JPH08325940A - Production of crosslinked acrylic fiber - Google Patents

Abstract

PURPOSE: To obtain a crosslinked acrylic fiber excellent in spinning property and resistance to microbes and useful for removal, etc., of moisture in air by applying a specific oil solution to an acrylic fiber subjected to hydrazine treatment. CONSTITUTION: A mixed oil solution comprising a quaternary ammonium-based oil solution and a nonionic oil solution in an amount of 0.1-10wt.% is applied to an acrylic fiber to which crosslinkage is introduced by hydrazine treatment. The mixed oil solution is prepared by mixing 20-95wt.% of a quaternary ammonium-based oil solution of the formula (R1 is a 10-18C alkyl, etc.; R2 is a 1-3C alkyl, etc.; R3 is a 1-3C alkyl, etc.; R4 is a 1-3C alkyl, etc.; X is I, Cl, Br, NO3 , etc.) and 80-5wt.% nonionic oil solution. The nonionic oil solution is selected from a copolymer of propylene oxide(PO) with ethylene oxide(EO) [having 5,000-15,000 weight-average molecular weight and PO/EO ratio of (40/60) to (10/90)] and a polyoxyethylene alkyl ether (the polymerization degree is 10-50; alkyl, etc., is 8-18C), etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a crosslinked acrylic fiber having excellent spinning properties and high antibacterial durability.

[0002]

2. Description of the Related Art Conventionally, an inorganic hygroscopic agent has been used as a means for removing moisture in the air, but it has drawbacks such as liquefaction after moisture absorption to contaminate others, difficulty in molding, and difficulty in regeneration. Had. As a method to solve this problem,
Acrylic fiber is hydrazine crosslinked to introduce a carboxyl group into a part of the remaining nitrile group.
No. 1 cross-linked acrylic fiber is proposed. This fiber has great features such as a large moisture absorption amount and a high moisture absorption / desorption rate, but the fiber has a large fiber / fiber friction force,
The spinnability was poor due to the drawbacks such as the easy occurrence of nep and the fact that the high speed card is easily charged with static electricity due to the absorption of the oil agent in the fiber.

On the other hand, the pH of the skin exceeds a normal range due to acid rain accompanying the recent environmental destruction and alkalinization of clothes due to washing, which is a cause of impairing healthy skin.
In order to keep the skin pH weakly acidic, it is desirable that the external acid or alkali be neutralized by clothes and that the fiber material itself that comes into contact with the skin be weakly acidic. In order to meet such a demand, the present inventors have previously proposed that the acrylic fiber was hydrazine-crosslinked, the carboxyl group was introduced into a part of the residual nitrile group, and a part of the carboxyl group was converted into a metal salt type. No. 6-36597, pH buffering crosslinked acrylic fiber was proposed. Although this fiber has practical properties such as high pH buffering performance and fast moisture absorption and desorption, it was liable to be charged with static electricity and poor spinnability like the crosslinked acrylic fiber.

The antibacterial property of the crosslinked acrylic fiber is presumed to be due to the crosslinked structure containing nitrogen produced by the reaction between the acrylic fiber and hydrazine, but the antibacterial property was somewhat unsatisfactory.

[0005]

SUMMARY OF THE INVENTION The present invention was devised in order to solve the problems of the prior art, and its object is spinnability for easy processing into knitted fabrics, woven fabrics, non-woven fabrics and the like. (EN) It is intended to provide a method for producing a crosslinked acrylic fiber containing a pH buffering hygroscopic acrylic fiber, which synergistically enhances both the antibacterial property and the antibacterial property.

[0006]

The above object of the present invention is to provide one or more quaternary ammonium-based oil agents represented by the following general formula [I] in an amount of 20 to 95% by weight and a weight average molecular weight. Copolymer of 5,000 to 15,000 propylene oxide (PO) and ethylene oxide (EO) (however, PO / EO ratio 40/60 to 10/90), polyoxyethylene alkyl ether (however, polymerization degree 10 to 50, carbon number 8 to 18). Alkyl group or alkenyl group), or polyethylene glycol, mono- or dialkyl ester (however, polyethylene glycol having a weight average molecular weight of 4000 to 6000, alkyl ester having a carbon number of 11 to 17)
One or more nonionic oil agents selected from 80
-5% by weight of the specific oil agent is added to the acrylic fiber in which the cross-linking is introduced by the hydrazine treatment in an amount of 0.1-0.1%.
It is achieved by adding 1.0% by weight.

Embedded image R ₁ : an alkyl group having 10 to 18 carbon atoms, or R ₅ CON
An alkylamidoalkyl group represented by HR _6- , provided that R
₅ is an alkyl group having 11 to 21 carbon atoms, R ₆ is 2 to 2 carbon atoms
5 alkylene group R ₂ : an alkyl group having 1 to 3 carbon atoms, or-(C ₂ H
₄ O) _n H (n = 1 to 10) R ₃ : an alkyl group having 1 to ₃ carbon atoms, an alkyl group having 12 to 18 carbon atoms, or-(C ₂ H ₄ O) _m H (m = 1 to 1)
0) R ₄ : an alkyl group having 1 to 3 carbon atoms, a benzyl group, a hydroxyethyl group, or a hydroxypropyl group X: I ⁻ , Cl ⁻ , Br ⁻ , NO ₃ ⁻ , CH ₃ SO _{4
^{-, C 2 H 5 SO 4}} -, OH - or

[Chemical 4]

The present invention will be described in detail below. First, the present invention relates to a method for producing a crosslinked acrylic fiber containing a pH buffering hygroscopic acrylic fiber.
No. 2585 and Japanese Patent Application No. 6-36597, the subject is a crosslinked acrylic fiber introduced with a crosslinking bond by a hydrazine treatment, but another method is the same as the fiber structurally. The crosslinked acrylic fiber produced in (1) is also preferably used. It should be noted that such a fiber can be called a crosslinked acrylic modified fiber in the sense that it is modified from acrylic.

The quaternary ammonium-based oil agent applied to the crosslinked acrylic fiber is one or two represented by the general formula [I].
It is necessary to use 20 to 95% by weight, preferably 30 to 80% by weight, based on the total amount of the oil agent, but if it is less than the lower limit, not only static electricity during spinning cannot be prevented, but also the antibacterial property of the fiber The synergistic effect of becomes smaller.

Examples of the quaternary ammonium-based oil agent according to the present invention include cationized products of long-chain alkyldimethylamine and methyl halide, cationized products of long-chain alkyldimethylamine and diethylsulfate, stearylamidopropyldimethyl β-hydroxyethylammonium. Examples thereof include nitrate, stearylamidoethyltrimethylammonium methylsulfate and the like.

On the other hand, as the nonionic oil agent according to the present invention, a copolymer of propylene oxide (hereinafter abbreviated as PO) and ethylene oxide (hereinafter abbreviated as EO) is 5 to 80% by weight, preferably 20 to 70% by weight based on the total amount of the oil agent. Use by weight%. If it is less than the lower limit, the frictional resistance between the fibers cannot be lowered, a large amount of nep is generated, fiber damage occurs, and the spinning yield decreases. When the amount exceeds the upper limit, the amount of the quaternary ammonium-based oil agent represented by the general formula [I] becomes small, so that it becomes impossible to prevent static electricity and the synergistic effect on the antibacterial property becomes small. The weight average molecular weight of the above copolymer is 5,000 to 15,000, preferably 9000 to 13,000. If the weight average molecular weight is less than the lower limit, the frictional resistance cannot be sufficiently reduced and nep occurs.
If it exceeds the upper limit, the solubility in water becomes small and it is difficult to uniformly apply the fibers.

The PO / EO ratio of the above copolymer is 4
0/60 to 10/90, preferably 30/70 to 20 /
80. When the PO ratio is more than the above value, the solubility in water becomes small, and it is difficult to uniformly apply it.

Other nonionic oil agents include polyoxyethylene alkyl ethers (however, the degree of polymerization is 10 to 50, preferably 20 to 50, and the number of carbon atoms is 8 to 18, preferably 12).
~ 18 alkyl or alkenyl groups) are used.
When the degree of polymerization and the number of carbon atoms exceed this range, the solubility in water becomes small, and it is difficult to uniformly apply it. When the degree of polymerization and the number of carbon atoms fall below this range, the friction resistance between fibers cannot be reduced. Examples of such nonionic oil agents include polyoxyethylene (20) stearyl ether, polyoxyethylene (25) lauryl ether, and polyoxyethylene (3
0) oleyl ether and the like can be exemplified.

As other nonionic oil agents, polyethylene glycol, mono- or dialkyl esters (however, polyethylene glycol (PEG) having a weight average molecular weight of 4,000 to 6000, alkyl esters having 11 to 17 carbon atoms) are used. It If the weight average molecular weight and the number of carbons are above this range, the solubility in water will be small and it will be difficult to uniformly apply. If it is below this range, the frictional resistance between the fibers cannot be reduced and a large amount of nep will occur. Occurs in. As such a nonionic oil agent, PEG (400
0) oleate, PEG (4000) stearate, P
EG (6000) laurate and the like can be exemplified.

The oil agent applied to the crosslinked acrylic fiber is
It is essential to employ a quaternary ammonium-based oil agent represented by the general formula [I] and a specific nonionic oil agent, but other than these as long as the moisture absorption / release property, pH buffering property, antibacterial property and spinnability are not impaired. It is also possible to use the above oil solution. However, the amount used is 20% by weight or less based on the total amount of the oil agent.

As a method for applying such an oil agent, a method of spraying an oil agent aqueous solution on dry fibers, a method of immersing dry fibers or wet fibers in the oil agent aqueous solution, or filling the fibers in a container equipped with a pump circulation system, Although any method such as circulating an oil solution may be adopted, a method of spraying onto dry fibers cannot impart durable antibacterial properties because the oil agent does not penetrate into the fibers. In order to impart good spinning property and durable antibacterial property, it is necessary to employ a dipping method or a circulation method in which the hygroscopic fiber is moistened and can be evenly applied to the inside in a swollen state. It is preferable because of the synergistic effect of enhancing the durability and durability such as washing.

The reason why the cross-linked acrylic fiber can obtain the synergistic effect of excellent spinning processability, high antibacterial property and its durability by the method of the present invention is considered to be mainly for the following reason. .

Permeation of the quaternary ammonium-based oil agent into the fiber can impart durable antibacterial properties, and preferentially adsorbs ions to the surface layer, thereby preventing generation of static electricity. Moreover, by effectively covering the fiber surface with the nonionic oil agent, the friction resistance between the fibers is reduced, and in order to suppress the generation of nep and the damage to the fiber, a good spinnability, a high antibacterial property, and a synergistic effect of its durability are achieved. It is presumed to bring.

[0018]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention. Parts and percentages in the examples are shown by weight unless otherwise specified.

[0019] The amount of deposited oil, the amount of nep, the static electricity of the card, and the antibacterial property were determined by the following methods.

(1) Adhesion amount of oil agent (%) About 3 g of sufficiently dried test fiber was precisely weighed (W1) g, and a Soxhlet extractor was used to obtain ethyl alcohol: benzene =
Reflux extract at 1: 1 for 1 hour. After evaporating the extract to dryness,
The weight (W2) g of the residue is measured, and the oil agent adhesion amount is calculated by the following formula.

(2) Nep amount (pieces / 10 g) 100 g of the test fiber is carded to form a web or sliver, and the number of neps in 10 g is visually counted.

(3) Card Static Electricity (KV) In an atmosphere of 20 ° C. and 60% RH, a test roller is defibrated with a mini roller card having a movement width of 20 inches, and at the card exit side, the distance from the web is 10 cm. Then, the generated static electricity was measured using a collector type potential measuring device KS-325 type (manufactured by Kasuga Electric Co., Ltd.).

(4) Antibacterial test strain: Staphylococcus aureus I
FO 12732 Test method: A broth suspension of the test bacteria was added to a sterilized sample cloth according to the method specified by the Textile Products Sanitary Processing Council (SEK), and the live bacteria after culturing at 37 ° C for 18 hours in a closed container. The number is measured, and it is determined by the difference between the increase and decrease in the number B of bacteria of the standard cloth and the number C of bacteria of the sample with respect to the number A of inoculum. Increase / decrease value = logC-logA Increase / decrease value difference = (logB-logA)-(logC-lo
gA)

Example 1 A spinning dope prepared by dissolving an acrylonitrile polymer of 90% acrylonitrile and 10% of methyl acrylate in a 48% aqueous solution of rhodanese was subjected to spinning, washing with water, stretching, crimping and heat treatment according to a conventional method to give 0. A raw material fiber of 0.8 denier × 70 mm was obtained. After adding 5 kg of 30% by weight hydrated hydrazine to 1 kg of this raw material fiber and crosslinking the mixture at 98 ° C. for 3 hours,
Wash with water, add 5 kg of 3% by weight sodium hydroxide, and add 9
It was hydrolyzed at 0 ° C. for 2 hours. It was washed with water to obtain a highly hygroscopic crosslinked acrylic fiber A. The fiber A had a carboxyl group content of 4.0 meq / g, a saturated moisture absorption rate of 42% and a tensile strength of 1.5 g / d at 20 ° C. and 65% RH.

The fiber A is treated with a 1N HNO ₃ aqueous solution to convert the carboxyl groups into H-form, washed with water and then with a 1N N solution.
Adjust the pH to 6.5 with aOH and calcium chloride 50g
Was added and treated with a metal salt at 60 ° C. for 2 hours. After washing with water, a calcium hydroxide aqueous solution was added to adjust the pH to 5.8. After thoroughly washing with water, dehydration and drying are performed to obtain hygroscopicity and pH.
A buffering crosslinked acrylic fiber B was obtained. Fiber B 20 ° C 6
5% RH saturated moisture absorption is 28% tensile strength is 1.8 g / d,
pH buffer capacity is 700μeq / g acid, 320μ alkali
It was eq / g.

The amount of carboxyl group, saturated moisture absorption rate, p
The H buffer capacity was determined by the following method.

(1) Total amount of carboxyl groups (meq /
g) About 1 g of sufficiently dried test fiber is precisely weighed (X) g, 200 ml of 1N hydrochloric acid aqueous solution is added thereto, left for 30 minutes, filtered through a glass filter, and water is added to wash. After repeating this hydrochloric acid treatment 3 times, the filtrate is sufficiently washed with water until the pH thereof becomes 5 or more. Next, after putting this sample in 200 ml of water and adding 1N hydrochloric acid aqueous solution to adjust to pH 2,
A titration curve was obtained using a 0.1N-caustic soda aqueous solution according to a conventional method. The caustic soda aqueous solution consumption (Y) cc consumed for the carboxyl groups was obtained from the titration curve, and the total amount of carboxyl groups was calculated by the following formula.

(2) Saturated moisture absorption rate (%) Sample fiber: about 5.0 g. Is dried with a hot air drier at 105 ° C. for 16 hours, and the weight is measured (W1) g. Next, the sample was placed in a thermo-hygrostat at a temperature of 20 ° C and a relative humidity of 65%.
Put in time. The weight of the sample thus absorbed is measured (W2) g. From the above results, it was calculated as follows.

(3) pH buffering capacity (μeq / g) About 0.4 g of sufficiently dried test fiber was precisely weighed (X) g, and 200 ml of water was added thereto, and then 0.1N hydrochloric acid aqueous solution or Add 0.1N caustic soda solution dropwise, and consume hydrochloric acid solution or caustic soda solution consumption (Y) cc until pH becomes 5.0 for hydrochloric acid solution and pH 7.0 for caustic soda solution. Then, the buffer capacity for acid or alkali was calculated by the following formula.

100 g of the fibers A and B were treated with an aqueous solution of various fiber oil solutions under the conditions shown in Table 1 by an oil solution treatment by a spraying method and a dipping method to obtain raw cotton products. The treated fiber was applied to a card in an atmosphere of 20 ° C. and 50% RH, and the generated static electricity, the amount of card web nep, and the spinning passability were tested. Next, wrap each 5 g of card web in a gauze bag, and after boiling for 30 minutes, wash it with a weak alkaline detergent 10 times in a home washing machine.
Antibacterial properties were determined by repeating dehydration-rinsing-drying. The results are shown in Table 2.

[0031]

[Table 1]

[0032]

[Table 2]

It can be seen that among the fibers 1 to 5 of the present invention, those treated with an oil agent by the dipping method have excellent antibacterial durability and excellent spinning processability. On the other hand, it can be seen that the spray method of the fibers 1 to 5 of the present invention example has excellent spinning processability but is inferior in antibacterial durability. On the other hand, the fiber of Comparative Example 3 in which the amount of the quaternary ammonium-based oil agent was less than 20% by weight had a slightly improved processability but a low antibacterial property.

The fibers of Comparative Example 1 which did not use the quaternary ammonium-based oil agent had a large amount of curling around the card, and the fibers of Comparative Example 2 generated a large amount of static electricity and could not pass through the card.
The fibers of Comparative Example 3 passed through the card but had many neps, and the yarn quality was poor. Moreover, the antibacterial durability was not sufficiently high.

Example 2 The fibers of Examples 1 and 5 of the present invention and Comparative Examples 1 and 3 were treated with boil for 30 minutes in tap water at a bath ratio of 1: 200, and then subjected to JIS L.
According to the method 103 of 0217, washing was repeated 10 times using Monogen Uni (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) as a detergent. The results of testing the antibacterial properties of the obtained fibers are shown in Table 3.
It was shown to.

[0036]

[Table 3]

The dipping method of the fibers 1 and 5 of the present invention was excellent in washing stability and had antibacterial properties. SE approved by the Sanitary and Textile Products Council (SEK) regarding antibacterial properties
The K mark product standard has an increase / decrease difference of 1.6 or more.

[0038]

EFFECTS OF THE INVENTION According to the present invention, the antibacterial ability of crosslinked acrylic fibers containing a pH buffering hygroscopic acrylic fiber and the washing durability thereof are enhanced, and the spinning passability of the fiber having low tensile strength is facilitated. It is noteworthy that the fibers can be processed into various forms such as non-woven fabrics, knitted fabrics, and woven fabrics, and can be used for various purposes such as clothing, daily life materials, and industrial materials.

Claims (2)

[Claims] 1. 20 to 95% by weight of one or more quaternary ammonium-based oil agents represented by the following general formula [I]:
And a copolymer of propylene oxide (PO) and ethylene oxide (EO) having a weight average molecular weight of 5,000 to 15,000 (however, PO / EO ratio is 40/60 to 10/90), polyoxyethylene alkyl ether (however, polymerization degree is 10).
50, an alkyl group or an alkenyl group having 8 to 18 carbon atoms, or polyethylene glycol, a mono or dialkyl ester (however, a weight average molecular weight of 4000 to 6000).
1 or 2 of nonionic oil agents selected from polyethylene glycol of (C11 to C17 alkyl ester)
A crosslinked acrylic resin, which comprises a step of adding 0.1 to 1.0% by weight of a specific oily agent of 80 to 5% by weight of a seed or more to acrylic fibers introduced with a crosslinking bond by hydrazine treatment. Method for producing a base fiber. Embedded image R ₁ : an alkyl group having 10 to 18 carbon atoms, or R ₅ CON
An alkylamidoalkyl group represented by HR _6- , provided that R
₅ is an alkyl group having 11 to 21 carbon atoms, R ₆ is 2 to 2 carbon atoms
5 alkylene group R ₂ : an alkyl group having 1 to 3 carbon atoms, or-(C ₂ H
₄ O) _n H (n = 1 to 10) R ₃ : an alkyl group having 1 to ₃ carbon atoms, an alkyl group having 12 to 18 carbon atoms, or-(C ₂ H ₄ O) _m H (m = 1 to 1)
0) R ₄ : an alkyl group having 1 to 3 carbon atoms, a benzyl group, a hydroxyethyl group, or a hydroxypropyl group X: I ⁻ , Cl ⁻ , Br ⁻ , NO ₃ ⁻ , CH ₃ SO _{4
^{-, C 2 H 5 SO 4}} -, OH - or ## STR2 ## 2. The method for producing a crosslinked acrylic fiber according to claim 1, wherein an oil agent is applied to the wet fiber, and then the fiber is dried.