JP2000096441A - Treatment of hollow fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for treating a hollow fiber by which a sufficient amount of a functionality imparting agent for the fiber is filled in a hollow part of the hollow fiber. SOLUTION: A monomer liquid containing a polymerization initiator is introduced from the fiber surface through communicating holes into a hollow part of a hollow fiber having the communicating holes of the hollow part and the resultant hollow fiber is then cured with heat, etc., to accelerate the polymerization of the monomer in the hollow fiber. The hollow fiber is subsequently treated with a solvent capable of dissolving the monomer to substantially remove the monomer sticking to the fiber surface and simultaneously complete the polymerization of the monomer in the hollow part. Otherwise, the monomer sticking to the fiber surface is removed and the polymerization of the monomer in the hollow part is then completed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for treating hollow fibers, and more particularly, to a method for treating hollow fibers that imparts high functionality and durability to the hollow fibers.

[0002]

2. Description of the Related Art Heretofore, in a hollow fiber having a communication hole to a hollow portion on a fiber surface, there are several proposals for obtaining a functional fiber by attaching a functional substance to the hollow portion. .

For example, Japanese Patent Application Laid-Open No. Hei 5-33978,
JP-A-6-17372 and JP-A-6-17373
Japanese Patent Application Laid-Open Publication No. H11-15083 proposes that a hollow portion of a hollow synthetic fiber having a communication hole from the fiber surface to the hollow portion is impregnated with a natural protein solution, crosslinked and insolubilized, and the durability of moisture absorption performance is improved.

[0004] However, since natural protein solutions generally have a high viscosity, it is extremely difficult to impregnate a hollow portion through a communication hole. On the other hand, when a natural protein solution is impregnated at a low concentration, there is a problem that the amount of the natural protein contained in the hollow portion decreases, and the level of the expressed moisture absorbing performance becomes insufficient.

Japanese Patent Application Laid-Open No. Hei 5-173167 discloses that a core-sheath composite fiber in which a part of the core component is exposed on the fiber surface is alkali-reduced, the core is dissolved and removed, and a hollow is formed in the longitudinal direction of the fiber. A hollow fiber formed with a splitting groove reaching the portion, a hygroscopic fiber obtained by adhering a hygroscopic agent formed from a monomer having a cloud point equal to or lower than the glass transition point of the fiber-forming polymer to the hollow portion of the hollow fiber. It has been disclosed.

However, in the above-mentioned method, it is difficult to completely dissolve and remove the core portion, so that the adhesion of the monomer becomes insufficient, and even if the core is dissolved and removed, the width and the length are too large. Since the grooves are formed, there is a problem that the hygroscopic agent falls off from the split grooves during washing or the like, resulting in poor durability.

Moreover, in the above method, since the hygroscopic polymer also adheres to the fiber surface, when the fabric is used,
There is a problem that the fabric becomes difficult to deform due to an increase in the frictional resistance at the yarn intersection or the yarn intersection is fixed, and the feeling becomes hard.

In order to solve such a problem, Japanese Patent Laid-Open No.
JP-A-26466 discloses that after a water-soluble monomer containing a fiber-function-imparting agent is suction-introduced through the communication hole into the hollow portion of the hollow fiber in which communication holes to the hollow portion are scattered on the fiber surface, There is disclosed a method of imparting various functions to the hollow fiber by polymerization.

However, in this method, the monomer remaining on the fiber surface is dissolved and removed with a solvent,
Although the texture of the obtained fabric is good, particularly when the function-imparting agent inhibits the polymerization, there is still a possibility that the monomer in the hollow fiber may be removed.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to propose a method for treating a hollow fiber in which the hollow portion of the hollow fiber is filled with a sufficient amount of a fiber-function-imparting agent. The present invention proposes a method of treating a hollow fiber in which a sufficient amount of a functionalizing agent can be filled in a hollow fiber even when the functionalizing agent is one that inhibits polymerization of a monomer.

[0011]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, the polymerization has started in the hollow portion of the hollow fiber in which communication holes from the fiber surface to the hollow portion are scattered. After introducing the monomer containing the agent, prior to selectively polymerizing only the monomer in the hollow fiber with a solvent capable of dissolving the monomer, the medium fiber is cured by heat or the like, and the inside of the hollow fiber is cured. It has been found that the objective fiber can be obtained by accelerating the polymerization of the monomer solution and then treating the hollow fiber with a solvent capable of dissolving the monomer, thereby completing the present invention.

That is, according to the present invention, a monomer liquid containing a polymerization initiator is introduced into the hollow portion of the hollow fiber having a communication hole from the fiber surface to the hollow fiber through the communication hole,
Next, after curing the hollow fiber by heat or the like to promote polymerization of the monomer in the hollow fiber, the hollow fiber is treated with a solvent capable of dissolving the monomer to substantially remove the monomer adhering to the fiber surface. At the same time or after the removal, the polymerization of the monomer in the hollow portion is completed.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
Examples of the hollow fibers used in the present invention include chemical fibers such as rayon and acetate, and synthetic fibers such as polyester and polyamide, and polyester hollow fibers are particularly preferred.

[0014] The polyester as used herein means terephthalic acid as a main dicarboxylic acid component and at least one glycol, preferably at least one alkylene glycol selected from ethylene glycol, trimethylene glycol, tetramethylene glycol and the like. Polyester as the main glycol component, etc., of which polyethylene terephthalate is particularly preferred.

The polyester contains, if necessary, a stabilizer, an antioxidant, a flame retardant, an antistatic agent, a fluorescent brightener, a catalyst, a coloring inhibitor, a heat-resistant agent, a coloring agent, inorganic particles and the like. Is also good.

The hollow fiber can be produced by a conventionally known method. For example, as described in Japanese Utility Model Publication No. 2-43879, the hollow fiber has an arc-shaped slit hole in which at least one portion is discontinuous. In the vicinity of the end of the slit hole, a method of melt spinning using a hollow fiber spinneret provided with a semicircular projection on the inner edge thereof is arbitrarily adopted.

The hollow ratio of the hollow fiber is required to maintain the mechanical properties of the fiber and to fill a sufficient amount of the polymer.
It is preferably 5 to 40%, more preferably 2 to 40%.
It is in the range of 0-40%.

A method for forming a large number of communication holes from the fiber surface to the hollow portion on the fiber surface is disclosed in
As disclosed in Japanese Patent No. 20319, for example, in the case of a polyester fiber, a polyester obtained by copolymerizing an organic sulfonic acid compound is mixed and melt-spun to form a hollow fiber, and the hollow fiber is subjected to alkali weight reduction treatment. A method of forming a communication hole is used.

If the hollow fiber having a hollow ratio of 20% or more is subjected to alkali treatment, a low-oriented portion and / or a strain-concentrated portion along the longitudinal direction of the fiber can be removed without using an organic sulfonic acid compound. As a mark, a communication hole can be formed.

Further, a method of dissolving or decomposing a core polymer of a core-sheath type conjugate fiber to obtain a hollow fiber having a communication hole in a sheath as disclosed in JP-A-7-26466 is used. Can also.

The communication hole thus formed preferably has a width of 0.2 to 10 μm and a length of 5 to 20 μm. If the width and length of the communication hole is out of this range, the introduction of the agent for imparting fiber functionality becomes insufficient,
It is not preferable because the polymer filled in the hollow fibers may easily fall off.

In the present invention, a monomer containing a polymerization initiator is introduced into the hollow portion of the hollow fiber having the communication hole. The monomer liquid used here is prepared by converting the monomer and the polymerization initiator into a suitable solvent such as water. A material that has been dissolved, dispersed, or emulsified and has as low a viscosity as possible to facilitate introduction into hollow fibers is used.

The monomer refers to a monomer that is soluble in a solvent such as an organic solvent or water and can be polymerized in the presence of a polymerization initiator. Examples thereof include butadiene, acrylonitrile, styrene, vinyl chloride, vinylidene chloride, and acetic acid. Examples include vinyl monomers such as vinyl, (meth) acrylic acid, (meth) acrylic acid derivatives, di (meth) acrylic acid, and di (meth) acrylic acid derivatives. These monomers may be used alone or in combination of two or more. As the polymerization initiator used here,
For example, peroxides such as potassium persulfate, ammonium persulfate, hydrogen peroxide and benzoyl peroxide, cerium ammonium salts such as ceric ammonium sulfate and ceric ammonium nitrate, or α, α'-azobisisobutyro Nitrile and the like can be mentioned. In addition, those to which a fiber-function-imparting agent is added as necessary are used for these monomers.

The agent for imparting functionality to fiber used in the present invention refers to an agent which imparts various functions to fibers, and examples thereof include the following.

(1) Substances having medicinal properties and plant incense (plant extracts, plant proteins); aloe, aloe vera, ougone (koganebana), oubak (kihada), cucumbers (kudzu), chamomile, cucumber, kouka (safflower), wheat , Rice, Sanshin (Gardenia), Shea, Sikon (Murasaki), Peony, Birch, Senkyu, Assemblage, Capsicum, Tissou (jujube), Dice, Cha (tea, green tea), Touki, Chimpi (Unshumikan), Spruce (daidai) ), Tomatoes, carrots, garlic, Baku monadou (Janohige), hammerellis, loofah, hops, peaches, yokinin (adlay), lemon,
Logwood, Altea, Arnica, Ginkgo, Hypericum, Epimedium, Kiwi, Kujin (Clara), Souhakuhi (Mulberry), Salvia, Sansho, Jio (Akaoyajio), Chowji (Clove), Tokinsenka, Juyaku (Hikiokoshi), Bodaiju, A solution or extract obtained by extracting astragalus, astragalus, kujin and the like with a solvent (for example, a 45% aqueous solution of propylene glycol), and then drying and pulverizing.

(2) Medical use for culturing bacteria, treating wounds, etc.
Physiological function-imparting substance (animal protein); human placenta, bovine placenta,
Human spleen band, bovine skin, pig skin, bovine ligament, bovine blood, bovine brain, swine stomach, cockscomb, lactococci, crab shell, milk, silk, brewer's yeast,
Whey, casein, etc.

(3) An electrical function-imparting substance (ceramic fine particles) for an electric conductor, a magnetic substance, or the like;
Single-component fine particles of a metal oxide, carbide, nitride or silicide of 01 to 1 μm, or mixed fine particles thereof. Specifically, titanium oxide, zinc oxide, colloidal silica, iron oxide, aluminum oxide, zirconium carbide,
Zeolite, spiolite, etc.

(4) Compounds having antibacterial and deodorant properties; compounds having antifungal properties, antiseptic properties, resistance to bacteria, repellency against insects or mites, or deodorant properties and deodorant properties A compound having the formula: Specifically, octacarboiron phthalocyanine, dimethyl phthalate, diethyl phthalate, methyl adipate, polyacrylonitrile copper sulfide complex (daidunite), organosilicon quaternary ammonium salts, 3,4,4'-trichloro Carbanilide, organic nitrogen compound, antibacterial zeolite, aromatic halogen compound, α-sinamic aldehyde, 2- (4
—Thiazolyl) benzimidazole and the like.

(5) Compounds having aromatic properties; for example, FC5696 (Rigusa) and FC5698 manufactured by Riken Kosaku Kogyo
(Jasmine), FC5697 (rose), FC128
4 (lemon oil), rose flavor 328 (O
S), Shoyaku flavor 3127 (OS), 315
5 (OS), FC5700 (Hinoki), FC5699
(Lavender), Forest Shower-NO.
86, mask melon flavor 1406 (WS), jasmine flavor 122 (OS) and the like.

(6) a compound having water absorbency or hygroscopicity; for example, a copolymer of polyethylene glycol and polyethylene terephthalate, a compound in which a group having a polyoxyylene oxide chain is bonded to a polyalkylene polyamine skeleton, and HLB is For example, those in the range of 6.0 to 16.0.

(7) A compound having water repellency; for example, a polyacrylic acid ester having a fluorocarbon group such as perfluoroalkyl in a side chain and having a repeating unit represented by the following formula as a main repeating unit, and Fluorinated polymers having a methacrylic acid ester-based polymer or the like in the main chain, dimethylpolysiloxane or silicone-based copolymers thereof.

[0032]

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(R1 represents hydrogen or a methyl group, and n is 3
To 21. In the present invention, the agent for imparting functionality to fiber is introduced into the hollow portion of the hollow fiber through the communication hole, and the method includes (1) adding the agent for imparting fiber functionality to hollow fiber. (2) immersing the hollow fiber in a liquid containing a fiber function-imparting agent, and then squeezing it with a mangle or the like to reduce the air in the hollow fiber to the fiber function. (3) Putting the hollow fiber in a closed container, depressurizing the air, evacuating the air in the hollow fiber, and then injecting a liquid containing a fiber function-imparting agent into the container. Examples of the method include introducing a fiber function-imparting agent into a part.

When introducing such a fiber-function-imparting agent, the hollow fiber can be subjected to treatment in any form such as yarn, spun yarn, woven fabric, knitted fabric, and non-woven fabric. It is appropriate to treat in the form of a fabric such as a knitted fabric from the viewpoint of workability.

The hollow fiber into which the monomer has been introduced as described above is cured by heat or the like to promote the polymerization of the monomer. Before the curing, the monomer adhering to the fiber surface by pressing or the like is removed. Removal is preferred from the viewpoint of improving the texture. Although any method may be used for the curing, it is particularly preferable to perform the curing by steam curing in consideration of the effect of the monomer liquid remaining on the surface of the hollow fiber on the fabric and the like.

After curing by heat or the like, the hollow fiber is immersed in a solvent capable of dissolving the monomer,
Alternatively, it is preferable to dissolve and remove the monomer attached to the fiber surface by, for example, applying a solvent capable of dissolving the monomer to the surface of the hollow fiber.

The solvent used here is capable of dissolving the monomer introduced into the hollow fiber, and does not inhibit the polymerization of the monomer introduced into the hollow fiber. Any material can be used as long as it does not have high permeability enough to elute the monomer.

For the monomers exemplified above, water, acetone, dimethylformamide, dimethylsulfoxide, benzene, toluene and the like are used. In particular, water is preferably used because it is inexpensive and easy to handle.

When the hollow fiber having the monomer liquid introduced into the hollow interior is treated with the above-mentioned solvent, the temperature of the solvent is set to a temperature equal to or higher than the polymerization initiation temperature of the monomer. Heating to a temperature of 50 to 100 ° C. is advantageous because the monomers adhering to the fiber surface can be dissolved and removed and the monomers introduced into the hollow fibers can be simultaneously polymerized. Further, it is preferable to add a polymerization inhibitor to the above-mentioned solvent, since the polymerization of the monomer remaining on the fiber surface is suppressed, and the removal of the monomer is further facilitated.

The polymerization inhibitor is capable of generating stable radicals, such as diphenylpicrylhydrazyl, galvinoxyl, and ferdazyl, as well as oxygen, sulfur, and the like which generate stable radicals by an addition reaction with a growing radical.
Examples thereof include benzoquinone derivatives, nitro compounds, and diphenylpicrylhydrazine, diphenylamine, hydroquinone, and tert-butylcatechol that generate a stable radical by a chain transfer reaction with a growing radical.

When a hollow fiber into which a monomer containing a fiber-functionality-imparting agent is introduced is treated with a solvent containing these polymerization inhibitors, the amount of the polymerization inhibitor in the solvent depends on the amount of the polymerizable monomer in the hollow fiber. Have a significant effect.

That is, when the amount of the polymerization inhibitor present in the solvent is too large, an amount of the polymerization inhibitor that can inhibit the polymerization enters the hollow portion from the communication hole, and not only the fiber surface, but also Polymerization of the monomer in the fiber is also suppressed, and as a result, a polymer may not be formed in the hollow fiber.

Accordingly, the amount of the polymerization inhibitor present in the solvent depends on the polymerization inhibiting ability of the polymerization inhibitor, but the minimum amount capable of capturing the reactive radical generated by heating from the monomer attached to the fiber surface by heating. Preferably, the amount is limited.

Further, it is preferable to add a soaping agent to the solvent, since the removal of the monomer adhering to the fiber surface is promoted. Examples of the soaping agent include an alkaline cleaning liquid containing sodium hydroxide or sodium carbonate as a main component, an ionic surfactant or a nonionic surfactant generally used for textile processing. An appropriate amount of the soaping agent added to the solvent is 0.1 to 5.0% by weight.

The method of curing the hollow fiber in which the monomer liquid and the fiber function-imparting agent have been introduced into the hollow part by heat or the like and then treating it with the above-mentioned solvent is as described above. The method is not particularly limited as long as it can dissolve and remove the monomer thus produced, but a method in which the hollow fiber is immersed in a solvent and stirred is preferably used.

After treating with a solvent in this manner to dissolve and remove the monomer adhering to the fiber surface, the monomer was polymerized by heating to a temperature at which the monomer in the hollow fiber could be polymerized, and introduced into the hollow portion. Fix the fiber functional additive and the like. Of course, as described above, by removing the solvent from the fiber surface and polymerizing the monomer in the hollow fiber, the solvent can be heated to a temperature at which the monomer can be polymerized.

[0047]

As described above, according to the present invention, a sufficient amount of a fiber function-imparting agent can be present in a hollow fiber, even if the fiber-function-imparting agent inhibits polymerization of a monomer. This makes it possible to obtain all kinds of high-performance fibers. That is, after the monomer liquid containing the polymerization initiator is introduced into the hollow portion, it is cured by heat or the like to promote the polymerization of the monomer in the fiber, so that the monomer adhering to the fiber surface is substantially removed. In addition, the fiber function-imparting agent in the hollow portion is not removed at the same time, and a sufficient amount of the function-imparting agent can be present in the hollow portion. On the other hand, since the monomer on the fiber surface is removed by the solvent, the polymer from the monomer does not exist on the fiber surface, and even when the fabric is used, the frictional resistance at the yarn intersection does not increase and the texture is improved. No problem such as hardening occurs.

[0048]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The functional agent filling rate and durability in the examples were measured by the following methods.

(1) Filling amount of functional agent The filling amount of the functional agent was calculated from the weight change of the fabric before and after the processing.

(2) Washing durability According to JIS L-1018-77 6.36, H method,
The washing was repeated 30 times.

Example 1 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. Next, the undrawn yarn is drawn to obtain a multifilament yarn having a round hollow cross section (50 denier / 20 filament,
(Amount of titanium oxide: 0.3% by weight).

The tricot knitted fabric knitted using the multifilament yarn is scoured and preset, and is treated in hot water (105 ° C.) containing 50 g / l of sodium hydroxide for about 10 minutes to reduce the weight loss rate. Alkali weight reduction treatment was performed to 20%.

When the multifilament yarn was taken out from the obtained fabric and its surface was observed with an electron microscope, the width was 0.2 to 2.0 μm and the length was 10 to 150 in the fiber axis direction.
μm microgrooves for each filament
At least one or more were observed per 00 μm.

Next, the cloth is placed in a closed container, the pressure in the container is reduced to 0.004 mmHg using a rotary pump, and then PEG-dimethacrylate represented by the following formula (2) is placed in the container. : 30 parts by weight, 0.1 part by weight of potassium persulfate, 65.9 parts by weight of water, and 4.0 parts by weight of water-insoluble VBE (vanillyl butyl ether).

[0055]

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After the injection of the monomer solution and VBE, the reduced pressure was maintained for 10 minutes using a rotary pump. At this time, the pressure in the container was 0.2 mmHg. Next, the pressure in the container was returned to a constant pressure, and after impregnating the above-mentioned monomer liquid into the cloth, the cloth was steam-cured for 3 minutes. Then, the cloth was immersed in hot water of 100 ° C. for 3 minutes while stirring. And heat-treated for drying.

The obtained fabric had a soft texture, showed a high loading of the functional agent as shown in Table 1, and maintained a high value even after washing.

[Comparative Example 1] In Example 1, the same treatment as in Example 1 was performed except that the steam curing treatment was not performed. The obtained fabric had a soft texture, but as shown in Table 1, the amount of the functional agent before and after washing was inferior to that of Example 1.

Example 2 As a monomer liquid, a monomer composed of 30 parts by weight of PEG-dimethacrylate represented by the above formula (2), 0.1 parts by weight of potassium persulfate, and 65.9 parts by weight of water A liquid and a liquid consisting of water-insoluble hinokitiol: 4.0 parts by weight were used.
The same procedure was followed. The obtained fabric had a soft texture, and as shown in Table 1, showed a high functional agent loading before and after washing.

[Comparative Example 2] In Example 2, the same treatment as in Example 2 was performed except that steam curing was not performed. Although the obtained fabric had a soft texture, as shown in Table 1, the filling amount of the functional agent before and after washing was inferior to that of Example 2.

[0061]

[Table 1]

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Torukei Matsui 3-4-1, Amihara, Ibaraki-shi, Osaka Teijin Limited Osaka Research Center F-term (reference) 4L033 AB02 AC03 AC06 AC07 AC10 AC15 CA01 CA22 CA45 CA70 DA00 DA03 DA06

Claims (4)

[Claims] 1. A monomer liquid containing a polymerization initiator 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 hollow fiber is cured by heat or the like. After ringing to promote the polymerization of the monomers in the hollow fibers, the hollow fibers are treated with a solvent capable of dissolving the monomers to simultaneously or substantially remove the monomers adhering to the fiber surface. And after that, the polymerization of the monomer in the hollow portion is completed. 2. The method for treating hollow fibers according to claim 1, wherein the monomer contains an agent for imparting function to fiber. 3. The method for treating hollow fibers according to claim 1, wherein water is used as the solvent. 4. The method for treating hollow fibers according to claim 1, wherein the temperature of the solvent is equal to or higher than the polymerization initiation temperature of the monomer.