JPH06287806A - Acrylic synthetic fiber improved in flame retrardancy and its production - Google Patents

Abstract

PURPOSE:To obtain the subject fibers good in producibility and post- processability, usable through blending with other fibers, resistant to washing, by incorporating a polymer for modacrylic fibers with antimony trioxide and a specific flame retardant. CONSTITUTION:A polymer from (A) 30-80wt.% of AN, (B) 20-70wt.% of PVC and/or vinylidene chloride and (C) 0-10wt.% of another unsaturated monomer is incorporated with (D) 3.0-20wt.% of antimony trioxide and (E) 3.0-20wt.% of a Br-based flame retardant of the formula, followed by being made into fibers. There is virtually no loss of the components D and E during the fibermaking process, thus improving the flame retardancy of the aimed fibers.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention uses a flame-retardant agent, which is highly flame-retarded and has excellent productivity, and also has good post-processability such as spinning. The present invention relates to a synthetic acrylic fiber having properties and a method for producing the same.

[0002]

2. Description of the Related Art Flame-retardant modacrylic fiber is produced by blending various easily flammable 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. When it is converted, the phenomenon that the flame retardancy is lowered occurs. For this reason,
With recent flame retardant regulations, more flame retardant modacrylic fiber has become necessary.

Conventionally, various flame retardants have been added to spinning dope or post-processed into fibers. For example, as a flame retardant for halogen-based organic compounds, Br is more preferable than Cl-based.
Although the flame retardant effect is greater in the system, there is an example in JP-A-48-4718 in which tetrabromobisphenol ether A and antimony trioxide are used in combination.

Further, as an inorganic flame retardant, JP-A-49-204
No. 36 discloses zirconium oxide, JP-A-53-287.
No. 28 discloses an example in which a large amount of each zinc compound is used alone or a Br-based organic compound such as hexabromobenzene or tetrabromobutane is used in combination.

However, the Br-based organic compounds listed therein are almost soluble in organic solvents, and in fact, many are lost during the spinning process and the subsequent manufacturing process.

In Japanese Patent Publication No. 4-18050, an antimony compound is added in a considerably large amount of 12 to 50% by weight to a halogen-containing polymer to form a flame-retardant reinforcing fiber, which is combined with a natural fiber to form a flame-retardant material. Although an example of forming a fiber composite is disclosed, as a practical matter, it is very difficult to add up to 50% by weight because of clogging during spinning and post-processability of the fiber, which is not only practical. From the viewpoint of flammability, it is preferable to combine several kinds of flame retardants such as a Br organic compound in combination. Addition of flame retardancy by post-processing has a problem of poor washing resistance.

[0007]

DISCLOSURE OF THE INVENTION The present invention meets the recent needs for advanced flame retardancy, that is, antimony trioxide and Br-based organic compounds which hardly fall out in the conventional manufacturing process. To provide an acrylic synthetic fiber having wash resistance, which is mainly used by mixing with other natural fibers and chemical fibers with flame retardant enhanced productivity and good post-processability due to the combined use effect thereof, and a manufacturing method thereof. is there.

[0008]

The gist of the present invention is that 30-80% by weight of acrylonitrile, 20-70% by weight of vinyl chloride and / or vinylidene chloride and 0-10% by weight of other unsaturated monomers. For a polymer consisting of
3.0-20 wt% antimony trioxide and general formula

[Chemical 5]

[Chemical 6] Flame retardant which is a Br-based organic compound represented by
It is a flame retardant reinforced acrylic synthetic fiber composed of 0% by weight.

Further, a polymer comprising 30 to 80% by weight of acrylonitrile, 20 to 70% by weight of vinyl chloride and / or vinylidene chloride and 0 to 10% by weight of another unsaturated monomer is added to dimethylformamide, dimethylacetamide or dimethylsulfoxide. 15 to the organic solvent selected from the group
After dissolving to 30% by weight, 15-40% by weight
Dispersion of antimony trioxide having a particle size of 1.5 μm or less and 1
General formula of 5-40% by weight

[Chemical 7]

[Chemical 8] An acrylonitrile-based polymer solution obtained by mixing a dispersion liquid of a flame retardant which is a Br-based organic compound represented by the above formulas so that each component has a concentration of 3.0 to 20% by weight with respect to the polymer is composed of an organic solvent and water. A method for producing a flame-retardant reinforced acrylic synthetic fiber, which comprises discharging into a coagulation tank and spinning.

The antimony trioxide used in the present invention has an average particle size of 1.5 μm or less. If it exceeds 1.5μ,
There is a drawback that it causes clogging during spinning. Also Br
The chemical structure of organic compounds

[Chemical 9]

[Chemical 10] When a compound having a molecular weight of 900 or more is used, the quality of the product is stable in the spinning process and the subsequent manufacturing process.

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 allyl sulfonate, sodium methallyl sulfonate, sodium vinyl sulfonate, sodium styrene sulfonate, sodium 2-acrylamido-2-methylpropane sulfonate, and the like. .

The organic solvent used in the wet spinning of the present invention includes dimethylformamide, dimethylacetamide or dimethylsulfoxide, which are preferable in terms of polymer solubility, solvent recovery and handling.

The antimony trioxide used in the present invention has a particle size of 1.5 μm or less, and is contained in an amount of 3.0 to 20% by weight based on the polymer. 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.

The Br organic compound used in combination has a molecular weight of 90.
General formula of 0 or more

[Chemical 9]

It is a Br-based organic compound represented by the formula: and is contained in an amount of 3.0 to 20% by weight based on the polymer.

If both antimony trioxide and Br organic compound are less than 3.0% by weight, the flame retardancy when blended with other fibers is insufficient. On the other hand, if it exceeds 20% by weight, clogging or the like will occur during spinning, resulting in poor operability.

Since these compounds have a large molecular weight to some extent and are structurally sparingly soluble in organic solvents, there are almost no omissions in the process of fiber production, which is advantageous in collecting and re-preparing the coagulating liquid, and is difficult to add. The quality is stable because the flame retardant effectively remains in the fiber.

Regarding the added amount of each flame retardant, when the total amount is the same, it is used in the present invention that the antimony trioxide and the Br type organic compound are almost equivalent or the Br type organic compound is slightly increased. The polymer had high flame retardancy and had little clogging during spinning. That is, it was found that the quality was superior to that obtained by adding a large amount of antimony trioxide alone or Br organic compound alone.

In the method of the present invention, the dispersion operation to be used may be any known wet pulverizer, but in order to continuously add the dispersion to the spinning dope, a sand grinder, a pearl mill, a Glen mill, A distribution tube type crusher such as Dynomill is suitable.

The dispersion concentration of the organic solvent solution of antimony trioxide and Br type organic compound used in the present invention is 15
-40% by weight, preferably 15-30% 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.

Spinning may be performed under the same conditions as for ordinary acrylic synthetic fibers, passing through several stages of baths, followed by sequential drawing, washing with water,
Dry and post-process.

[0022]

EFFECT OF THE INVENTION The flame-retardant reinforced acrylic synthetic fiber of the present invention has excellent flame retardancy and has the same fiber performance as that of ordinary acrylic synthetic fibers, and the flame retardancy is deteriorated by washing resistance. There is almost no. 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 fibers obtained by the present invention can be used as a mixture with ordinary fibers such as cotton, wool, etc., and chemical fibers to maintain the properties such as texture and hygroscopicity of each fiber and also have flame retardancy. It becomes a textile product.

[0024]

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 JIS-K7201.
The value is determined 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 and then about 0.
5 g of cotton was taken, this was evenly stretched to a length of 25 cm, and twisted 70 times with a twisting machine to fold it in half to make a twisted rod. Then, in the mixed gas of nitrogen gas and oxygen gas, the upper end of the twisted bar was contacted with flame, and the twisted bar was 5 cm.
The oxygen gas concentration in the mixed gas at the time of only burning was measured and determined by the following formula. LOI = [oxygen gas / (nitrogen gas + oxygen gas)] × 10
0

Examples 1 to 5 and Comparative Examples 1 to 3 Acrylonitrile / vinylidene chloride (VCl ₂ ) / sodium allyl sulfonate (SAS) = 57/40/3 dimethylformamide solution of acrylic copolymer was prepared. . A liquid obtained by preliminarily dispersing 40% of antimony trioxide in dimethylformamide with respect to the acrylic copolymer by using a sand grinder and the general formula

[Chemical 11] A brominated aromatic triazine compound represented by or a general formula

[Chemical 12] A solution prepared by dispersing 40% of decabromodiphenyl ether shown in 1 above in dimethylformamide was added to the acrylic copolymer solution in an amount shown in Table 1 and stirred to prepare a spinning dope.

The above spinning solution was spun into an aqueous solution of dimethylformamide at 20 ° C. and 60%, washed with water while being drawn with a solvent, applied with an oil agent, and dried and densified. After crimping the fibers, they were heat-treated at 115 ° C. to obtain flame-retarded acrylic synthetic fibers.

The fibers obtained by the above method were mixed with cotton in the amounts shown in Table 1 to obtain flame retardance and characteristics of cotton (sensory test:
It was examined whether or not it had a judgment of 3). In addition, clogging during spinning, yarn breakage, and post-processability were also evaluated.

As a comparative example, antimony trioxide, Br
An example was given in which the amount of the organic compound added was outside the range of the present invention.

[0031]

[Table 1]

In Comparative Example 1, clogging was observed because of the large amount of antimony trioxide, but it was possible to make fibers for the time being. However, the characteristics as cotton decreased, and the LOI value was low in spite of the large amount of antimony trioxide added. Comparative Example 2 had a low LOI value because antimony trioxide was not added.

Example 6 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% each of antimony trioxide and Br-based organic compound decabromodiphenyl ether were added to the acrylic copolymer and stirred to prepare a spinning dope.

The above spinning solution was spun into an aqueous solution of dimethylformamide at 20 ° C. and 60%, washed with water while stretching while removing the solvent, and then an oil agent was added to dry and densify it. After crimping the fibers, they were heat-treated at 115 ° C. to obtain flame-retarded acrylic synthetic fibers. At that time, the spinnability was good.

The fibers obtained by the above method were mixed with 70% wool and put in a tetron net, and after 10 or 20 times of home washing, it was examined whether or not it had characteristics of flame retardancy and wool.

As a result, as shown in Table 2, it was found that it has good performance even after 20 times of washing.

Washing conditions Commercial small electric washing machine use Temperature x time 40 ° C x
5 minutes Neutral detergent 1g / l Washing with water 10 minutes Bath ratio 1: 100 Drying 80 ℃ ×
1 hour

[0038]

[Table 2]

Claims (2)

[Claims] 1. 3.0 to 20 relative to a polymer comprising 30 to 80% by weight of acrylonitrile, 20 to 70% by weight of vinyl chloride and / or vinylidene chloride and 0 to 10% by weight of another unsaturated monomer. Wt% antimony trioxide and the general formula: [Chemical 2] Flame retardant which is a Br-based organic compound represented by
Flame-retardant reinforced acrylic synthetic fiber containing 0% by weight. 2. A polymer consisting of 30 to 80% by weight of acrylonitrile, 20 to 70% by weight of vinyl chloride and / or vinylidene chloride and 0 to 10% by weight of another unsaturated monomer is added to dimethylformamide, dimethylacetamide or dimethylsulfoxide. After being dissolved in an organic solvent selected from the group of 15 to 30% by weight, a dispersion of 15 to 40% by weight of antimony trioxide having a particle size of 1.5 μ or less and 15 to 4
0% by weight of the general formula [Chemical 4] An acrylonitrile-based polymer solution obtained by mixing a dispersion liquid of a flame retardant which is a Br-based organic compound represented by the above formulas so that each component has a concentration of 3.0 to 20% by weight with respect to the polymer is composed of an organic solvent and water. A method for producing a flame-retardant reinforced acrylic synthetic fiber, which comprises discharging into a coagulation tank and spinning.