with other combustible fibers. The present inventors have discovered that a flame-retardant fiber composite can be obtained in which the degree of deterioration in flame retardance is extremely small compared to conventional flame-retardant fibers, and has completed the present invention. In other words, the present invention provides fibers (hereinafter referred to as "fibers") in which a polymer containing 17 to 86% (by weight, the same shall apply hereinafter) of halogen contains 12 to 50% of an Sb compound based on the polymer.
(also referred to as halogen Sb-containing fibers) 85 to 20 parts (by weight, the same shall apply hereinafter) and 15 to 80 parts of at least one type of fiber selected from the group consisting of natural fibers and chemical fibers (hereinafter also referred to as other fibers) 100 parts of the flame-retardant fiber composite, which has the desired flame retardancy and meets consumer expectations such as visibility, texture, moisture absorption, washing resistance, and durability. It satisfies increasingly diverse and sophisticated requirements. The above-mentioned flame-retardant fiber composites are those produced by blending or blending halogen Sb-containing fibers with other fibers, twisting and twisting halogen Sb-containing fibers and other fibers, or manufacturing using the above-mentioned blends or blends. The concept includes interweave or interknit products produced using threads or intertwisted products, as well as products obtained by combinations thereof. [Example] In the present invention, a polymer containing 17 to 86%, preferably 17 to 73%, of halogen is added to the polymer.
Fibers containing 12-50% Sb compounds are used. Examples of the polymer containing 17 to 86% halogen used in the present invention include polymers of halogen-containing monomers, polymers added with halogen-containing compounds, and halogen-impregnated polymers obtained by post-processing. Specific examples of such polymers include homopolymers or copolymers of two or more halogen-containing vinyl monomers such as vinyl chloride, vinylidene chloride, vinyl bromide, vinyldene bromide, and acrylonitrile-chloride. Vinylidene, acrylonitrile
Vinyl chloride, acrylonitrile-vinyl chloride-vinylidene chloride, acrylonitrile-vinyl bromide,
Copolymers of halogen-containing vinyl monomers such as acrylonitrile-vinylidene chloride-vinyl bromide, acrylonitrile-vinylidene chloride-vinyl bromide, and acrylonitrile, halogens such as vinyl chloride, vinylidene chloride, vinyl bromide, vinylidene bromide, etc. A copolymer of one or more vinyl monomers containing acrylonitrile and a vinyl monomer copolymerizable with these, a polymer obtained by adding a halogen-containing compound to an acrylonitrile homopolymer, a halogen-containing polyester, etc. However, it is not limited to these. Further, the above-mentioned homopolymers and copolymers may be appropriately mixed and used. Note that the polymer containing 17 to 86% halogen referred to herein does not contain partially acetalized polyvinyl alcohol in any form. Examples of the copolymerizable vinyl monomers include acrylic acid, esters thereof, methacrylic acid, esters thereof, acrylamide, methacrylamide, vinyl acetate, vinylsulfonic acid, salts thereof, methacrylsulfonic acid, salts thereof, and styrene sulfone. Examples include acids and salts thereof, and one or a mixture of two or more thereof may be used. The polymer containing 17 to 86% of the halogen is 30 to 70% of acrylonitrile and 70 to 70% of the halogen-containing vinyl monomer.
In the case of polymers consisting of ~30% and 0 to 10% of vinyl monomers copolymerizable with these, the resulting fibers have the desired flame retardancy and the feel of acrylic fibers. preferable. Further, it is preferable that at least one of the copolymerizable vinyl monomers is a sulfonic acid group-containing vinyl monomer because dyeability is improved. If the halogen content in the polymer containing 17 to 86% halogen is less than 17%, it will be difficult to make the fiber flame retardant, and if it exceeds 86%, the physical properties (strength, elongation) of the produced fiber will deteriorate. performance (such as heat resistance, heat resistance, etc.), dyeability, and texture, all of which are unfavorable. The Sb compound used in the present invention is used as a flame retardant, and specific examples include inorganic compounds such as antimony oxide (Sb ₂ O ₃ , Sb ₂ O ₄ , Sb ₂ O ₅ , etc.), antimonic acid, and antimony oxychloride. Examples include, but are not limited to, antimony compounds. These may be used alone,
Two or more types may be used in combination. The amount of Sb compound is 12-50%, preferably 12-40%, more preferably 12-30% based on the polymer containing 17-86% halogen. If the amount is less than 12%, in order to obtain the flame retardancy required as a flame retardant fiber composite,
It is necessary to increase the mixing ratio of fibers made of a polymer containing 17 to 86% halogen and an Sb compound (hereinafter referred to as halogen Sb-containing fibers) in a flame-retardant fiber composite. When the mixing ratio of halogen SB-containing fibers is increased in this way, it becomes difficult to obtain properties other than flame retardancy of the flame-retardant fiber composite, such as visibility, texture, absorbency, washing resistance, and durability. . On the other hand, if the amount exceeds 50%, nozzle clogging during fiber production and a decrease in fiber properties (strength, elongation, etc.) may occur, causing problems in the production and quality of highly flame-retardant fibers. , undesirable. In the present invention, the Sb compound may be used in combination with other flame retardants as long as the amount of the Sb compound is maintained at 12-50% based on the polymer containing 17-86% halogen. Other flame retardants that can be used in combination with the Sb compound include aromatic halides such as hexabromobenzene, aliphatic halides such as chlorinated paraffin, tris(2,3-
Halogen-containing phosphorus compounds such as dichloropropyl) phosphate, organic phosphorus compounds such as dibutylaminophosphate, inorganic phosphorus compounds such as ammonium polyphosphate, inorganic magnesium compounds such as MgO, Mg(OH) ₂ and MgCO ₃ , and stannic oxide. , metastannic acid, inorganic tin compounds such as stannous oxyhalide, stannic oxyhalide, and stannous hydroxide. The amount of other flame retardants used is 0.
~10% is preferred. In the present invention, halogen Sb-containing fibers 20 to 85
100 parts of the flame-retardant fiber composite of the present invention is produced from 100 parts of the flame-retardant fiber composite of the present invention. 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 is determined by the flame retardance, visibility, texture, moisture absorption, and washing resistance required for the final product. It is determined by performance such as durability and durability. In addition, the type of halogen Sb-containing fiber and its composition ratio,
When using other flame retardants, the proportion used in the first period is determined by the type and amount of the flame retardant, the type and combination of fibers to be mixed, etc. If the halogen Sb-containing fiber is less than 20 parts, that is, if the proportion of mixed natural fibers or chemical fibers exceeds 80 parts, the flame retardance of the fiber theater composite will be insufficient; Beyond the department,
If the proportion of natural fibers or chemical fibers mixed is less than 15 parts, the flame retardance is excellent, but other performances such as visual appearance, texture, moisture absorption, selectivity resistance, and durability are insufficient. Neither is desirable. In order for the flame-retardant fiber composite of the present invention to have the desired flame retardancy and to bring out the characteristics of the natural fibers and chemical fibers to be mixed, it is necessary to mix halogen Sb-containing fibers at 85 to 20 parts. It is preferable that the proportion of natural fibers or chemical fibers is 15 to 80 parts. The reason why the flame-retardant fiber composite of the present invention has excellent flame retardancy is that the halogen Sb-containing fiber contains a large amount of Sb compound that produces a gas-type flame retardant effect. This is thought to be because gases such as halogens and antimony halides are generated at relatively low temperatures, and the nonflammable decomposition products coat combustible fibers. In addition, the flame retardancy of the flame-retardant fiber composite of the present invention does not depend on the composite method such as blending, twisting, blending, interweaving, interweaving, etc., and shows almost the same performance in flame retardant tests. This is thought to be because, compared to the size of the flame, the structure is extremely dense and uniform not only in blended spinning, open twist, and mixed cotton, but also in mixed weaving and mixed knitting. Specific examples of the natural fiber include cotton,
Plant fibers such as hemp, wool, camel hair, goat hair,
Animal fibers such as silk, and specific examples of chemical fibers include recycled fibers such as viscose rayon fibers and Kyupra fibers, semi-synthetic fibers such as acetate fibers, and synthetic fibers such as nylon fibers, polyester fibers, and acrylic fibers. Examples include, but are not limited to, these. These natural fibers and chemical fibers alone contain halogen Sb.
It may be combined with the containing fiber, and two or more types of halogen
It may be combined with Sb-containing fibers. The halogen Sb-containing fiber used in the present invention contains a large amount of flame retardant such as an inorganic metal compound, but during production, the flame retardant such as the inorganic metal compound is thoroughly crushed using a vibrating mill or the like, and the particle size is adjusted to 2 μm or less. As a result, it is possible to produce the yarn by a normal yarn-proofing method without or without causing problems during spinning such as nozzle clogging or yarn breakage. The flame-retardant fiber composite may be produced by blending or blending in the form of single fibers.
They may be intertwisted, interwoven or knitted after each yarn is produced, or they may be made into a mass during spinning into a slab or net, or they may be wound. Note that the fiber composite in the present invention refers to long fibers,
The concept includes not only so-called fibers such as staple fibers, but also textile products such as threads, woven fabrics, knitted fabrics, and non-woven fabrics. It goes without saying that the flame-retardant fiber composite of the present invention may contain an antistatic agent, a thermal coloring inhibitor, a light resistance improver, a whiteness improver, a devitrification inhibitor, etc., as necessary. That's true. The flame-retardant fiber composite of the present invention obtained in this way has desired flame retardancy, and also has properties such as visual appearance, texture, moisture absorption, washing resistance, and durability of other fibers with which it is mixed. It also has. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited only to these Examples. The flame retardancy of the fibers in Examples was measured by the oxygen index method (LOI method) as follows. Generally speaking, the flame retardancy of fibers is measured and evaluated in the form of woven fabrics, but in woven fabrics, there are differences in combustibility depending on the number of twists, thickness, number of threads, etc. This is because it is not possible to evaluate correctly. (Flammability) Take 2g of cotton mixed at a prescribed ratio and add 8g of this
Divide the sample into eight pieces of approximately 6cm each and place them upright in the holder of the oxygen index tester.Measure the minimum oxygen concentration required for this sample to continue burning for 5cm.
It was taken as the LOI value. The higher the LOI value, the more difficult it is to burn and the higher the flame retardancy. Production examples 1-2 Acrylonitrile 49.0% and vinyl chloride 51.0%
% copolymer in acetone at a resin concentration of 27.0
%. A portion of the resulting resin solution was diluted 3 times with acetone, and antimony trioxide was added to the solids concentration of 50% and dispersed using a vibration mill. This dispersion was added to and mixed with the resin solution so that antimony trioxide was 20% based on the resin to prepare a spinning dope. The resulting spinning dope was extruded into a 30% acetone aqueous solution using a nozzle with a nozzle diameter of 0.08 mm and 300 holes, washed with water, dried at 120°C, then hot stretched three times, and further heated at 140°C. By performing the treatment for 5 minutes, modacrylic fibers containing halogen Sb were obtained (Production Example 1). Instead of antimony trioxide, 10% magnesium oxide was added to the resin and spun in the same manner to obtain modacrylic fiber (Production Example 2). Examples 1 to 3 and Comparative Examples 1 to 10 The halogen Sb-containing modacrylic fiber obtained in Production Example 1 and the modacrylic fiber obtained in Production Example 2 were mixed with cotton in the proportions shown in Table 1, and the flammability A test sample was prepared and the LOI value was measured. The results are shown in Table 1 and illustrated in FIG. In addition, a sensory test was conducted to determine whether the fiber composite had the characteristics (visual feel, texture, etc.) of cotton. The results are shown in Table 1. In Table 1, ◯ indicates that the material has the characteristics (hygroscopicity) of cotton, and × indicates that it does not.

【table】

[Table] As is clear from the results in Table 1 and FIG. 1, the halogen Sb-containing modacrylic fibers (Production Example 1) and the modacrylic fibers of Production Example 2 used in the present invention are different from those of the fibers of Production Example 2 when used alone. However, when mixed with these cottons to form a fiber composite, it is better to use the halogen Sb-containing modacrylic fiber used in the present invention than the modacrylic fiber of Production Example 2. It can be seen that the decrease in flame retardance is much smaller than that using cotton, and when the mixing ratio of cotton is 15 parts or more, the LOI value is high, indicating that the flame retardance is excellent. Examples 4 to 5 and Comparative Examples 11 to 12 50 warp yarns made of bulk yarn (30/2) of a fiber composite obtained by mixing 70 parts of the modacrylic fibers obtained in Production Examples 1 and 2 with 30 parts of cotton. Book/inch x latitude 30, 40,
As a result of flame retardant testing of 50 pieces/inch plain weave trial woven fabrics (Example 4 and Comparative Example 11, respectively) using the method specified in the Fire Service Act, the fabric using the fibers of Production Example 1 passed, and The sample using fiber No. 2 was rejected. In addition, 100% modacrylic fibers obtained in Production Examples 1 and 2 (20/1) were used as weft yarns at a rate of 130 pieces/inch, and 100% cotton spun yarns (30/1) were used as wefts.
A mixed woven plain weave fabric (Example 5 and Comparative Example 12, respectively) with a modacrylic fiber/cotton weight ratio of 50/50 using 85 yarns/inch as the warp was flame-retardant by the method specified in the Fire Service Act. As a result of the test, Manufacturing Example 1
The sample using the fiber of Production Example 2 passed the test, and the sample using the fiber of Production Example 2 failed. From the above, it can be seen that both blended and mixed weaves have similar effects. Production Examples 3 to 11 A copolymer consisting of 50% acrylonitrile, 34% vinyl chloride, 15% vinylidene chloride and 1.0% sodium methacrylsulfonate was dissolved in dimethylformamide so that the resin concentration was 25%. A vibrating mill dispersion of antimony trioxide obtained in the same manner as in Production Example 1 was added to the resulting solution, and antimony trioxide was added to the resin in an amount of 0%, 2%, 6%, 8%, 12
%, 15%, 20%, 50%, and 70% (Production Examples 3 to 11, respectively) to prepare a spinning dope. Modacrylic fibers were obtained by spinning in the same manner as in Production Example 1, except that the obtained stock solution was extruded into a 60% dimethylformamide aqueous solution. The spinnability in each case was good, except for Production Example 11 in which the nozzle was clogged and yarn breakage occurred. Examples 6 to 9 and Comparative Examples 13 to 17 Fifty parts of each of the modacrylic fibers obtained in Production Examples 3 to 11 were blended with 50 parts of cotton to obtain fiber composites. The obtained fiber composite LOI value was measured, and the difference from the LOI value of the modacrylic fiber alone without any cotton blending was determined. The results are shown in Table 2.

【table】

[Table] Decrease from value.
From the results in Table 2, it is clear that when the amount of antimony trioxide added is 12% or more (when the products obtained in Production Examples 7 to 11 are used), there is a clear reduction in the decrease in the LOI value. I know that it will happen. However, as explained in Production Examples 3 to 11, when the amount of antimony trioxide added reaches 70%, yarn protection problems such as nozzle clogging and yarn breakage occur. Example 10 A composite fiber was obtained by blending 60 parts of the modacrylic fiber obtained in Production Example 9 to which 20% antimony trioxide was added and 40 parts of various fibers shown in Table 3 other than cotton. The LOI value of the obtained composite fiber and the LOI value of the unmixed modacrylic fiber alone were measured, and the difference between them was determined. The results are shown in Table 3. Comparative Example 18 Instead of antimony trioxide used in Production Example 9,
A modacrylic fiber was obtained by spinning in the same manner as in Production Example 9, except that metastannic acid was added to the resin at a concentration of 20%. The obtained modacrylic fibers were mixed in the same manner as in Example 10 to obtain a fiber composite. The LOI value of the resulting fiber composite and the LOI value of the unmixed modacrylic fiber alone were measured, and the difference between them was determined. The results are shown in Table 3.

[Table] From the results in Table 3, the fiber composite using modacrylic fibers obtained in Production Example 9 (Example 10)
It can be seen that the LOI value decreases less than the fiber composite of Comparative Example 18. [Effects of the Invention] When the flame-retardant fiber composite of the present invention is used, it has the desired flame retardancy, and also has visual appearance, texture, moisture absorption, and properties that are difficult to obtain from a single flame-retardant fiber alone. It is possible to obtain textile products for interior decoration, clothing, and bedding that have characteristics such as wash resistance and durability, and to meet the increasingly diverse and sophisticated demands of consumers.

[Brief explanation of drawings]

FIG. 1 is a graph showing the relationship between the cotton blend ratio and the LOI value when the modacrylic fibers obtained in Production Examples 1 and 2 were blended with cotton and the LOI value was measured.

Claims (1)

[Scope of Claims] 1. 85 to 20 parts by weight of fibers made of a polymer containing 17 to 86% by weight of halogen and 12 to 50% by weight of an Sb compound based on the polymer, natural fibers and chemical fibers. At least one type of fiber selected from the group consisting of
A flame-retardant fiber composite made by combining 15 to 80 parts by weight to 100 parts by weight. 2 The polymer contains 30 to 70% by weight of acrylonitrile, 70 to 30% by weight of a halogen-containing vinyl monomer, and 0 to 10% of a vinyl monomer copolymerizable with these.
The flame-retardant fiber composite according to claim 1, which is a copolymer consisting of % by weight. 3 At least one copolymerizable vinyl monomer
The flame-retardant fiber composite according to claim 2, wherein said monomer is a sulfonic acid group-containing vinyl monomer.