JPH1136174A - Filling of gel into hollow fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To remove starchiness, etc., of fibers while preventing the gel quantity filled into hollow parts of the fibers from decreasing, by filling liquid capable of gelation into the hollow parts through interconnecting holes and then giving bending and/or wrinkling action(s) to the fibers in any fluid after gelation. SOLUTION: The purpose of this invention is achieved by filling liquid capable of gelation into the hollow parts of a hollow fiber through scatteringly existing interconnecting holes penetrated from the fiber surface to the hollow parts of the fiber to cause gelation and then giving the hollow fiber bending and/or wrinkling action(s) in any fluid with e.g. the high pressure liquid dyeing machine to remove some or all of gelled product adhered to the surface of the fiber.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for filling a hollow portion of a hollow fiber with a gel.

[0002]

2. Description of the Related Art Conventionally, as a proposal regarding a method of filling a substance such as a function-imparting agent into a hollow portion of a hollow fiber in which communication holes from the fiber surface to the hollow portion are scattered, Japanese Patent Laid-Open Publication No.
373 and JP-A-6-173167, all of which have insufficient target function levels, insufficient durability of functions, or texture and quality. Has one or more drawbacks, such as impairment. As a method aimed at solving such a drawback, JP-A-8-188967 discloses a method in which a water-soluble monomer containing a polymerization initiator is suction-filled through the above-described communication hole, and then the monomer is charged. To form a water-insoluble polymer in the hollow portion of the hollow fiber. Although this method substantially solves the above-mentioned drawbacks, the texture is still at an insufficient level for apparel applications.

Further, in order to solve such a problem,
The present inventors have previously introduced a water-soluble monomer containing a polymerization initiator through the communication hole, and then treated the hollow fiber with a solvent capable of dissolving the monomer to remove the monomer adhering to the fiber surface. A method has been proposed in which the monomer in the hollow portion is polymerized at the same time as or after the substantial removal (JP-A-9-78463). This method can be used for clothing as desired, but gives a sensual texture.
In order to treat the hollow fiber with a solvent that can dissolve the monomer before polymerization, a part of the monomer near the communication hole that is the entrance to the monomer hollow flows out, so that the final gel into the hollow The problem remains that the filling volume is reduced to a considerable extent.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method in which a gelled liquid which is introduced into a hollow fiber through a communication hole without causing the filled gellable liquid to flow out of the hollow fiber is formed, and the texture and the quality are improved. It is an object of the present invention to provide a method for filling a hollow fiber with a gel in which a desired function level is sufficiently maintained and the durability of the function is sufficient without impairing the gel.

[0005]

According to the present invention, a hollow portion of a hollow fiber in which communication holes from the fiber surface to the hollow portion are scattered is filled with a gellable liquid through the communication hole, and then the liquid is gelled. After forming the hollow fiber in a fluid by imparting a bending or kneading action in a fluid, a method of filling the hollow fiber with a gel, characterized in that at least a part of the gelled substance adhering to the fiber surface is removed. is there. Here, it is preferable to perform the bending and kneading action in a liquid dyeing tank. Also,
The liquid capable of gelling is preferably a monomer solution containing a polymerization initiator. Furthermore, it is preferable that the liquid capable of gelling contains a fiber-functional additive.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The hollow fibers used in the present invention include synthetic fibers such as rayon and acetate, and synthetic fibers such as polyester and polyamide. Polyester hollow fibers are particularly preferred. Here, the polyester includes terephthalic acid as a main dicarboxylic acid component and at least one glycol, preferably a polyester having at least one alkylene glycol selected from ethylene glycol, trimethylene glycol and the like as a main glycol component. No. These fibers may contain a stabilizer, an antioxidant, a flame retardant, an antistatic agent, a fluorescent brightener, a catalyst, a coloring inhibitor, a heat-resistant agent, inorganic particles, and the like, if necessary.

[0007] The hollow fibers can be produced by a conventionally known method. For example, actual fair 2-43487
The method described in Japanese Patent Publication No. 9 can be arbitrarily adopted. The hollow ratio of the hollow fiber is preferably from 5 to 50%, more preferably from 20 to 40%, in order to maintain necessary properties as a fiber and to fill a sufficient amount of gel. If it is less than 5%, the amount of gel to be filled is small relative to the hollow fibers, and the effect of the function to be imparted may be insufficient. On the other hand, if it is more than 50%, the hollow portion of the hollow fiber is liable to be crushed or the hollow fiber is broken during the processing step.

In the hollow fiber used in the present invention, as a method for forming a communication hole from the fiber surface to the hollow portion, for example, in the case of a polyester fiber, a polyester obtained by copolymerizing an organic sulfonic acid compound is mixed and melt-spun. ,
A method of forming a large number of communicating portions (micropores) by subjecting a hollow fiber to an alkali weight reduction treatment (Japanese Patent Laid-Open No. 1-20319). Further, a method of forming a large number of communicating portions (micropores) from the fiber surface to the hollow portion by subjecting the polyester hollow fiber to which the metal salt of an organic sulfonic acid is added and blended to an alkali reduction treatment (Japanese Patent Publication No. 61-60188, JP-B-61-31231) can also be employed.

Further, if the hollow fiber having a hollow ratio of 20% or more is subjected to alkali weight reduction treatment, a low-oriented portion and / or deformation along the longitudinal direction of the fiber can be obtained without using the above-mentioned organic sulfonate. A large number of communication holes (microgrooves) can be formed as traces for removing the strain concentration portion (Japanese Patent Application Laid-Open No. 7-26466). Also, a method for obtaining a hollow fiber having a communicating portion (split groove) extending from the fiber surface to the hollow portion in the longitudinal direction of the fiber by subjecting the core-sheath type composite fiber to an alkali weight reduction treatment and decomposing and removing the core polymer (Japanese Patent Laid-Open No. 6-
173167) is also used.

Next, in the present invention, a liquid capable of gelling is defined as a state in which the state changes from a liquid to a gel in a reversible or irreversible manner by receiving a physical or chemical stimulus, or simply by the passage of time. What can change. The liquid capable of gelling includes a solution containing a monomer and a polymerization initiator, and a liquid containing a monomer capable of causing a high molecular weight and / or a three-dimensional network structure by polymerization and / or crosslinking reaction ( A liquid that undergoes a sol-gel transition, such as an aqueous solution of a natural protein (hereinafter, also referred to as an “protein aqueous solution”), and the like.

Preferred examples of the monomer used in the monomer solution include a water-soluble monomer represented by the following general formula (I).

In the above formula (I), X represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group. Group, sec-butyl group, t-butyl group and the like. Y is a hydrogen atom or a carbon atom
To 80 organic groups, preferably an aliphatic organic group, for example, a 2-hydroxyethyl group, a dimethylaminoethyl group,
Examples thereof include a diethylaminoethyl group, a (chlorinated) trimethylaminoethyl group, a hydroxypolyethylene glycol group, a methoxypolyethylene glycol group, an acryloylglyceryl group, a methacryloylglyceryl group, an acryloylpolyethyleneglycol group, and a methacryloylpolyethyleneglycol group.

Specific examples of these water-soluble monomers include methacrylic acid, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, methoxypolyethylene glycol methacrylate, and dimethylaminoethyl methacrylate quaternary salt. Acryloyl glyceryl acrylate, acryloyl glyceryl methacrylate, methacryloyl glyceryl acrylate, methacryloyl glyceryl methacrylate and the like.

Since these water-soluble monomers do not have an aromatic group, they have a low viscosity and are easy to penetrate into the hollow portion. Can be formed, and the polymer is extremely unlikely to fall off.

Examples of the polymerization initiator used in the above-mentioned monomer solution include peroxides such as potassium persulfate, ammonium persulfate, hydrogen peroxide and benzoyl peroxide, ceric ammonium sulphate and ceric ammonium nitrate. Cerium ammonium salt or α, α′-azobisisobutyronitrile. Specific examples of the monomer solution include polyethylene glycol di (meth) acrylate and a polymerization initiator,
Further, an aqueous solution containing (meth) acrylic acid (or an alkali metal salt thereof) as needed.

The natural proteins used in the protein aqueous solution include gelatin, collagen, fibroin, soy protein, casein, sericin and the like. Specific examples of the aqueous protein solution include a liquid that undergoes sol-sol transition, such as an aqueous solution of a natural protein such as collagen. The above monomer solution,
Alternatively, the aqueous protein solution may be used alone or in combination of two or more.

[0017] The above gellable liquid, when gelation occurs during the step of transferring into the hollow portion of the hollow fiber or when the viscosity is significantly increased, the progress of the transfer step substantially proceeds at that point. It is not preferable because it does not work. Therefore, when such a risk element is contained, it is desirable to appropriately add a component for temporarily preventing or delaying gelation. For example, in the case of a monomer solution capable of performing the above-mentioned polymerization and cross-linking reaction, it is generally known that an enzyme delays the reaction [for example, it is described in Hisazu Mizutani, “Synthetic Chemistry of Polymers” (Industry Research Committee). The gelation reaction can be delayed by adding the enzyme-generating substance in a necessary amount.

The gellable liquid may optionally contain a fiber-functionalizing agent. Examples of the agent for imparting fiber functionality include medicinal properties such as aloe, cucumbers, and garlic, substances having plant flavors (plant extracts, plant proteins), bacterial cultures such as collagen, keratin, and sericin, and medical and physiological applications such as wound treatment. Functional substances (animal proteins), electrical functional substances (ceramic fine particles) for conductors such as titanium oxide, silica, alumina, zeolite, etc., octacarboiron phthalocyanine, dimethyl phthalate, organic silicon Substances having antibacterial and deodorizing properties such as quaternary ammonium and organic nitrogen compounds, various flavors (flavors and fragrances), substances having water absorption, moisture absorption and water retention properties such as polyethylene glycol, and having a perfluoroalkyl group Water repellent and oil repellent substances such as compounds can be appropriately mentioned.

In the present invention, a liquid capable of gelation is introduced and filled into the hollow portion of the hollow fiber in which communication holes from the fiber surface to the hollow portion are scattered, and then the liquid is gelled. After the gelation, the hollow fiber is characterized in that at least a part of the gelled substance adhering to the fiber surface is removed by imparting a bending or kneading action in the fluid.
Here, as a method for introducing and filling a gellable liquid through the communication hole into the hollow portion of the hollow fiber in which communication holes from the fiber surface to the hollow portion are scattered, refer to WO95-19461.
And the method disclosed in Japanese Patent Application Laid-Open No. HEI 8-188964, and the method proposed by the present inventors by padding a hollow fiber and then leaving it to stand to utilize the capillary phenomenon ( Japanese Patent Application No. 8-129864) can be arbitrarily adopted.

Next, the liquid capable of gelation introduced and filled into the hollow portion is gelled. The following method is exemplified as a method of filling the hollow portion with a liquid capable of gelling and gelling. The gellable liquid is converted into hollow fiber (weaving and weaving hollow fiber,
Or a non-woven fabric (hereinafter the same)), followed by heating. A method in which hollow fibers are immersed in a liquid capable of gelling, air and liquid are replaced, and then heating is performed. A method in which hollow fibers are immersed in a liquid capable of gelling, squeezed with a mangle or the like to replace air and liquid, and then heated. A method in which a hollow fiber is placed in a closed container, the pressure is reduced, the air in the hollow portion is evacuated, a gellable liquid is injected into the container, filled in the hollow portion, and then heated.

Next, in the present invention, only the gelled substance adhering to the fiber surface is selectively removed. For this purpose, a method of imparting a bending or kneading action to hollow fibers in a fluid is employed. In this method, the selectivity is higher than that of a gelled substance that is dissolved or decomposed and removed by a chemical operation, and there is no change in fiber deterioration or color tone after the operation. Further, the operation can be easily performed.

The above-mentioned operation of removing the gelled substance of the present invention can be performed by a dyeing apparatus which circulates the cloth by a high-pressure or normal-pressure liquid stream or air stream which is introduced in many general dyeing plants. It is. In this treatment, it is important to selectively remove only the gelled matter adhering to the fiber surface at least to a level that does not inhibit the bending of the fabric structure, and it is not always necessary to remove all the gelled matter. . That is, this treatment is to remove the gel in the attached state that inhibits the bending of the fabric structure in order to impart a bending or kneading action to the fabric in the first place. Therefore, the portion other than the inside of the hollow portion where the gelled product of the treated fabric exists is not between the multifilaments but mainly between the single fibers, and does not hinder the texture. In addition, in this operation, the removal of the gelled substance does not reach the hollow part at all, and the gelated substance is not removed more than necessary, so that the level of the desired imparting function is clearly higher than that processed by the conventional technique. high. In other words,
According to the present invention, it is possible for the first time to provide a high performance which cannot be achieved by the conventional technology, with high durability and without hindering the texture. Therefore, the object of the present invention is to gel all without flowing out the gellable liquid introduced / filled into the hollow fiber through the communication hole, and without impairing the feel and quality. It is possible to carry out processing in which the level of function is sufficiently maintained and the durability of the function is sufficient.

A specific example of the above-mentioned treatment operation is to treat a cloth (knitted fabric, woven fabric or non-woven fabric) composed of hollow fibers treated with a gellable liquid and gelling the liquid with a high-pressure liquid jet dyeing machine. Used, bath ratio 1/10 to 1/200, preferably 1
/ 50 to 1/150, temperature 80 to 150 ° C, preferably 120 to 150 ° C, time 10 to 90 minutes, preferably 30
Bending and kneading action is applied to the dough for ~ 60 minutes. This bending and kneading action may be performed simultaneously with the dyeing, or may be performed in another step (either before or after the dyeing).

[0024]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. (1) Preparation of Work Cloth Polyethylene terephthalate having an intrinsic viscosity of 0.61 was melted, and a hollow fiber undrawn yarn having a hollow ratio of 40% was obtained using a hollow spinneret. Next, this yarn is drawn and a round hollow 50 denier / 20 filament (amount of titanium oxide;
0.3% by weight) of a multifilament. A cross-sectional image was taken with an electron microscope, and the inner radius of the hollow fiber was measured. A knitted fabric (tricot) was prepared from the multifilament according to a conventional method, and refining and presetting were performed. This was treated in hot water (100 ° C.) containing 50 g / L sodium hydroxide for 10 minutes,
The weight loss rate was 20%.

(2) Preparation of Gelable Liquid A liquid was prepared according to the following formulation. The viscosity of this liquid is
7 centipoise at 10 ° C, 4 centipoise at 20 ° C, 4
It was 2 centipoise at 0 ° C. In addition, this liquid is 0
It did not solidify at a temperature of at least 20 ° C., did not gel at least at 10 days at a temperature of at most 20 ° C., and gelled within 2 minutes at a temperature of at least 80 ° C.
In addition, the viscosity (centipoise) of the liquid was measured with a vibration type viscometer model MV-100-L manufactured by Yamaichi Electric Co., Ltd. <Formulation formula> Acrylic acid; 15.0 parts by weight [Metoquinone 200 ppm content product, manufactured by Nippon Shokubai Co., Ltd.] Sodium hydroxide; 7.5 parts by weight (Reagent 1st grade, manufactured by Wako Pure Chemical Industries, Ltd.) Blemmer PDE- 400; 1.0 parts by weight [PEG400 dimethacrylate, manufactured by NOF Corporation] Potassium persulfate: 0.5 parts by weight [Reagent 1st grade, manufactured by Wako Pure Chemical Industries, Ltd.] Water: 76.0 parts by weight

(3) Processing procedure The knitted fabric (width 120 cm, length 20 m) prepared in the above (1) is immersed in the liquid prepared in the above (2), so that the amount of liquid adhered to the knitted fabric is It was squeezed and wound to 100%, covered with a polyethylene bag, and allowed to stand for 7 days in an atmosphere kept at 20 ° C. to transfer a part of the liquid existing between the fibers to the inside of the hollow portion. . Thereafter, the knitted fabric was taken out of the bag and subjected to the respective “gelling treatment”.

(4) Evaluation The solid content retention rate (%) was calculated as an increase rate with respect to the fiber weight as described below, where V ₀ and V ₁ were the fabric weight before and after processing, respectively. Solids retention (%) = [(V ₀ −V ₁ ) / V ₀ ] × 10
0 The moisture absorption (%) was determined by preliminarily drying the sample at 50 ° C. for 2 hours and then absolutely drying the sample at 105 ° C. for 2 hours.
₀ ). Next, the sample is placed in a desiccator at 20 ° C. × 90% RH for 3 days, and then weighed (referred to as W ₁ ).
Was measured and calculated by the following equation. Moisture absorption (%) = [(W ₁ −W ₀ ) / W ₀ ] × 100 Washing was carried out 20 times by a method according to JIS L1018-77 6.36, method H.

Example 1 The above-mentioned "gelation treatment" was carried out by exposing the dough to 3 kg / cm ² of pressurized steam (steam) for 10 minutes and drying, and then applying a high-pressure jet dyeing machine [Hisaka Seisakusho Co., Ltd.] , Circular S
UT-RA type], soda ash 2 g / L, bath ratio 1/6
The treatment was carried out at 0 and 70 ° C. for 30 minutes. The texture was soft and the quality was good. Solids retention is 2
The owf was 0% and the moisture absorption was 9%. The solids retention after washing was 18% owf, and the moisture absorption was 9%. Also, from comparison of the cross-sectional photographs of the electron microscope before and after applying to the high-pressure jet dyeing machine, the removal of the gelled matter by the high-pressure jet dyeing machine was only between the multifilaments.

Comparative Example 1 The above-mentioned "gelation treatment" was performed by immersing the dough in water at 20 ° C. for 30 seconds, and then exposing the dough to 3 kg / cm ² of pressurized steam (steam) for 10 minutes. The texture was soft and the quality was good. 8% ow solids retention
f, The moisture absorption was 4%. Solids retention after washing is 7
% Owf and moisture absorption were 4%. In addition, from the comparison of the cross-sectional photograph of the cloth before being subjected to the high-pressure jet dyeing machine of Example 1 and the cloth after the treatment in this example, in this comparative example,
Removal of the gellable liquid, which is the precursor solution of the gel,
It extends between the multifilaments, between the single fibers, and partly in the hollow part.

Comparative Example 2 The above-mentioned "gelling treatment" was carried out using hot water (10
(0 ° C.) for 10 minutes. The texture was soft and the quality was good. The solids retention was 10% owf and the moisture absorption was 5%. The solids retention after washing was 9% owf, and the moisture absorption was 5%. Also, from a comparison of the cross-sectional photographs of the fabric before being subjected to the high-pressure jet dyeing machine of Example 1 and the fabric after the treatment in this example, in this comparative example, it is a gelled product or a precursor solution of the gelled product. Removal of the gellable liquid ranged between the multifilaments and between the single fibers and partially within the hollow space.

Comparative Example 3 The above "gelling treatment" was carried out by exposing the dough to 3 kg / cm ² of pressurized steam (steam) for 10 minutes. The texture was rough and rigid, and the quality was not good. The solids retention was 27% owf and the moisture absorption was 12%. The solids retention after washing was 20% owf, and the moisture absorption was 9%. In addition, the presence of the gelled material by cross-sectional observation of the cross-sectional photograph of the electron microscope was in the hollow portion, between the single fibers, and between the multifilaments.

[0032]

According to the present invention, the gellable liquid introduced / filled into the hollow portion of the hollow fiber through the communication hole is all gelled without flowing out, and the feeling and quality are impaired. In addition, it is possible to perform processing in which a desired function level is sufficiently maintained and the durability of the function is sufficient.

Claims (4)

[Claims] 1. Filling a hollow portion of a hollow fiber, in which communication holes from the fiber surface to the hollow portion are scattered, with a liquid that can be gelled through the communication hole, and then gelling the liquid,
A method for filling a hollow fiber with a gel, comprising removing at least a part of a gelled substance adhering to the fiber surface by imparting a bending or kneading action to the hollow fiber in a fluid. 2. The method for filling gel into hollow fibers according to claim 1, wherein the imparting of the bending or kneading action is carried out in a liquid dyeing tank. 3. The method according to claim 1, wherein the gellable liquid is a monomer solution containing a polymerization initiator. 4. The method for filling a hollow fiber with gel according to claim 1, wherein the gellable liquid contains a fiber-functionalizing agent.