JPH11350353A - Filling of solid material into hollow fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To fill a solid material into the hollow part of a fiber by introducing a liquid having a gel-forming capacity into the hollow part of a hollow fiber, removing the liquid having the gel-forming capacity from the surface of the fiber in a liquid capable of dissolving the liquid having the gel-forming capacity, gelling, and then performing a bending action, etc., against the hollow fiber in a liquid containing a functionality-imparting agent. SOLUTION: This method for filling a solid material into the hollow part of a hollow fiber, is provided by introducing a liquid having a gel-forming capacity such as a monomer solution containing a polymerization initiator, into the hollow part of the hollow fiber having communicating holes from the surface of the fiber to its hollow part, then treating the hollow fiber with a liquid capable of dissolving or dispersing the liquid having the gel-forming capacity for removing the liquid having the gel-forming capacity on the surface of the hollow fiber substantially, at the same time or after the removal gelling the liquid having the gel-forming capacity, and then subjecting the hollow fiber under a bending and/or a crumpling action in a liquid containing a functionality- imparting agent such as sodium dodecylbenzene sulfonate, etc., for filling the solid material into the hollow fiber.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for filling a hollow portion of a hollow fiber with a solid material.

[0002]

2. Description of the Related Art Conventionally, there has been proposed a method of filling a hollow portion of a hollow fiber having a communication hole from a fiber surface to a hollow portion with a substance such as a function-imparting agent in Japanese Patent Application Laid-Open No. 6-17373. Japanese Unexamined Patent Publication No. Hei 6-173167 discloses that all of them have insufficient target function levels, insufficient function durability, or impaired texture or quality. Had disadvantages.

[0003] As a method for solving such a drawback, Japanese Patent Application Laid-Open No. Hei 8-18867 discloses a water-soluble monomer containing a polymerization initiator by adding an agent for imparting functionality to fibers (hereinafter referred to as a fiber-functionalizing agent). A method of forming a water-insoluble polymer in a hollow portion of a hollow fiber after polymerizing the monomer after suction-filling the same through a communication hole with the addition of an agent. Although this method almost eliminates the above-mentioned disadvantages, the texture is still at an insufficient level for use in clothing.

In order to further solve such a problem, the present inventors first introduced a water-soluble monomer containing a fiber function-imparting agent and a polymerization initiator through the through-hole, and then added the monomer. The hollow fiber is treated with a solvent capable of dissolving, and simultaneously or after substantially removing the monomer adhering to the fiber surface, the monomer in the hollow portion is polymerized, and the agent for imparting fiber function is added. A filling method has been proposed (JP-A-9-78463). This method finishes a texture that can be used for clothing as intended, but a communication hole that is an entrance to the hollow portion of the monomer in order to treat the hollow fiber with a solvent that can dissolve the monomer before polymerization. A part of the monomer flows out in the vicinity of, and there remains a problem that the gel filling amount in the final hollow portion and the agent for imparting fiber functionality are reduced to a considerable extent.

[0005]

DISCLOSURE OF THE INVENTION The present inventors gel a liquid having a gel-forming ability introduced into a hollow portion of a hollow fiber through a communication hole, and add an agent for imparting fiber functionality to the gel. It is an object of the present invention to propose a treatment method which can maintain a high level of functionality without impairing the feel and quality by containing the same, and has sufficient durability.

[0006]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present invention introduces a liquid having a gel forming ability into the hollow portion of a hollow fiber, and the gel forming ability in the hollow portion. Is gelled, and then the hollow fiber is subjected to a bending and / or kneading action in a liquid containing a fiber-function-imparting agent, whereby the fiber-function-imparting agent is applied to the hollow portion. The present inventors have found that they can be migrated and contained in existing gels, whereby the amount of the agent for imparting fiber functionality in the hollow fibers can be increased, and the present invention has been achieved.

That is, according to the present invention, a gel-forming liquid is introduced into the hollow portion of a hollow fiber having a communication hole from the fiber surface to the hollow portion through the communication hole, and then the gel formation is performed. The hollow fiber is treated in a liquid capable of dissolving or dispersing the liquid having the ability to substantially remove the liquid having the gel-forming ability on the surface of the hollow fiber, or after the removal, A method of filling a hollow fiber with a solid material, comprising: gelling a liquid having a gel-forming ability in a hollow portion, and then subjecting the hollow fiber to a bending and / or kneading action in a liquid containing a function-imparting agent. It is in. Here, it is preferable that the liquid having gel forming ability is a monomer solution containing a polymerization initiator.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
As the hollow fibers used in the present invention, those made of synthetic fibers such as rayon and acetate, and synthetic fibers such as polyester and polyamide can be appropriately mentioned, and those using polyester fibers are particularly preferable. Further, these fibers contain a stabilizer, an antioxidant, a flame retardant, an antistatic agent, an optical brightener, a catalyst, a coloring inhibitor, a heat-resistant agent, a coloring agent, inorganic particles, and the like, as necessary. Is also good.

Such a hollow fiber can be produced by a conventionally known method. For example, actual fair 2-
The method described in JP-A-43879 can be arbitrarily adopted. Further, the hollow fiber has a hollow ratio in the range of 5 to 60%, more preferably 20 to 50%.
Is in the range. As a result, it is possible to maintain the necessary properties as fibers and to fill a sufficient amount of gel. When the hollow ratio is less than 5%, the amount of the gel to be filled becomes smaller than that of the hollow fiber, and the amount of the fiber function-imparting agent contained therein may be insufficient. Conversely, if the hollow ratio exceeds 60%, the hollow portion of the hollow fiber is liable to be crushed, and the hollow fiber may break during the processing step, which is not preferable.

As a method of forming a communication hole from the fiber surface of the hollow fiber 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 the hollow fibers to alkali reduction treatment (Japanese Patent Laid-Open No. 1-20319) is used. 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. 61-6018)
No. 8, JP-B-61-31231).

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. Numerous communication holes (microgrooves) can be formed as traces for removing the strain concentration portion (see Japanese Patent Application Laid-Open No. 7-26466).

Further, a method of obtaining a hollow fiber having a communication hole (split groove) extending from the fiber surface to the hollow 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 (FIG. JP-A-6-173167) may be used.

Next, the liquid having a gel-forming ability used in the present invention means that the liquid is reversibly converted from the state into a gel under a physical or chemical stimulus or simply after a lapse of time. Or, what can be irreversibly changed.

Specifically, the polymerization and crosslinking reaction of an aqueous solution containing polyethylene glycol dimethacrylate and a polymerization initiator, and, if necessary, acrylic acid or an alkali metal salt thereof, increase the molecular weight or reduce
Examples thereof include a liquid containing a monomer capable of causing a three-dimensional network structure, a liquid that undergoes a sol-gel transition such as an aqueous solution of a natural protein such as collagen, and the like.

Examples of the polymerization initiator include peroxides such as potassium persulfate, ammonium persulfate, hydrogen peroxide and benzoyl peroxide, and cerium ammonium salts such as ceric ammonium sulfate and ceric ammonium nitrate. Alternatively, α, α'-azobisisobutyronitrile and the like can be mentioned.

The gel-forming liquid is preferably used because gelation occurs during the process of moving into the hollow interior of the hollow fiber, or when the viscosity is significantly increased, the process substantially stops at that point. Absent. Therefore, when there is such a concern, it is desirable to appropriately add a component that temporarily stops or delays gelation.
For example, in the case of a liquid containing a monomer capable of undergoing the above-mentioned polymerization and cross-linking reaction, it is preferable to add an oxygen-generating substance in a necessary amount since oxygen delays the reaction as generally known.

In the present invention, such a liquid having a gel-forming ability is introduced from the fiber surface to the hollow portion through a communication hole. This introduction method is described in PCT WO95-19461 and JP-A-8-188964. And a method in which the hollow fiber proposed by the present inventors is padded, and then left and utilized by utilizing the capillary phenomenon (Japanese Patent Laid-Open No. 9-310278).
Etc. can be arbitrarily adopted.

Next, the hollow fiber is treated (washed) in a liquid capable of dissolving or dispersing the gel-forming liquid at a temperature not lower than the gelation start temperature of the gel-forming liquid. Thus, the liquid having a gel-forming ability attached to the fiber surface is substantially removed. Then, simultaneously with or after the washing and removal, the liquid having a gel forming ability in the hollow portion is gelled. In this method, the gel or the precursor thereof attached to the fiber surface by a chemical operation is dissolved or decomposed, and has higher selectivity than removal by decomposing, and has a gel forming ability in the hollow portion. The liquid can be surely gelled, and there is no fiber deterioration or change in color tone after the treatment.

The liquid used for the washing and removal is capable of dissolving the monomer introduced into the hollow fiber, and
Any material can be used as long as it does not inhibit the polymerization of the monomer introduced into the hollow fiber and has high permeability enough to elute the monomer introduced into the hollow fiber.

Specifically, for example, water, acetone, dimethylformamide, dimethylsulfoxide, benzene,
Toluene or the like is used. In particular, water is preferably used because it is inexpensive and easy to handle.

Thereafter, in the present invention, the hollow fiber is subjected to a bending and / or kneading action in a liquid containing the fiber function-imparting agent, whereby the fiber-function-imparting agent is treated. It can be transferred and contained in the gel existing in the hollow part. Such a bending and / or kneading action may be performed within the range of the stress within the elastic limit of the fiber, whereby the air in the space remaining in the hollow fiber is extruded, and the agent for imparting fiber function is provided. The contained liquid is introduced into the hollow fiber promptly and in a large amount.

Further, such a treatment can be easily performed on hollow fibers processed into a fabric (fabric) form. That is, the fabric is rotated in a swirl type washing tub having a reversal of water flow, or processed by a dyeing apparatus that is installed in many general dyeing processing plants and circulates the fabric with a high-pressure or normal-pressure liquid flow or air flow. Alternatively, the treatment can be performed in a continuous scouring tank having a liquid flow. This treatment is preferable because the removal of the gel existing in the hollow portion does not proceed at all and the necessary amount of gel is maintained.

Examples of the agent for imparting fiber functionality used in the present invention include sodium dodecylbenzenesulfonate, low molecular weight polyethylene glycol, acrylates, methacrylates, polyacrylates, and polymethacrylates. , Hygroscopic, water-retentive substances, medicinal properties such as aloe, cucumbers, garlic, substances with plant fragrance (plant extracts, plant proteins), bacterial culture of collagen, keratin, sericin, etc., medical treatment for wound treatment, etc. Physiological function-imparting substances (animal proteins), electrical function-imparting substances (ceramic fine particles) for conductors such as titanium oxide, silica, alumina, zeolite, etc., octacarboiron phthalocyanine, dimethyl phthalate, organic silicon Antibacterial and deodorant substances such as quaternary ammonium and organic nitrogen compounds Fee (flavor, fragrance),
Water repellency such as a compound having a perfluoroalkyl group,
An oil-repellent substance or the like can be appropriately mentioned. Further, in order to remarkably increase the amount of fixation, a part of them may be introduced simultaneously with a liquid having a gel forming ability in advance.

[0024]

Thus, according to the present invention, a gel-forming liquid introduced into a hollow fiber through a communication hole is gelled, and a large amount of a fiber-function-imparting agent is contained in the gel. The fabric can be fixed promptly, satisfying a desired level of functionality and maintaining sufficient durability of the function without impairing the feel and quality.

[0025]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

(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 fiber spinneret. Polyester multifilament yarn having a hollow cross section by drawing the undrawn yarn (50 denier / 20 filaments, titanium oxide content: 0.3% by weight)
I got A cross-section was photographed with an electron microscope, and the inner radius of the hollow fiber was measured. The polyester multifilament yarn was knitted into a circular knitted fabric according to a conventional method, and then scouring and presetting were performed. This was treated in a buffer solution containing 0.5 g / liter of sodium carbonate at a temperature of 130 ° C. for 30 minutes using a high-pressure jet dyeing machine to obtain a knitted fabric composed of hollow fibers having communication holes.

(2) Preparation of Liquid Having Gel Forming Capability A liquid having the following formulation was prepared. The viscosity of this liquid is temperature: 10
7 centipoise at 20 ℃, 4 centipoise at 20 ℃, 40 ℃
Was 2 centipoise. The liquid did not solidify at 0 ° C. or higher, did not gel at 20 ° C. or lower for at least 10 days, and gelled at 80 ° C. or higher within 2 minutes. Acrylic acid [15 parts by weight] (Product containing 200 ppm of methoquinone; manufactured by Nippon Shokubai Co., Ltd.) Sodium hydroxide [6.25 parts by weight] (Reagent 1st grade; manufactured by Wako Pure Chemical Industries, Ltd.) Blemmer PDE-400 [10 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 [68.25 parts by weight] The viscosity of the liquid (unit) The centipoise (cps) is a vibration type viscometer model MV-100-L manufactured by Yamaichi Electric Co., Ltd.
Was measured.

(3) Processing procedure: The knitted fabric (width: 120 cm, length: 20 m) prepared in (1) is immersed in the liquid prepared in (2), and the amount of the liquid adhered to the knitted fabric Squeezed and rolled to 100%, and covered with a polyethylene bag. Temperature: left in an atmosphere maintained at 20 ° C. for 7 days to transfer a part of the liquid present between the fibers into the hollow interior to obtain a work cloth.

(4) Evaluation i) The solid content retention (unit:%) was calculated by the following formula by measuring the fabric weights V ₀ and V ₁ before and after processing, respectively. Solids retention (%) = [(V ₁ −V ₀ ) / V ₀ ] × 100 ii) The moisture absorption was determined by pre-drying the sample at a temperature of 50 ° C. for 2 hours and then stopping at a temperature of 105 ° C. for 2 hours. -dried (the weight at this time is W _0). Next, after placing in a thermo-hygrostat at 20 ° C. × 90% RH for 3 days, the weight: W ₁ was measured, and the moisture absorption was calculated by the following formula. Moisture absorption (%) = [(W ₁ −W ₀ ) / W ₀ ] × 100 iii) Washing is performed according to JIS L-1018-77 6.3.
6. Repeated 20 times by a method based on the H method.

Example 1 The work cloth prepared in the above (3) was kept in hot water at 95 ° C. for 10 minutes to remove the liquid adhering to the fiber surface, and at the same time, the liquid inside the hollow was gelled. Was. At this point, the solids retention was 13% and the moisture absorption was 7.6%. Further, the work cloth is treated with water containing 0.5 g / liter of sodium dodecylbenzenesulfonate (reagent 1 grade, manufactured by Wako Pure Chemical Industries, Ltd.) in a reversing spiral washing tub while giving a kneading effect to give a solid content. Retention: 14.0%, moisture absorption: 11.6%. The treated cloth was washed again by the method (4) iii) and measured again. As a result, the solids retention was 13.6%,
The moisture absorption was 10.0%, indicating good functional durability.

Comparative Example 1 The work cloth prepared according to the above (3) was treated in hot water at 95 ° C. in the same manner as in Example 1, and at the same time, only the liquid in the hollow portion was gelled. At this time, the solid content retention rate was 12%, and the moisture absorption rate was 7.5%. Furthermore, when this processed cloth is treated only with water while imparting a kneading effect in an inverted spiral type washing tub, the solid content retention rate is 1%.
1.7% and the moisture absorption was 7.3%.

[Comparative Example 2] In Example 1, instead of being treated in an inverted whirlpool type washing tub, only one day of immersion in water containing 0.5 g / liter of sodium dodecylbenzenesulfonate was used. In Example 1, the solids retention was 11.5% and the moisture absorption was 7.4%.

Example 2 Instead of treating sodium dodecylbenzenesulfonate with water containing 0.5 g / liter of sodium dodecylbenzenesulfonate in a reverse whirlpool type washing tub in Example 1, a jet dyeing machine was used at 130 ° C. The treatment was carried out in the same manner as in Example 1 except that the work cloth was rubbed in water containing 0.7 g / l of sodium dodecylbenzenesulfonate at a temperature for 10 minutes and then treated while bending. The resulting treated cloth has a solids retention of 12.9% and a moisture absorption of 10.9%.
%Met.

Example 3 Instead of using sodium dodecylbenzenesulfonate in the washing tub of Example 1 for treatment, a continuous scouring tub equipped with a device for spraying a water stream from above and below the knitted fabric was used. The treatment was carried out in the same manner as in Example 1 except that the treatment was carried out at a temperature of ° C. while bending in water containing 0.6 g / l of sodium dodecylbenzenesulfonate so that the residence time was 7 minutes. The resulting treated cloth has a solids retention of 13.4% and a moisture absorption of 1
0.6%.

Example 4 Instead of using the liquid having gel-forming ability of the above (2), a liquid prepared according to the following formulation was used, and the other conditions were the same as in Example 1. Acrylic acid [15 parts by weight] (Product containing 200 ppm of methoquinone; manufactured by Nippon Shokubai Co., Ltd.) Sodium hydroxide [6.25 parts by weight] (Reagent 1st grade; manufactured by Wako Pure Chemical Industries, Ltd.) Blemmer PDE-400 [10 parts by weight (PEG400 dimethacrylate; manufactured by NOF CORPORATION) Sodium dodecylbenzene sulfate [5 parts by weight] Potassium persulfate [0.5 parts by weight] (Reagent 1st grade; manufactured by Wako Pure Chemical Industries, Ltd.) Water [63.25 weight Part] The viscosity of this liquid is 8 centipoise at 10 ° C., 20
It was 4 centipoise at 40 ° C and 2.5 centipoise at 40 ° C. This liquid does not solidify at 0 ° C or higher,
In the following, gelling did not occur for at least 10 days, but gelled within 2 minutes at 80 ° C or higher. The obtained treated cloth had a solids retention of 15.3% and a moisture absorption of 13%.

Example 5 Instead of using sodium dodecylbenzene sulfate in Example 1, the average molecular weight was as follows:
Sodium polyacrylate of 2600 (average molecular weight: 200)
Polyacrylic acid (reagent 1 grade; manufactured by Wako Pure Chemical Industries, Ltd.) treated with a predetermined amount of sodium hydroxide.
Treated with water containing 0.6 g / l. The solid content retention of the obtained treated cloth is 12.5%, and the moisture absorption is 1
0.8%.

Example 6 The procedure of Example 1 was repeated, except that water containing 1 g / liter of water-soluble collagen was used instead of sodium dodecylbenzenesulfate. The solid retention of the obtained treated cloth was 12.8%, and the moisture absorption was 10.4%.

Claims (5)

[Claims] 1. A liquid having a gel-forming ability is introduced into said hollow part of a hollow fiber having a communication hole from a fiber surface to a hollow part through said communication hole, and then said liquid having a gel-forming ability is dissolved. Or, treating the hollow fiber in a dispersible liquid to substantially remove the liquid having gel-forming ability on the surface of the hollow fiber, or at the same time or after removing the gel-forming liquid in the hollow portion. A method for filling a hollow fiber with a solid material, comprising: gelling a liquid having a function; and then subjecting the hollow fiber to a bending and / or kneading action in a liquid containing a function-imparting agent. 2. The method according to claim 1, wherein the gel-forming liquid is a monomer solution containing a polymerization initiator. 3. The method according to claim 1, wherein the bending and / or kneading action is performed in a washing tub. 4. The method according to claim 1, wherein the bending and / or kneading action is performed in a liquid dyeing tank. 5. The method according to claim 1, wherein the bending and / or kneading action is carried out in a continuous scouring tank.