JPH0978344A - Flame-retardant acrylic synthetic fiber excellent in weather resistance and yellowing resistance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject fiber good in dyeabilility, transparency and operability and capable of being sufficiently applied to outdoor tents, parasols, etc., by adding a specific UV light-absorbing copolymer and a heat stabilizer to a modified acrylic fiber polymer. SOLUTION: The flame-retardant acrylic synthetic fiber is produced by adding (A) 0.1-3wt.% of a copolymer having a mol.wt. of 2000-50000 and containing 20-60wt.% of an UV light-absorbing monomer of formula I (X is H, CH3 ) and (B) 0.05-2wt.% of a heat stabilizer of formula II, 9,10-dihydro-9-oxa-10- phosphaphenanthrene-10-oxide, to (C) an acrylonitrile polymer containing vinyl chloride and/or vinylidene chloride, and subsequently processing the mixture into the fiber.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant acrylic synthetic fiber excellent in weather resistance and yellowing resistance.

[0002]

BACKGROUND OF THE INVENTION Acrylic synthetic fibers are widely used for clothing and bedding because of their excellent texture and dyeability. However, the fibers easily turn yellow due to light or heat, and their applications and processing methods are limited. In particular, modacrylic fibers containing halogen such as chlorine as a copolymerization component have a problem that they tend to yellow.

In order to solve such a problem, for example, Japanese Patent Publication No. 63-57522 and Japanese Patent Publication No. 2-15642 disclose modacrylic fibers containing a UV absorber which is a benzotriazole compound, and JP-A-2-33315. Japanese Unexamined Patent Publication (Kokai) proposes modacrylic fiber to which organic tin is added. However, in wet spinning, which is widely used in the production of acrylic fibers, the ultraviolet absorber and the organic tin are eluted into the coagulation bath, resulting in poor yield and adversely affecting dyeability and transparency. Also, when using these fibers outdoors,
Additives fall off due to rain, and deterioration of weather resistance and light resistance cannot be avoided.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a flame-retardant acrylic synthetic fiber which has good dyeability, transparency, operability, weather resistance and yellowing resistance.

[0005]

The above-mentioned problems can be solved by using a general formula for an acrylonite-based polymer containing vinyl chloride and / or vinylidene chloride.

Embedded image A copolymer having a molecular weight of 2,000 to 50,000 containing 20 to 60% by weight of an ultraviolet absorbing monomer represented by
3% by weight and

Embedded image The heat-resistant agent represented by 9,10-dihydro-9-oxa-1
Excellent weather resistance and yellowing resistance, characterized in that the content of 0-phosphaphenanthrene-10-oxide (hereinafter referred to as DOPO) is 0.05 to 2% by weight based on the acrylonitrile polymer. Achieved by flame retardant acrylic synthetic fiber.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION As the acrylonitrile polymer containing vinyl chloride or vinylidene chloride used in the present invention, acrylonitrile (AN) is 30 to 80% by weight, vinyl chloride or vinylidene chloride is 20 to 70% by weight and unsaturated. It is composed of 0 to 10% by weight of a monomer. Among the unsaturated monomers, a sulfonic acid group-containing monomer is particularly preferable because it imparts denseness and dyeability to the fiber. The acrylonitrile-based polymer containing vinyl chloride or vinylidene chloride is produced by a known method such as ordinary aqueous suspension polymerization, emulsion polymerization or solution polymerization, and is not particularly limited.

The ultraviolet absorbing monomer used in the present invention has a general formula

Embedded image And a benzotriazole-based compound given by. The amount contained in the copolymer of the above monomers is 20 to 60.
% By weight, preferably in the range 30 to 50% by weight. If it is less than 20% by weight, the effect of improving the weather resistance is insufficient, and if a large amount of a copolymer having a content of less than 20% by weight is added, the fiber physical properties such as the flame retardance and heat resistance of the obtained fiber are reduced. It has an adverse effect. On the other hand, when it exceeds 60% by weight, the copolymer is colored and heat resistance is deteriorated, which is not preferable.

General formula

[Chemical 6] 40 to 8 used in addition to the ultraviolet absorbing monomer represented by
0% by weight of the monomer is not particularly limited,
Examples thereof include methacrylic acid derivatives such as methyl methacrylate and acrylic acid derivatives such as methyl acrylate. It is also possible to partly use acidic monomers such as sodium allyl sulfonate, sodium methallyl sulfonate, and sodium vinyl sulfonate.

The molecular weight of the copolymer used in the present invention must be 2,000 to 50,000 in terms of polystyrene equivalent in gel permeation chromatograph (GPC). If the molecular weight is less than 2000, it is eluted in the coagulation bath during wet spinning and the yield is poor. Also, 50
If it is 000 or more, the viscosity of the polymer solution becomes high and it is difficult to add it to the spinning dope.

To obtain the effect of improving weather resistance, a general formula is used.

[Chemical 7] The content of the UV-absorbing monomer represented by is 0.1 to 3% by weight, preferably 0.5 to
It is preferable to set it to 1.5% by weight. If the content is 0.1% by weight, no sufficient effect can be obtained, and if it exceeds 3% by weight, the effect is saturated and the flame retardancy and fiber physical properties are deteriorated.

The DOPO used in the present invention is

Embedded image Which is 0.
It is necessary that the content is 05 to 2% by weight. If it is less than 0.05% by weight, the anti-coloring effect cannot be obtained. On the other hand, if it exceeds 2% by weight, the coloring may be severe, which is not preferable.

In the present invention, the general formula

Embedded image A copolymer containing an ultraviolet absorbing monomer of

Embedded image The DOPO represented by 1 may be added directly to the spinning stock solution in which the acrylic polymer is dissolved, or may be added to the spinning stock solution after being dispersed or dissolved in an organic solvent. General formula

Embedded image A copolymer containing a UV-absorbing monomer of

[Chemical 12] By adding DOPO represented by the above formula to the acrylic polymer in the above content range, the weather resistance and yellowing resistance are dramatically improved.

In the present invention, the general formula

Embedded image A copolymer containing an ultraviolet absorbing monomer of

Embedded image The spinning stock solution to which DOPO is added is formed into fibers by a usual wet method, a dry method, a dry method, or the like. For example, in the case of wet spinning, the same method as in the case of ordinary flame-retardant acrylic synthetic fibers may be used, and fibers are obtained by sequentially stretching, washing with water, drying and post-treating through several baths.

[0014]

The present invention will be specifically described below with reference to examples. For the measurement and evaluation of weather resistance and yellowing resistance, the obtained flame-retardant acrylic synthetic fiber was spun by an ordinary method and circular knitted was prepared as a sample. Then, this sample is 150 W / in high energy type xenon fade meter.
m ² , black panel temperature 63 ° C., relative humidity 50%, irradiation time 200 hours, and the discoloration degree was evaluated. In addition, 6 with a sunshine carbon weather meter
The strength / elongation retention rate was measured and evaluated as a single fiber that was treated under the conditions of 0 W / m ² and a black panel temperature of 63 ° C. for 400 hours.

The strong energy type xenon fade meter is a light source that emits a large amount of light as compared with a normal xenon fade meter and emits high energy particularly in the ultraviolet region, and can shorten the processing time.

Examples 1 to 4, Comparative Examples 1 to 4 Acrylonitrile (AN) / vinylidene chloride / (VCl
A dimethylformamide (DMF) solution of a polymer consisting of ₂ ) / 2-acrylamido-2-methylpropanesulfonic acid sodium (SAM) = 58/40/2 was prepared as a spinning stock solution. In addition, 50% of 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole (HMB) and 50% of methyl methacrylate.
% Of polystyrene-converted copolymer having a molecular weight of 10,000
A 0% DMF solution was prepared. This was added to the above spinning solution as shown in Table 1.
The mixture was added and mixed in an addition amount of and spun into a 60% DMF aqueous solution. The spun tow was washed with water, applied with a fiber oil, and dried and densified at 140 ° C. using a roller dryer. Then, a mechanical crimp was applied, and the crimp was set at 110 ° C. under moist heat. The obtained fiber was cut and spun, and then a circular knit fabric was prepared and subjected to the above weather resistance test. Comparative Example 4 is a weather-resistant polypropylene widely used as a fiber for outdoor tents. The results are summarized in Table 1.

[0017]

[Table 1]

[0018]

EFFECTS OF THE INVENTION The flame-retardant acrylic synthetic fiber obtained by the present invention is a fiber excellent in weather resistance and yellowing resistance, and can be used in outdoor tents, parasols, etc., which are limited by the conventional flame-retardant acrylic synthetic fiber. It can be used for various purposes.

Claims (1)

[Claims] 1. Acrylonitrile-based polymer containing vinyl chloride and / or vinylidene chloride is represented by the general formula: A copolymer having a molecular weight of 2000 to 50000 containing 20 to 60% by weight of an ultraviolet absorbing monomer represented by
3% by weight and The heat-resistant agent represented by 9,10-dihydro-9-oxa-1
The content of 0-phosphaphenanthrene-10-oxide is 0.05 to 2 based on the acrylonitrile polymer.
A flame-retardant acrylic synthetic fiber having excellent weather resistance and yellowing resistance, which is characterized by being in a weight percentage.