JPH08269813A - Flame retardant acrylic synthetic fiber and its production - Google Patents

Abstract

PURPOSE: To produce a highly flame retardant acrylic synthetic fiber good in resistance to washing and whiteness degree even in mixing with other fibers by adding an antimony oxide and a guanidine-based compound to a polymer for a modacrylic fiber. CONSTITUTION: This flame retardant acrylic synthetic fiber contains an antimony oxide in an amount of 2.0-10wt.% and a guanidine-based compound in an amount of 0.1-5wt.% based on a polymer comprising 30-80wt.% acrylonitrile, 20-70wt.% vinyl chloride and/or vinylidene chloride and 0-10wt.% other unsaturated monomers. The flame retardant acrylic synthetic fiber is obtained by forming the polymer into fiber.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant acrylic synthetic fiber having highly enhanced flame retardancy and good washing resistance and whiteness, and a method for producing the same.

[0002]

2. Description of the Related Art Modacrylic fibers are commercialized by blending various combustible fibers such as polyester, wool and cotton according to the purpose such as clothing, bedding such as blankets and sheets, interior products such as curtains and carpets. If
The phenomenon that flame retardancy is reduced occurs. For this reason, with the recent flame-retardant regulation, more flame-retardant modacrylic fiber has been required. Metal oxides have been widely added to increase the flame retardancy of modacrylic fiber, but among them, the effect of antimony oxides such as antimony trioxide and antimony pentoxide is large and economical. Target.

On the other hand, interior products, especially curtains, occupy a considerable weight as a cause of fires, and flame retardation of curtains is becoming more and more important. Most of the curtains are made of polyester as warp, and the flame-retardant of polyester is generally done by post-processing an organic phosphorus compound. However, in such post-processed products, it is inevitable that the flame retardant will fall off unless a binder such as aminoplast resin or acrylic ester resin is used, and such resin improves flammability and hardens the texture. There is a problem such as causing it, and it cannot be said to be a preferable method. There are also examples of adding phosphorus-based flame retardants during the production of polyester fibers,
At present, such phosphorus-based flame retardants are very expensive.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made in response to the needs for the recent advancement of flame retardancy.
In particular, it is an object of the present invention to provide a flame-retardant acrylic synthetic fiber having good washing resistance and whiteness, which is mainly used by mixing with polyester, and a method for producing the same.

[0005]

The gist of the present invention is that acrylonitrile is 30 to 80% by weight, vinyl chloride and / or vinylidene chloride is 20 to 70% by weight, and other unsaturated monomers are 0 to 10% by weight. 2. for polymers consisting of
0-10 wt% antimony oxide and 0.1-5.0
It is a flame-retardant acrylic synthetic fiber containing a guanidine compound by weight. Further, 2.0 to 10% by weight of antimony oxide is added to an organic solvent solution of a polymer constituting the flame-retardant acrylic synthetic fiber, wet spinning is performed, and the gel is swollen after washing with water. A flame-retardant acrylic synthetic fiber, characterized in that 0.1 to 5.0% by weight of the guanidine compound is contained in the fiber weight by applying a guanidine compound and an aromatic sulfonic acid to the fiber and then densifying the fiber by drying. Is a manufacturing method.

The polymers used in the present invention are 30-80% by weight of acrylonitrile, 20-70% by weight of vinyl chloride and / or vinylidene chloride, and 0-10 of other unsaturated monomers.
% By weight. Among the unsaturated monomers, a sulfonic acid group-containing monomer is preferable because it imparts denseness and dyeability to the fiber. Examples of the sulfonic acid-containing monomer used in the present invention include sodium allylsulfonate, sodium methallylsulfonate, sodium vinylsulfonate, sodium styrenesulfonate, and sodium 2-acrylamido-2-methylpropanesulfonate.

As the organic solvent used in the wet spinning of the present invention, dimethylformamide, dimethylacetamide or dimethylsulfoxide is used as a solvent for the dissolution of the polymer, recovery of the solvent,
It is preferable in terms of handleability.

The antimony oxide used in the present invention is preferably antimony trioxide or antimony pentoxide, which is atomized to a particle size of 1.5 μm or less, and is 2.0 to 10 with respect to the polymer. It is contained by weight%. If it exceeds 1.5μ, there is a drawback that clogging occurs during spinning. If necessary, the surface treatment of a titanate or silane coupling agent improves the dispersibility in an organic solvent and the compatibility with a polymer. If the amount of antimony oxide added is less than 2.0% by weight, the flame retardancy when other fibers are mixed is insufficient.
Further, if it exceeds 10% by weight, it is not preferable in terms of productivity and manufacturing cost.

In the method of the present invention, any known wet pulverizer may be used as a dispersing device, but a sand grinder, a pearl mill, a grain mill, a dyno mill may be used to continuously add the dispersion liquid to the spinning stock solution. Distribution tube type crushers such as The dispersion concentration of the organic solvent solution of antimony oxide used in the present invention is 15 to 4
It is 0% by weight, preferably 15 to 30% by weight. If the concentration is less than 15% by weight, the concentration of the spinning dope is lowered, the spinnability is lowered, and the fiber properties are lowered, depending on the amount of the fine powder added. On the other hand, if it exceeds 40% by weight, good uniform finely dispersed state cannot be obtained, and it becomes difficult to industrially manufacture.

In the present invention, wet spinning is carried out under the same conditions as in the case of ordinary acrylic synthetic fibers, and the fibers in gel swelling state after drawing and washing with water are treated with anionic, nonionic or cationic surface active agents as process oil agents. After applying the agent, the guanidine compound and the aromatic sulfonic acid, the mixture is dried and densified, so that the guanidine compound is added to the inside and the surface of the fiber in an amount of 0.1 to 5.
It contains 0% by weight. The surfactant is not particularly limited, but if it contains a phosphate-based component, it has an antistatic effect and improves process passability and spinnability.

The guanidine compound in the present invention means an acid-base pair type compound of guanidine or a derivative thereof and various acidic substances, and specifically, guanidine sulfamate, guanidine phosphate, guanidine methylol phosphate,
Guanidine hydrochloride, guanidine carbonate, guanidine tetraborate, guanidine tetraphosphate and the like can be mentioned. Among them, guanidine sulfamate and guanidine phosphate are particularly preferable. Originally, there are almost no examples in which a guanidine-based compound was applied to an acrylic fiber for the purpose of imparting flame retardancy. Particularly, considering the flame retardancy when mixed with polyester, the content of the guanidine compound was 0 depending on the mixing ratio. If it is less than 1% by weight, sufficient performance cannot be obtained, and if it exceeds 5.0% by weight, not only the flame retardant performance is saturated, but also coloring in the drying and densifying step is severe.

Examples of the aromatic sulfonic acid in the present invention include benzenesulfonic acid, o-toluenesulfonic acid,
p-toluenesulfonic acid, p-phenolsulfonic acid,
Examples thereof include o-phenol sulfonic acid and p-chlorobenzene sulfonic acid. In the present invention, it is essential to coexist aromatic sulfonic acid with a guanidine compound and impart it to the fiber. The amount of the aromatic sulfonic acid used may be determined so as to keep the pH of the surfactant and the guanidine compound solution at 6.0 or less. When the pH exceeds 6.0, the content of the guanidine compound in the fiber is 5. Even if it is less than 0% by weight, coloring occurs in the drying and densifying step and the commercial value is lowered.

In the present invention, the conditions for the drying and densification are preferably carried out in a hot air dryer in which the roller dryer has a surface temperature of 120 to 160 ° C. and / or a dry heat of 120 to 180 ° C. The drying time is preferably 1 to 7 minutes. In the present invention, it is preferable that the heat treatment after the dry densification is usually performed at a dry heat of 180 ° C. or lower and / or a wet heat of 120 ° C. or lower.

[0014]

Industrial Applicability The flame-retardant acrylic synthetic fiber of the present invention has excellent flame retardancy and has the fiber performance of ordinary acrylic synthetic fiber as it is, and also has a decrease in flame retardancy due to washing resistance. There is almost no one. Further, the method for producing an acrylic synthetic fiber of the present invention can industrially easily and inexpensively produce such a fiber under ordinary acrylic synthetic fiber production conditions and equipment. The fiber obtained by the present invention is a natural fiber such as cotton or wool, or a compound fiber, especially a polyester fiber, which is mixed with a fiber to maintain the texture and hygroscopicity of each fiber and also have flame retardancy. Become a product.

[0015]

EXAMPLES The present invention will be specifically described below with reference to examples. In the examples, "%" means "% by weight". The limiting oxygen index (hereinafter referred to as "LOI") used in the present invention is specified in JIS-K7201, and the value was obtained by performing the following test. To obtain the LOI, the fibers of the present invention and other fibers are mixed and defibrated with a hand card, about 0.5 g of cotton is taken, and this is evenly stretched to a length of 25 cm, and then a twisting machine is used. A twist bar was made by applying 70 twists and folding in half. Then, in the mixed gas of nitrogen gas and oxygen gas, the upper end of the twisted rod is contacted with flame, and the oxygen gas concentration in the mixed gas when the twisted rod burns by 5 cm is measured and calculated by the following formula. I did it. LOI = [oxygen gas / (nitrogen gas + oxygen gas)] × 100 The attached amount of the guanidine-based compound is the amount of phosphorus and sulfur contained in the compound, and the fluorescent X-ray analyzer 3270 manufactured by Rigaku Co., Ltd.
It was quantified using a mold and converted into a guanidine compound attached to the fiber. Raw cotton whiteness is 1.0 g after unwinding with a hand card
The obtained cotton was put in a cell and evaluated by b ^* value using a colorimeter CE-7000 manufactured by Macbeth.

Examples 1 to 4, Comparative Examples 1 to 4 Acrylonitrile / vinylidene chloride (VCL ₂ ) / 2-
A dimethylformamide (DMF) solution of an acrylic copolymer composed of acrylamido-2-methylpropanesulfonic acid sodium (SAM) = 57/40/3 (weight ratio) was prepared. A solution in which 40% of antimony trioxide was previously dispersed in dimethylformamide with respect to the acrylic copolymer by using a sand grinder was added to the acrylic copolymer solution in an amount shown in Table 1 and stirred to obtain 25%. This was the spinning dope. The above spinning dope was spun into a 58% DMF aqueous solution at 20 ° C., and the gel swollen fiber after the usual drawing and washing process was treated with p-toluene sulfone so that the guanidine compound shown in Table 1 and the pH of the treating solution would be the same. The acid was applied with the fiber oil. Then, it was dried and densified at 140 ° C. using a roller dryer. Wet heat after applying mechanical crimp 1
Crimp setting was performed at 10 ° C. to obtain 3d fibers. The fiber obtained by the above method was cut to a constant length of 51 mm, and the flame retardancy and raw cotton whiteness were examined. In addition, flame retardant is polyester (P
ET) 3d × 51 mm mixed with 50% was also examined. Comparative Example 1 did not contain a guanidine compound and thus lacked flame retardancy in a PET mixture, and Comparative Example 3 lacked antimony trioxide and thus lacked overall flame retardancy.
In Comparative Example 2, the pH was not adjusted properly and the fiber turned yellow.

Example 5 Acrylonitrile / vinylidene chloride / 2 sodium acrylamido-2-methylpropanesulfonic acid (SAM) = 5
A dimethylformamide solution of acrylic copolymer consisting of 3/44/3 was prepared. 8.0% / p of antimony trioxide was added to the acrylic copolymer and stirred to prepare a spinning dope. The spinning solution was spun into a 58% DMF aqueous solution at 20 ° C., and the gel swollen fiber after the usual stretching and washing step was added with guanidine phosphate at 2.0% / p, and the pH of the treatment solution was 5. P-toluene sulfonic acid was added together with the fiber oil so that the amount became 5. Then, it was dried and densified at 140 ° C. using a roller dryer. Next, a mechanical crimp was applied, and then crimp setting was performed at 110 ° C. in moist heat to obtain 3d fibers. Polyester is added to the fiber obtained by the above method.
% Cotton was mixed and put in Tetron net, and the flame retardancy after 10 and 20 times of home washing under the following conditions was examined. As a result, as shown in Table 2, it was found that even after 20 washes, the performance was good. Washing conditions Commercially available small electric washing machine Temperature x time 40 ° C x 5 minutes Neutral detergent 1g / l Water wash 10 minutes Bath ratio 1: 100 Dry 80 ° C x 1 hour

[0018]

[Table 1]

[0019]

[Table 2]

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Claims (2)

[Claims] 1. Acrylonitrile 30 to 80% by weight, vinyl chloride and / or vinylidene chloride 20 to 70% by weight,
And 2.0 to 10% by weight of antimony oxide and 0.
A flame-retardant acrylic synthetic fiber containing 1 to 5.0% by weight of a guanidine compound. 2. Acrylonitrile 30 to 80% by weight, vinyl chloride and / or vinylidene chloride 20 to 70% by weight,
And 2. a solution of a polymer composed of 0 to 10% by weight of another unsaturated monomer in an organic solvent, and 2. added antimony oxide to the polymer.
The guanidine compound and the aromatic sulfonic acid are added to the above-mentioned fiber in the gel swelling state after adding 0 to 10% by weight, wet spinning, and drawing and washing with water, and then dried and densified, and the guanidine compound is added to the fiber weight. A method for producing a flame-retardant acrylic synthetic fiber, characterized by containing 0.1 to 5.0% by weight.