JPH10121327A - Production of modified polyester fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject fiber improved in water absorbancy and hygroscopicity and useful for clothes, etc., good in antistaticity, comfortableness, etc., by graft-polymerizing to polyester fibers a hydrophilic unsaturated compound such as acrylic acid or methacrylic acid in the presence of a specific catalyst. SOLUTION: A hydrophilic unsaturated compound of the formula: CH2 =CR<1> COX (R<1> is H, methyl; X is hydroxyl, amino, a hydroxyl group-containing alkoxy, a hydroxyl group-containing oxyalkoxy) in an amount of 3-60wt.% is graft-polymerized to polyester fibers in an aqueous redox catalyst solution containing hydrogen peroxide and a divalent iron salt (e.g. ferrous sulfate, ferrous dichloride).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a modified polyester fiber.

[0002]

2. Description of the Related Art Polyester fibers are the most frequently used synthetic fibers because of their excellent physical and chemical properties, but they are not always satisfactory in all, and various modifications are required. It has been done. Graft polymerization of vinyl monomers is one of them. Conventionally, benzoyl peroxide has been used as a polymerization initiator when graft copolymerizing a vinyl monomer to a polyester fiber (Journal of the Fiber Society of Japan Vol. 36 N
o.10 1980), celium salt (ibid. Vol.28 No.9 1972),
Irradiation (Tex. Res. Joul. Vol. 61 No. 8 1991, etc.), azobisisobutyronitrile (Textile Society of Japan Vol 21 No. 3 1
965). However,
An inexpensive catalyst for efficiently graft copolymerizing a hydrophilic unsaturated compound such as acrylic acid or methacrylic acid has not been proposed.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for efficiently and inexpensively graft-copolymerizing a hydrophilic unsaturated compound with a polyester fiber.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, in an aqueous solution containing hydrogen peroxide and a divalent iron salt, the following general formula CH ₂ ＣＲCR ¹ COX (1) (where R ¹ is a hydrogen or methyl group) Wherein X represents a hydroxyl group, an amino group, a hydroxyl group-containing alkoxy group or a hydroxyl group-containing oxyalkoxy group), wherein a hydrophilic unsaturated compound represented by the following formula is graft-copolymerized: Is provided.

[0005] As the polyester fiber used in the present invention, various commercial products can be used.
It is preferred to use what can be dyed at a temperature of up to 100 ° C. in the atmosphere, which is called a normal pressure dyeable polyester fiber in the market. Examples of such commercially available fibers include Toray Tetron A216, Teijin Tetron TKO4P, Toyobo Ester D93, and the like. The polyester fiber used in the present invention may contain a fiber other than the polyester fiber. The shape of the fiber can be a thread, cotton, cloth, tow, non-woven fabric, or the like.

In the present invention, the monomer to be graft-copolymerized on the polyester fiber is a hydrophilic unsaturated compound represented by the above general formula (1). In the formula (1), the hydroxyl group-containing alkoxy group includes a hydroxyl group-containing alkoxy group having 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms.
Is used. As such a hydroxyl group-containing alkoxy group, for example, those represented by the following general formula (2) are preferably used. -OCnH ₂ nOH ₍₂₎ (wherein, n is a number of 1 to 6) As the hydroxyl-containing oxy alkoxy group, carbon atoms containing hydroxyl groups is 2 to 12, preferably from 4 to 10 An oxyalkoxy group is used. As such a hydroxyl group-containing oxyalkoxy group, for example, those represented by the following general formula (3) are preferably used. —O (CmH ₂ mO) pH (3) (wherein, m represents a number of 2 to 4 and p represents a number of 2 to 6) The amino group is a substituted or unsubstituted amino group In the case of a substituted amino group, it is preferably an amino group substituted with a hydroxyl group-containing alkyl group having 1 to 4 carbon atoms.

[0007] As the ferrous salt, any one can be used as long as it releases ferrous ions in water.
Such materials include ferrous sulfate, ferrous chloride, ammonium ferrous sulfate, ferrous nitrate, and the like. The combination of these divalent iron salts and hydrogen peroxide constitutes a redox catalyst and promotes the graft copolymerization reaction of the hydrophilic unsaturated compound. The concentration of hydrogen peroxide in the aqueous solution is from 0.01 to 0.
The concentration is 1 mol / l, preferably 0.03 to 0.06 mol / l, and the concentration of the ferrous salt is 0.5 to 2 mmol / l, preferably 0.7 to 1.5 mmol / l.

An acid can be added to the aqueous solution containing hydrogen peroxide and a ferrous salt used in the present invention, if necessary. The addition of this acid improves the grafting rate of the hydrophilic unsaturated compound. Examples of the acid include an inorganic acid such as sulfuric acid, hydrochloric acid, and phosphoric acid, and an organic acid such as acetic acid and formic acid.
The concentration of the acid in the aqueous solution is 2-4 mmol / l, preferably 2.
5-3.5 mmol / l. Furthermore, a polyvalent carboxylic acid-based sequestering agent such as EDTA and NTA can be added to the aqueous solution in addition to a conventionally known sequestering agent, for example, a phosphoric acid-based or phosphonic acid-based sequestering agent. The weight ratio of the aqueous solution to the polyester fiber is 5 to 30, preferably 5 to 15. The reaction temperature is 70-110 ° C, preferably 85-100 ° C,
The reaction time is 20 to 90 minutes, preferably 30 to 60 minutes. The proportion of the hydrophilic unsaturated compound used in the present invention is 5 to 100 parts by weight, preferably 10 to 60 parts by weight, based on 100 parts by weight of the polyester fiber. If the proportion of the hydrophilic unsaturated compound used is less than this, the modifying effect is not sufficient, while the more the proportion, the greater the proportion of introduction of the hydrophilic group, but even if the proportion exceeds the above range, the effect is particularly improved. Not economical.

In the modified polyester fiber of the present invention, the grafting ratio of the hydrophilic unsaturated compound (weight ratio of the grafting reaction of the hydrophilic unsaturated compound to the fiber) is 3 to 60% by weight, preferably 5 to 40% by weight. is there. If the grafting ratio exceeds the above range, the graft copolymerization reaction takes a long time and is not economical. On the other hand, if it is less than the above range, a sufficient reforming effect cannot be obtained. The grafting ratio can be adjusted by the use ratio of the hydrophilic unsaturated compound to the fiber and the reaction conditions. The graft copolymerized fiber obtained as described above can be reacted with a salt-forming cation via a carboxyl group contained in the hydrophilic unsaturated compound, if necessary. The cations in this case include sodium ions, calcium ions, ferric iron ions, ferric iron ions, monovalent copper ions, divalent copper ions,
Examples include zinc ions, manganese ions, silver ions, and quaternary ammonium ions from various amines.

[0010]

Next, the present invention will be described in more detail with reference to examples. In addition,% shown below is% by weight.

Example 1 Hydrogen peroxide (35% H ₂ O ₂ ) 0.3%, ferrous sulfate 0.02%,
10 g of well-washed polyester fiber (Toray Tetoron A261 2.5d x 64 mm) in an aqueous solution containing 1.5% methacrylic acid, 0.03% of Chilest NTB (sequestering agent, Kyresto Chemical Co., Ltd.) and 0.06% of sulfuric acid (50 ° Be) Is immersed and gradually heated from room temperature to 100 ° C. with stirring, treated at this temperature for 40 minutes, and then thoroughly washed with water and dried. There was no adhesion of the homopolymer in the processing machine and on the surface of the fiber. The graft ratio calculated by chemical analysis was 11%.

Example 2 The procedure of Example 1 was repeated, except that the fiber used in Example 1 was changed to Teijin Tetron TK04P, 3d × B64 mm. The graft ratio was 10.7%.

Example 3 0.5% aqueous hydrogen peroxide, 0.02% ferrous sulfate, 1.5% 2-hydroxyethyl methacrylate, 0.05% Cyles NTB,
Immerse well washed polyester fiber (Toyobo ester D93 2d x 64mm) in 100ml of aqueous solution containing 0.1% sulfuric acid,
The treatment was performed in the same manner as in Example 1. The rate of increase in fiber weight after processing was 12.8%.

Example 4 Toray Tetoron A261 was added to an aqueous solution containing 0.5% hydrogen peroxide, 0.02% ferrous sulfate, polyethylene glycol methacrylate (Blemmaar PME100, Nippon Oil & Fat), 0.05% Chillest NTB, and 0.1% sulfuric acid. , 2.5 d × 64 mm 10 g, and treated in the same manner as in Example 1. The rate of increase in fiber weight after processing is 1
2.5%.

[0015]

According to the present invention, a modified polyester fiber obtained by graft copolymerizing a hydrophilic unsaturated compound can be obtained efficiently and at low cost. Since the modified polyester fiber obtained in the present invention contains a hydrophilic unsaturated compound in its molecule, the water-absorbing and moisture-absorbing properties are improved, and the antistatic property and comfort are improved. At the same time, it has excellent adsorption of odors such as ammonia, amine odor and human urine odor, and can be advantageously used as a deodorizing fiber.When copper or silver is introduced via a carboxyl group in a water-soluble unsaturated compound, , Can be advantageously used as an antibacterial fiber.

Claims (3)

[Claims] In an aqueous solution containing hydrogen peroxide and a ferrous iron salt, a polyester fiber has the following general formula: CH ₂ ＣＲCR ¹ COX (1) (wherein R ¹ represents a hydrogen or methyl group. X represents a hydroxyl group, an amino group, a hydroxyl group-containing alkoxy group or a hydroxyl group-containing oxyalkoxy group), wherein a hydrophilic unsaturated compound represented by the following formula is graft-copolymerized: Production method. 2. The graft ratio of the hydrophilic unsaturated compound to the polyester fiber is 3 to 60% by weight.
the method of. 3. The method according to claim 1, wherein the polyester fiber is a normal pressure dyeable polyester.