JPH0473216A - Antistatic acrylic fiber and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject fiber having excellent antistaticity and durability and useful for clothes, etc., by conjugating a plurality of specific acrylonitrile copolymer spinning dopes immediately before extruding through a spinning nozzle and coagulating the extruded fiber. CONSTITUTION:The objective fiber is produced by the conjugate spinning of (A) an acrylonitrile copolymer composed of (i) >=60 wt.% of acrylonitrile and (ii) 0.1-40 wt.% of a monomer of formula (R1 to R5 are H or lower alkyl; m is <=10) and (B) an acrylonitrile copolymer composed of >= 70 wt.% of the component (i) and (iii) < 30 wt.% of a polymerizable vinyl compound other than the compound of formula. At least a part of the outer circumference of the cross-section of the fiber is made of the component A and the ratio of the component A to the component B is 1:(1-500). The conjugate fiber can be produced by conjugating the spinning dope of the component A and the spinning dope of the component B immediately before extruding through a spinning nozzle and coagulating the conjugated extrudate.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to acrylic fibers with permanent antistatic properties.

(Conventional technology) Generally, acrylic fiber has heat retention, shape stability, light resistance,
It has excellent texture, dyeability, etc., and is used for clothing, interior decoration, etc. However, it generates significant static electricity, and when used for clothing or interior decoration, it causes discomfort to the human body. It has the disadvantage of giving. Also, when used in the precision electronics field, static electricity is generated, which can be a source of trouble (JR).

It may be a cause.

In order to improve these drawbacks, it has been common practice to treat fibers with an antistatic agent consisting of a surfactant (Japanese Patent Publication No. 45-21892). As another method, it has been proposed to use an acrylonitrile copolymer obtained by copolymerizing a hydrophilic monomer containing an ethylene oxide chain with acrylonitrile (Japanese Patent Application Laid-Open No. 6262912).

(Problems to be Solved by the Invention) As described above, when fibers are treated with an antistatic agent, they exhibit excellent antistatic properties initially, but the antistatic properties often deteriorate significantly with repeated washing.

In response, attempts have been made to copolymerize vinyl monomers containing ethylene oxide chains to provide permanent antistatic performance; The current situation is that it has not reached the point where it can demonstrate its performance. Furthermore, the use of this vinyl monomer also poses manufacturing problems such as generation of bubbles during polymerization.

The purpose of the present invention is to solve the above-mentioned problems and to provide an antistatic fiber using a novel acrylonitrile copolymer that has permanent and excellent antistatic performance.・ (Means for solving the problem) As a result of intensive studies on the various problems mentioned above, the present inventors have discovered a fiber that uses a new acrylonitrile copolymer and has permanent and extremely excellent antistatic performance. Ta.

The gist of the present invention is to provide an acrylonitrile copolymer (D1) consisting of 60% by weight or more of acrylonitrile and 0.1 to 40% by weight of a monomer represented by the following formula (A), and 70% by weight of acrylonitrile.
Acrylonitrile copolymer (
A fiber obtained by composite spinning D2), in which at least a part of the outer periphery of the fiber cross section is composed of the copolymer (D1),
The ratio of both copolymers (D1) and (D2) is 1:1 to 1:5
00 antistatic fiber.

OR.

[A]

(R, to R5 are hydrogen or lower alkyl groups, and may be the same or different. m is an integer of 10 or less.) In the present invention, the acrylonitrile copolymer (D1)
Among them, the monomer shown by (A) has a 0. 1-40% by weight
If it is less than 0.1% by weight, sufficient antistatic performance cannot be obtained, and if it exceeds 40% by weight, the effect is small and uneconomical.

In the present invention, it is also possible to contain less than 40% by weight of other copolymerizable monomers.

Other copolymerizable unsaturated vinyl compounds include vinyl acetate, acrylic acid, methacrylic acid, methyl acrylate, acrylamide, methacrylamide, vinylidene chloride, and the like.

The acrylonitrile copolymer (D2) may be a polymer used for ordinary acrylic fibers, but the acrylonitrile content is required to be 70% by weight or more. If it is less than 70% by weight, the properties of the acrylonitrile polymer will be lost. It is also possible to contain less than 30% by weight of other copolymerizable monomers. Examples of other polymerizable unsaturated vinyl compounds that can be copolymerized include vinyl acetate, acrylic acid, methacrylic acid, acrylamide, methacrylamide, and vinylidene chloride.

The intrinsic viscosity of these copolymers must be 0.8 to 10; if it is less than 0.8, the resulting fibers will not have sufficient flexibility and will become brittle. . Moreover, when it exceeds 10, formability becomes very poor.

Any radical polymerization initiator can be used as the polymerization initiator. For example, azo compounds such as azobisisobutyronitrile or 2.2°-azohis (2,2 dimethylvaleronitrile), organic peroxides such as aliphatic diacyl peroxides, or peroxyesters, or persulfates and Examples include redox initiators that are a combination of these and a reducing agent. The amount of initiator used must be adjusted as appropriate from the viewpoint of degree of polymerization, polymerization stability, or initiator efficiency.

As the polymerization method, emulsion polymerization, suspension polymerization, and solution polymerization are preferred. As a suspension polymerization method, it is also possible to perform polymerization in a mixed medium of water and an organic solvent in addition to an aqueous system.

When producing the fiber of the present invention, the above (D1), (D2)
Examples of the solvent used in the spinning stock solution of the acrylonitrile copolymer include organic solvents such as dimethylacetamide, dimethylformamide, dimethyl sulfoxide, ethylene caponate, and γ-butyrolactone, and inorganic solvents such as nitric acid and an aqueous solution of sodium thiocyanate.

The spinning stock solutions obtained from the antistatic acrylonitrile copolymer (D1) and the acrylonitrile copolymer (D2) are simultaneously discharged to perform so-called composite spinning. At this time, it is preferable to combine the two spinning stock solutions immediately before discharge from the spinning hole and then discharge them into the coagulation liquid. At this time, at least a part of the outer periphery of the polymer solution discharge hole of the spinneret is arranged so that the weight ratio of the antistatic acrylonitrile copolymer (D1) and the acrylonitrile copolymer (D2) is 1:1 to 1:500. Perform composite spinning. If (D1)/(D2) is smaller than 11500, sufficient antistatic properties cannot be obtained, and (D1)/(D2)
) is larger than 1, the effect is small and uneconomical.

Examples of the composite spinning method include core-sheath type composite spinning and side-by-side type composite spinning. The spinning method is not particularly limited, and wet spinning, dry-wet spinning, and dry spinning are performed. After solidification, washing, stretching, and drying are performed in the usual manner.

In the thus obtained fiber, the antistatic acrylonitrile copolymer (D1) is localized so as to constitute at least a part of the outer periphery with respect to the cross section of the fiber, and the copolymer (D1) is located in the axial direction of the fiber. It has a morphology that forms a continuous phase, and both (D1) and (D2) are copolymers based on acrylonitrile, which have good adhesion and permanently exhibit excellent antistatic performance. It is.

(Example) Hereinafter, the present invention will be specifically explained with reference to Examples.

In addition, "%" in the following description represents weight %.

Moreover, the "limiting viscosity" was measured by dissolving the copolymer in dimethylformamide at 25°C.

"Antistatic property" was determined by humidity-conditioning the sample for two days and nights in a constant temperature and humidity room at 20°C and various relative humidity conditions, and then measuring the half-life using a static honest meter (Soybean Shokai) under the following conditions.

"Washing resistance" was measured using a household electric washing machine using Monogen Uni (trade name) 2 g/l, bath ratio 1150 to 1/100.
After placing the sample in a 40°C bath and washing it for 10 minutes,
The operation of washing with water for 0 minutes and drying was repeated, and the antistatic property was measured and evaluated as described above.

Control ■To1L:MeH3 Applied voltage: 10,000 volts Application time = 30 seconds Sample rotation speed: LOOOrpm Atmosphere = 20°C Various humidity conditions Acrylonitrile and antistatic monomer [I] were copolymerized as shown in Table 1. The copolymer obtained by copolymerizing acrylonitrile and vinyl acetate was dissolved in dimethylacetamide to a concentration of 300 to 400 poise at 70°C to prepare a spinning stock solution.

These stock solutions were discharged from a core-sheath type composite spinneret at various discharge ratios into a coagulation bath that is a mixed solution of DMAc and water, stretched 5 times with wet heat, washed, oiled, and dried.
Antistatic acrylic fibers were obtained.

Table 1 shows the antistatic performance of each.

The copolymer of Example 1 was spun alone on the sieve, and an antistatic acrylic fiber was obtained in the same manner as in Example 1.

This antistatic performance is shown in Table 1.

Comparative Example I Acrylonitrile and antistatic monomer [X] were copolymerized and wet-spun in the same manner as in Comparative Example 1 to obtain antistatic acrylic fibers.

Its antistatic performance is shown in Table 1.

Comparison 1 Acrylonitrile and antistatic monomer [Y] were copolymerized, and composite spinning was performed in the same manner as in Example 1 to obtain antistatic acrylic fibers.

Its antistatic performance is shown in Table 1.

(Hereinafter, blank spaces) (Effects of the invention) As is clear from the above explanation, the acrylic fiber according to the present invention exhibits superior antistatic performance with a small amount of antistatic polymer blended, compared to conventional acrylic fibers. Moreover, it is an antistatic acrylic fiber with excellent durability, and can be expected to be applied in a wide range of fields such as clothing, interior decoration, and materials.

Claims (2)

[Claims] (1) An acrylonitrile copolymer (D1) consisting of 60% by weight or more of acrylonitrile and 0.1 to 40% by weight of a monomer represented by the following formula, and an acrylonitrile copolymer (D1) consisting of 70% by weight or more of acrylonitrile and a monomer other than that represented by the following formula. A fiber obtained by composite spinning an acrylonitrile copolymer (D2) comprising less than 30% by weight of a polymerizable unsaturated vinyl compound,
At least a part of the outer periphery of the fiber cross section is composed of the copolymer (D1), and the ratio of both copolymers (D1) and (D2) is 1:
An antistatic acrylic fiber having a ratio of 1 to 1:500. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R_1 to R_5 are hydrogen or lower alkyl groups,
They may be the same or different. m is an integer of 10 or less. ) (2) Production of the fiber according to claim 1, characterized in that the spinning dope of the acrylonitrile copolymer (D1) and the spinning dope of the acrylonitrile copolymer (D2) are combined and solidified immediately before discharge from the spinning hole. Law.