JPS59211613A - Flame-retardant fiber and its manufacture - Google Patents

Abstract

PURPOSE:To obtain a fiber having high flame-retardance and excellent gloss, by using a spinning dope comprising a mixture of an aqueous emulsion of a halogen-containing polymer and an aqueous solution of PVA, mixing the dope with an aqueous solution of an inorganic tin compound at a specific ratio just before the spinning nozzle, and spinning the mixture. CONSTITUTION:An aqueous emulsion of a halogen-containing polymer (preferably a polymer having a halogen content of >=20%, e.g. PVC) is mixed with an aqueous solution of PVA at a weight ratio (halogen-containing polymer/PVA) of 6:4-4:6 to obtain a spinning dope. The dope is mixed with a water-soluble inorganic tin compound (e.g. stannic chloride, preferably losing its water-solubility in water of 2-7pH and giving a water-insoluble stannic acid, etc.) just before the spinning nozzle. The objective fiber containing 0.5-8wt%, preferably 0.5- 5wt%, based on the whole polymer, of said tin compound in the form of stannic acid (derivative) having an average particle diameter of <=100mmu, preferably <=20mmu can be manufactured by this process.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a flame-retardant fiber whose main components are a halogen-containing polymer and polyvinyl alcohol (including its acetalized product) (hereinafter, polyvinyl alcohol is abbreviated as PVA), and a method for producing the same. More specifically, the weight ratio of halogen-containing polymer and PV A is 6:4 to 4:6.
(including its acetalized product) is the main component ~
The present invention relates to a flame-retardant fiber containing 8% by weight, which has both excellent gloss and a high degree of flame-retardant oil, and a method for producing the same.

In recent years, there has been a strong emphasis on highly flame-retardant reinforced fibers for interior decoration, clothing, etc. to prevent fires. Fibers whose main components are halogen-containing molecules and PVA are
Although rice is technically flame retardant, it is not sufficient to meet social demands. Therefore, various flame retardant reinforcement methods have been developed in the past.

It is well known that tin compounds are effective in reinforcing the flame retardancy of fibers whose main components are halogen-containing polymers and PVA. 57-29566), a method of adding metastannic acid [Japanese Patent Publication No. 52-25452], etc.

However, fibers reinforced with flame retardancy by methods such as (71) and (71) lose their luster significantly, and their value as second-hand goods inevitably decreases. However, in recent years, in the interior design industry, there has been a strong demand not only for the short-burning function but also for the glossiness and vividness of dyed materials from a decorative standpoint.

As a result of intensive research in view of the current situation, wood researchers have found that by converting the tin compounds contained in the cut fibers into ultra-(a) particles, they can achieve a high level of carbon dioxide, which was previously unheard of. The present invention has been completed by successfully achieving both the contradictory functions of durability and excellent gloss.

That is, in the first aspect of the present invention, the weight ratio is 6:4 to
4:6(7) Cl-containing IJ Mart J:)V
The content of the flame retardant fiber is A, and the second invention is characterized in that the weight ratio of the halogen-containing polymer and PVA is 6.
A mixture of an aqueous emulsion of a halogen-containing polymer and an aqueous PVA solution having a ratio of: 4 to 4:6 is used as a spinning stock solution, and then a water bath of an inorganic tin compound is mixed with the spinning stock solution immediately before the spinning nozzle. The method of producing a flame-retardant fiber is characterized in that the compound is contained in a polymer in an amount of 0.5 to 8% by weight substantially in the form of stannic acid or its derivative, and then the fiber is spun.

The halogen-containing polymer used in the present invention is vinyl chloride,
Homopolymers of halogen-containing monomers such as vinylidene chloride,
It is a copolymer or a graft polymer, and may be used alone or as a mixture of two or more thereof. Further, it is desirable that the chlorine content of the halogen-containing polymer is 20% or more in order to maintain twist resistance.

The weight ratio of halogen-containing polymer and PVA is 6:4 to 4:
6 is so good. If the amount of the halogen-containing polymer is less than the above range, a high degree of 74111, which is one of the main objects of the present invention,
Flammability cannot be obtained. On the other hand, if the amount of the halogen-containing polymer is increased beyond the range specified in nIJ, the stability of the spinning dope consisting of the aqueous emulsion of the halogen-containing polymer and the VA aqueous solution mixture f's decreases, resulting in poor spinnability. 12 is not a good idea. In particular, Il in which an aqueous solution of a water-bathable inorganic tin compound is added to the spinning stock solution, 1. The influence on the stability of l is significant.

Next, the water bath tin compound used in the present invention is stannic chloride, sulfuric acid, sulfuric acid, sulfuric acid, nitric acid, sulfuric acid, A1: 1st stannous l: 1'i of strong acid j'ilA angle of stannic acid,
and stannic acid sorter, soot acid power 111:j, + soot ゛lIl alkali J''!j+ etc., etc., I] 1
Water in an aqueous system where 1 is 1 to 8, preferably 2 to 7? Any substance may be used as long as it loses its solubility and turns into a water-unbathable stannic acid or a derivative thereof.

Further, the uniform particles of stannic acid or its derivative ijJ body contained in the fiber i''f: 100 nl 1 or less, preferably 501TI 1t, more preferably 20 mμ
If it exceeds +1 100 mμ, the scattering of light by the tin compound particles increases and the fiber loses its luster. There is no stannic acid or its derivatives in the fiber.
．． Contains 5 to 8% by weight, preferably 0.5 to 5% by weight.
L. Must be. If it is 0.5% by weight, it is insufficient to obtain the desired high degree of flame retardancy, and if it exceeds 8% by weight, the transparency and gloss of the fiber will decrease. Incorporation of 100 mp or less of stannic acid or a derivative thereof into the fiber, which is one of the requirements of the present invention, can be achieved, for example, in the following manner.

That is, an aqueous emulsion of a halogen-containing polymer and 1-'
The mixture of the VA aqueous solution is used as the spinning solution (1.1), and then the above-mentioned water/i; #1 raw solid tin compound water bath solution is mixed with the spinning stock solution just before the spinning nozzle, and then the spinning is carried out. This is achieved by

It is well known that the transparency and gloss of fibers can be improved by reducing the particle size of the flame retardant to the wavelength of visible light or less. However, in the past, it was not possible to obtain fibers that were compatible with both gloss and flammability by adding tin compounds such as metastannic acid and stannic oxide. This is because a concise method (J method) for reducing the particle size of a compound has not been discovered. Equity 1I (356-38685 and Japanese Patent Publication No. 56-38686, react with an alkali or acid to eliminate the water bath 11. A water bath, i.
A method has been developed in which a fine powder aqueous dispersion of a tin compound is prepared and then the aqueous dispersion is added to a spinning dope. However, in the method of applying force, it is certainly 4. (The particle size of the tin compound contained in 1 is slightly η (1, but 05 to 1.011 islands)
However, it is not possible to obtain a flame retardant fiber that exhibits the excellent gloss which is the main object of the present invention.

According to the method of the present invention, stannic acid or its compound in the fiber is highly Oi1! luu j, l: l is not certain about whether the gloss of the fiber and the transparent outer side are normalized, ]) 1) Adding the water-bathable soot compound mentioned above to the spinning solution i) the secondary aggregation of the stannic acid or its derivatives produced is prevented by the dispersing action of VA;
It is presumed that this is due to the fact that the particles are mostly present in the spinning dope in the form of primary particles.

In the present invention, when a water bathing inorganic soot compound is added to the spinning dope, it is necessary to uniformly mix the tin compound water bathing solution immediately before the spinning nozzle with a mixer.

It is preferable that the time after mixing until the mixture is discharged from the nozzle is within 60 seconds. Mixing in the spinning dope tank, mixing power)
If the time until spinning is long, the spinning dope becomes unstable and gelation may occur, which is undesirable. As for the mixing method, a mixer of 1RF or 1RF may be used as long as it can disperse uniformly. -1: The concentration of the water bathing tin compound added to the spinning stock solution is preferably 30% or more, and more preferably 15% or less. , gloss and transparency are lost.

The wet spinning of the present invention uses sulfuric acid) IJum, zinc sulfate, M
A concentrated aqueous solution of salts such as ammonium carbonate is coagulated (performed overnight. After neutralization, the spun fibers are subjected to moist heat treatment, washed with water, dried, and then acetalized to obtain the final fiber.

The woven fabric woven from the fibers produced according to the present invention is
Completely passed the flame retardant test method stipulated by the Fire Service Act, and received 1.
π degree) 1 [indicates flammability. Also, in washing, F, I P
Furthermore, various textile products made from the fibers produced according to the present invention exhibit excellent luster, and dyed products have excellent luster. It has a unique color development and hue.

The present invention will now be described in detail with reference to Examples and Comparative Examples, but it goes without saying that the present invention is not limited by these.

Example 1 31' uniformity degree 17 o o, '7-tonization ff99%]
PVA was dissolved in water at 70"C to give 16% PV by weight.
A spinning stock solution of water:PVA=5:5 was prepared. Next, a separately prepared aqueous solution of stannic chloride with a concentration of 7% by weight was mixed with the spinning dope in a line mixer immediately before the spinning nozzle, and then wet-spun into a sodium sulfate bath solution, followed by wet heat stretching, washing with water, and drying. , subjected to dry heat stretching and shrinkage,
Further, the fibers were acetalized in an acetalization bath, washed, and treated with a finishing oil to obtain fibers 2 (1).

The amount of tin compound contained in the fiber is 3% by weight. PVC:PVA=50:50. The average particle diameter of the tin compound (substantially stannic acid or its derivative) contained in the fiber was 10 mμ, the fiber had excellent gloss, and the dyed product had a clear hue.

In addition, a test fabric made of this fiber (spun yarn) completely passed the flame retardant test stipulated by the Fire Service Act, and exhibited a high degree of flame retardancy.

Ratio 1 Bite Example 1 One tlffi of metastannic acid was ground in a magnetic vibrating ball mill for 2 hours to prepare an aqueous dispersion of metastannic acid with an average particle size of 1 μm. 1) Mix the water solution of the lever into the spinneret U of Example 1, 2, and perform the same treatment to obtain the composition power P V C: P
VA: Metas, X acid = 50: 2 of 50:3
d17) A fiber braid was obtained.

A sample fabric of this fiber, till- or ['-1, successfully passed the flame retardant test 1 stipulated in the Fire Service Act, and showed "M flammability" of the lining. The average particle diameter of the acid was l 1+, the gloss of the yarn 11 was dull, and it was inferior to Example 1 by 12 times.

Example 2: Oxidized 2nd soot from rlJ1 was processed using a vibrating hole mill with a sand column.
411. An oxidized second Sunu water dispersion with an average particle size of 2 μm was prepared using 111 yen of powder and an average particle size of 2 μm. Then, this aqueous dispersion was mixed with the spinning yarn of Example 1, and the same process was carried out in the same way.
: 2dO' of stannic oxide = 50:5U:3) fibers were obtained.

This fiber test fabric completely passed the flame retardant test stipulated by the Fire Service Act and exhibited a flame retardancy of 1π degree. sword・
However, the average particle of stannic oxide contained in the fiber -r
The diameter was 2//, the fibers were l1ll+, and the gloss was excellent.

Example PVA with an average degree of polymerization of 1700 and a degree of saponification of 99% was heated at 70°C.
A 16% by weight PVA aqueous solution was prepared by bath dissolving it in water, and to this was added 30% by weight PVA craft l''V.
Add C emulsion and stir well [PVC: PVA
A spinning stock solution of V6O130 was prepared.

Next, a separately prepared 7% by weight concentration of secondary chloride water bath solution was mixed with the spinning stock solution in the same manner as in Example 1, and spun -PVC.
:PVA:tin compound-50:50:3 fibers were obtained.

The test fabric made of this fiber passed the flame retardant test stipulated in the Clothing Protection Law, and demonstrated the flame retardant performance of the lining.

The average particle of the soot compound (substantially soot acid or its derivative) contained in the sweet fiber (L is 1.01TI 1i), the fiber has excellent luster, and the dyed product also has a clear hue. Indicated.

Patent applicant Kanebuchi Chemical Industry Co., Ltd.

Claims (1)

[Scope of Claims] 1. A fiber mainly composed of 14 components (including its acetalized product) of halogen-containing M molecules topolyvinyl alcohol (including its acetalized product) in a weight ratio of 6:4 to 4.6. Characteristic rows [combustion fibers] 2. Halogen-containing [1] Halogen-containing l' in which the ratio of Wa molecules to polyvinyl alcohol is 6:4 to 4:6 in city JJK ratio
A mixture of an aqueous emulsion and a polyvinyl alcohol water bath solution for 1'6 minutes is used as a spinning stock solution, and then a water bath solution of a water-based inorganic tin compound is mixed with the spinning stock solution immediately before the spinning nozzle to dequality the tin compound. 1. A method for producing flame-retardant fibers, which comprises adding 0.5 to 8% by weight of a polymer (μ7'-1) in the form of stannic acid or a derivative thereof to a'j, and spinning the mixture.