JPS6189339A - Composite fire retardant fiber - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention is a mixture of halogen-containing fibers highly flame-retardantly reinforced with a flame retardant and other fibers, which has excellent texture and hygroscopicity.
The present invention also relates to a composite flame-retardant fiber having n-flammability. More specifically, at least one type selected from the group consisting of halogen-containing fiber containing a large amount of Sb compound, which is a flame retardant, natural fiber, and chemical 17 navy blue! It concerns composite flame-retardant fibers mixed with l fibers.

[Conventional technology] In recent years, there has been a strong demand for flame retardancy not only for interior decorations but also for textile products for clothing and bedding. Demand for performance is also increasing.

Traditionally, research on flame retardancy in fibers has been carried out on individual fibers such as modacrylic fibers and volicral fibers, as well as polyester fibers and viscose rayon fibers. Although some products with excellent fuel performance are available, the current situation is that they hardly meet the increasingly diverse and sophisticated demands of consumers. Therefore, necessarily i! It is necessary to mix, blend, or weave flammable fibers with other fibers.
There are few studies on flame retardancy for composite fibers that are a mixture of two or more different types of fibers.

For example, composite 41M (Special Publication No. 52
-21612 ff1), composite fibers made by mixing polyfural i [containing stannic acid and antimonic acid with polyester 'aN, acrylic fiber, cotton, etc.
6617) is said to be effective, but it cannot be said to be sufficient in terms of flame retardancy, texture, hygroscopicity, etc.

[Problems to be solved by the invention] The present invention is a 1Mfffl that meets the increasingly diverse and sophisticated demands of consumers for flame retardancy, visibility, texture, moisture absorption, washing 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 have developed a method of mixing fibers made of a halogen-containing polymer containing a large amount of Sb compounds with other combustible fibers. The inventors have discovered that when composite IIH is made, the degree of decrease in flame retardancy is significantly smaller than that of conventional flame retardant fibers, and the present invention has been completed.

That is, in the present invention, the halogen content is 17 to 86% (@amount%,
(same below) 6 to 50% of the polymer
100 parts of 85 to 15 parts (by weight, the same shall apply hereinafter) containing an Sb compound and 15 to 85 parts of at least one type of fiber selected from the group consisting of natural fibers and chemical miscellaneous fibers. This relates to a composite flame-retardant IIN that has the desired flame retardancy and has visual appearance, texture,
It satisfies the increasingly diverse and sophisticated demands of consumers, such as moisture absorption, wash resistance, and durability.

[Example] In the present invention, a polymer containing halogen in an amount of 17 to 86%, preferably 17 to 73%, has a halogen content of 6 to 5%, based on the polymer.
m-fiber containing 0% Sb compound is 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 of halogen-containing vinyl monomers such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinylidene bromide;
i or more copolymers, acrylonitrile-vinylidene chloride, acrylonitrile-vinyl chloride, acrylonitrile-
Copolymer of 7-crylonitrile with a halogen-containing vinyl monomer such as vinyl chloride-vinylidene chloride, acrylonitrile-vinylidene bromide, acrylonitrile-vinylidene chloride-vinyl bromide, acrylonitrile-vinylidene chloride-vinyl bromide, vinyl chloride , vinylidene chloride, vinyl bromide,
1 of halogen-containing vinyl monomers such as vinylidene bromide
A copolymer of at least one species of acrylonitrile and a vinyl monomer copolymerizable with these, or a polymer obtained by adding a halogen-containing compound to an acrylonitrile homopolymer,
Examples include, but are not limited to, halogen-containing polyesters. 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, vinyl sulfonic acid, salts thereof, methacryl sulfonic acid, salts thereof, Examples include styrene sulfonic acid and its salts, and one or a mixture of two or more thereof may be used.

The polymer containing 17 to 86% of halogen is 30 to 70% of acrylonitrile and 70 to 70% of halogen-containing vinyl monomer.
30% and vinyl monomer copolymerizable with these O~
A polymer containing 10% is preferable because the resulting fibers have the desired flame retardancy and the feel of acrylic fibers. 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% of 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 a specific example thereof is antimony oxide (5b2
03.5b2o a % 5biOs), antimonic acid, and antimony compounds such as antimony oxychloride, but are not limited thereto.

These may be used alone or in combination of two or more.

The ratio of the Sb compound to the polymer containing 17 to 86% of halogen is 6 to 50%, preferably 8 to 40%, and more preferably 10 to 30%. If the Sb content is less than 6%, in order to obtain the flame retardancy required as a composite flame retardant fiber, the composite flame retardant fiber consisting of a polymer containing 17 to 86% halogen and an Sb compound (hereinafter referred to as halogen Sb-containing fiber) is required. It is necessary to increase the mixing ratio in the combustion fiber. When the mixing ratio of the halogen Sb-containing fiber is increased in this way, it becomes difficult to obtain the properties other than the flame retardance of the composite flame-retardant fiber, such as visibility, feel, moisture absorption, washing resistance, and durability. On the other hand, if this ratio exceeds 50%, nozzle clogging during AM production and a decrease in fiber properties (strength, elongation, etc.) occur, causing problems in the production and quality of highly flame-retardant reinforced m-fibers. occurs, which is not desirable.

In the present invention, as long as the amount of Sb compound is maintained at 6 to 50% with respect to the polymer containing 17 to 86% of halogen,
It may also be used in combination with other flame retardants.

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-dichloropropyl) phosphate, etc. Halogen-containing phosphorus compounds, organic phosphorus compounds such as dibutylaminophosphate, inorganic phosphorus compounds such as ammonium polyphosphate, tLQo, di(OH) 2 , H(
Examples include inorganic magnesium compounds such as IC (h), inorganic phosphorus compounds such as stannic acid, metastannic acid, stannous oxyhalide, stannic oxyhalide, and stannous hydroxide. The amount of flame retardant used is preferably 0 to 10%.

In the present invention, halogen Sl+ containing fiber (fiber 15 to 85
and 85 to 15 parts of at least one type of fiber selected from the group consisting of natural fibers and chemical fibers to produce 100 parts of the composite fiber H of the present invention.

In the present invention, the use of halogen Sb-containing fibers and at least one selected from the group consisting of natural fibers d3 and chemical fibers can achieve the flame retardancy, visibility, texture, and moisture absorption properties required for the final product. It is determined by performance such as washing resistance and durability.

In addition, the type of halogen Sb-containing m fiber and its composition ratio,
When using other flame retardants, the usage ratio is determined by the type and amount of the flame retardant, the type and combination of the FFL to be mixed, etc.

When the halogen Sb-containing #l miscellaneous is less than 15 parts, that is, when the proportion of mixed natural fibers and chemical fibers exceeds 85 parts, the flame retardance of the composite m fiber is insufficient;
If the amount of b-containing fiber exceeds 85 parts and the proportion of mixed natural miscellaneous or chemical fibers is less than 15 parts, although it has excellent flame retardancy, other visual appearance, texture, moisture absorption, and resistance Performances such as washability and durability are insufficient, and both are unfavorable.

In order for the composite flame-retardant fiber of the present invention to have the desired flame retardancy and to bring out the characteristics of the natural fibers and chemical fibers with which it is mixed, it is necessary to use halogen Sb-containing p! 4 sheets are 85-20 copies,
It is more preferable that the proportion of natural fibers and chemical fibers to be mixed is 15 to 80 parts.

The reason why the composite flame retardant II material of the present invention has poor flame retardancy is that S
Since a large amount of B compounds are mixed, nonflammable gases such as hydrogen halides, halogens, and antimony halides are generated at relatively low temperatures, and the nonflammable decomposition products coat the flammable m fibers. It is speculated that this is because the

Specific examples of the natural fibers include vegetable fibers such as cotton and hemp, animal fibers such as wool, camel hair, goat hair, and silk, and specific examples of the chemical fibers include viscose rayon fibers, Regenerated fibers such as cupro fibers,
Examples include semi-synthetic mN such as acetate fibers, synthetic fibers such as nylon fibers, polyester fibers, and acrylic fibers, but are not limited to these.

These natural fibers and chemical fibers may be used singly in combination with the halogen Sb-containing fiber, or two or more types may be combined with the halogen Sb-containing fiber.

The halogen Sb-containing YEAH used in the present invention contains a large amount of flame retardant such as an inorganic metal compound, but! During spinning, flame retardants such as inorganic metal compounds are thoroughly pulverized using a vibrating mill, etc., and the particle size is made equal to 2 or less. This eliminates spinning problems such as nozzle clogging and yarn breakage, and allows normal spinning. It can be manufactured by the method.

Methods for producing composite fibers include blending or blending in the form of lJi fibers, intertwisting, interweaving after producing each type of yarn, or interweaving after producing each yarn. Sometimes it can be made into chunks and made into slabs or neps, or rolled.

Note that the term "fiber" in the present invention is a concept that includes not only so-called fibers such as long fibers and short fibers, but also m-fibrous products such as yarn, woven fabric, knitted fabric, and nonwoven fabric.

The composite flame retardant fiber of the present invention may contain an antistatic agent, if necessary.
It goes without saying that a thermal coloring inhibitor, a light fastness improver, a 0 degree improver, a devitrification inhibitor, etc. may be contained.

The composite flame-retardant fiber 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 is also owned.

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. In addition, in the example! The flame retardancy of 1 fiber is determined by the B prime index method (L
It was measured by OI method) as follows. this is,
Generally, 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 flammability cannot be evaluated correctly.

(Flammability) Take 2q of cotton blended at a prescribed ratio, divide it into 8 equal parts, make 8 pieces of about 6cm each, and stand them upright in the holder of an oxygen index tester. The required minimum oxygen concentration was measured and used as the LOI value.

Culms with a large LOT value are difficult to burn and have high flame retardancy.

Production Examples 1-2 Acrylonitrile 49.0% and vinyl chloride 51.0%
% copolymer to acetone! 1@concentration 27.0
%. A portion of the obtained resin solution was diluted three times with acetone, and antimony trioxide was added to the solution so that the solid content was 50%, and dispersed using a vibration mill. This dispersion was added 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 to 3 times its original size, and further heated at 140°C. A halogen Sb-containing modacrylic fiber was obtained by heat treatment for 5 minutes (Production Example 1).

A modacrylic fiber was obtained by adding 10% magnesium oxide to the resin instead of antimony trioxide and spinning in the same manner (Production Example 2).

Examples 1 to 4 and Comparative Examples 1 to 9 Halogen Sb-containing modacrylic t[
The modacrylic fibers obtained in Production Example 2 and cotton were mixed in the proportions shown in Table 1 to prepare samples for flammability testing, and the LOr 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 composite 417Ili had the characteristics (visual feel, texture, etc.) of cotton. The results are shown in Table 1. Note that O in Table 1 indicates that the material has characteristics as cotton, and × indicates that it does not.

[Margins below] Table 1 As is clear from the results in Table 1 and FIG.
) and the modacrylic fiber of Production Example 2, although the fiber of Production Example 2 has better flame retardancy when used alone,
When these are blended with cotton to form Composite III, on the contrary, the flame retardance of the halogen Sb-containing modacrylic fiber used in the present invention is significantly lower than that of the modacrylic fiber of Production Example 2. It can be seen that when the blending ratio of cotton is 15 parts or more, the LOI value is high and the flame retardance is excellent.

Example 5 and Comparative Example 10 Composite fiber spun yarn prepared by mixing 70 parts of modacrylic mft17 obtained in Production Example 1.2 and 30 parts of cotton (
30/2) 50 longitudes/inches x latitude 30.40.50
This/inch flat test fabric (Example 5 and Comparative Example 1, respectively)
0) was subjected to a flame retardant test according to the method specified in the Fire Service Act. As a result, the one using the ° fiber of Production Example 1 passed, and the one using the fiber of Production Example 2 failed.

Production Examples 3 to 9 Acrylonitrile 50%, vinyl chloride 34%, vinylidene chloride 15% and sodium methacrylsulfonate 1.0
% was dissolved in dimethylformamide to a resin concentration of 25%. A vibrating mill dispersion of antimony trioxide obtained in the same manner as in Production Example 1 was added to the resulting solution so that antimony trioxide was 0% or 2% based on the resin.
, 6%, 10%, 20%, 50%, and 70% (corresponding to Production Examples 3 to 9, 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 9 in which the nozzle was clogged and yarn breakage occurred.

Examples 6-9 and Comparative Examples 17-13! ! Fifty parts of each of the 17 modacrylic fibers obtained in Examples 3 to 9 were blended with 50 parts of cotton to obtain 17 composite fibers.

The LOI value of the resulting composite material was measured, and the difference from the LOI value of the unmixed modacrylic fiber alone was determined. The results are shown in Table 2.

[Margins below] Table 2 From the results in Table 2, it is clear that when the amount of antimony trioxide added is 6% or more (when the products obtained in Production Examples 5 to 9 are used), LOI It can be seen that a decrease in the value is observed. However, as explained in Production Examples 3 to 9, when the amount of antimony trioxide added reaches 70%, problems occur during spinning such as nozzle clogging and yarn breakage.

Example 10 A composite fiber was obtained by blending 60 parts of the modacrylic fiber obtained in Production Example 8 to which 20% antimony trioxide was added and 40 parts of various fibers shown in Table 3 other than wire.

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 14 Modacrylic 4J! was spun in the same manner as in Production Example 8, except that instead of the antimony trioxide used in Production Example 8, metastannic acid was added to the resin at a concentration of 20%. i(t) was obtained. Using the obtained modacrylic fiber, it was mixed in the same manner as in Example 10 to obtain a composite fiber.

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.

Table 3 From the results in Table 3, the modacrylic l obtained in Production Example 8
It can be seen that the composite m fiber (Example 10) using an I-thread has a smaller decrease in 101 value than Composite 21 of Comparative Example 14.

[Effects of the Invention] When the composite flame retardant [1 of the present invention] is used, it has the desired flame retardancy, and also has visual appearance, texture, hygroscopicity, The textile products for interior decoration, clothing, and bedding, which have characteristics such as wash resistance and durability, can be changed to meet the increasingly diverse and sophisticated demands of consumers.

[Brief explanation of drawings]

Figure 1 shows modacrylic 1iif obtained in Production Examples 1 and 2.
It is a graph showing the relationship between the cotton blend ratio and the LOI value when the LOI value is measured by blending T and cotton. Figure 21: jL bond τ・1/f#, (ship

Claims (1)

[Scope of Claims] 1. 85 to 15 parts by weight of fibers made of a polymer containing 17 to 86% by weight of halogen and 6 to 50% by weight of an Sb compound based on the polymer, natural fibers and chemical fibers. A composite flame-retardant fiber comprising 100 parts by weight of at least one fiber selected from the group consisting of 15 to 85 parts by weight. 2 The polymer contains 30 to 70% by weight of acrylonitrile,
The composite flame-retardant fiber according to claim 1, which is a copolymer consisting of 70 to 30% by weight of a halogen-containing vinyl monomer and 0 to 10% by weight of a vinyl monomer copolymerizable with these. 3. The composite flame-retardant fiber according to claim 2, wherein at least one of the copolymerizable vinyl monomers is a sulfonic acid group-containing vinyl monomer.