JPH11107169A - Treatment of hollow staple - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for treating a hollow staple, capable of extremely improving removal resistance (durability) of a monomer and a functionality providing agent packed in a hollow part of a highly hollow staple. SOLUTION: A hollow staple having 10-65% hollow ratio, 0.5-50 de fineness and 10-150 mm fiber length is treated with a monomer solution containing a polymerization initiator. The monomer solution containing the polymerization initiator is introduced into the hollow part. The hollow staple is washed with a solvent capable of dissolving the monomer. The monomer attached to the surface of the staple is removed. The monomer in the hollow part is polymerized simultaneously with the removal of the monomer or after the removal of the monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating short staple fibers, and more particularly to a short staple fiber having a high porosity, which can be filled with a monomer solution and an agent for imparting functionality. The present invention relates to a method for treating fibers.

[0002]

2. Description of the Related Art Heretofore, there have been several proposals for obtaining functional fibers by attaching a function-imparting substance to hollow portions of hollow continuous fibers or short fibers.

For example, Japanese Patent Application Laid-Open No. Hei 5-33978,
JP-A-6-17372 and JP-A-6-1737
No. 3 discloses that a hollow synthetic fiber having a communication hole communicating from a fiber surface to a hollow portion is treated in a natural protein solution, the natural protein solution is introduced into the hollow portion, and is insolubilized by a cross-linking reaction to impart moisture absorption performance. It is disclosed.

Japanese Patent Application Laid-Open No. 5-173167 discloses that a core-sheath type composite fiber in which a part of the core component is exposed on the fiber surface is reduced in alkali, the core is dissolved and removed, and a hollow portion is formed in the longitudinal direction of the fiber. A hollow fiber with a split groove that reaches
A hygroscopic fiber in which a hygroscopic agent is attached to the hollow portion of the hollow fiber is disclosed.

In these methods, the amount of alkali is reduced in order to form a communication hole from the fiber surface to the hollow portion. However, it is very difficult to control the communication hole to an appropriate size by reducing the alkali, and the hole diameter is too small. When the pore size is too large, a problem occurs in that the functional material falls off quickly and the durability is poor.

For example, in the former case, since the natural protein solution generally has a high viscosity and the aqueous solution may gel, it is extremely difficult to impregnate the hollow portion through the communicating hole. On the other hand, in the latter case, by removing the core,
Since a split groove having an excessively large width and length is formed, there is a problem that the hygroscopic agent falls off from the split groove during washing or the like, resulting in poor durability.

On the other hand, Japanese Patent Application Laid-Open No. Hei 7-268772 discloses that a hollow fiber having no communicating hole in a cross-sectional direction is immersed in a low-viscosity liquid containing a drug of 5 centipoise or less and the liquid is introduced into the hollow portion of the hollow fiber. It is disclosed to be introduced.

However, in this method, after the low-viscosity liquid is introduced into the hollow fibers, the liquid is not subjected to solidification such as gelling, so that it is easily washed away during washing and the durability is poor. there were.

[0009]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned conventional problems and reduces the falling-off resistance (durability) of the monomer and the function-imparting agent filled in the hollow portion of the short fiber having a high hollow ratio. It is an object of the present invention to provide a method for treating hollow short fibers, which has greatly improved.

[0010]

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, have used a short fiber having a high hollow ratio, and communicated from the fiber surface to the hollow portion as in the prior art. It has been clarified that a desired hollow short fiber can be obtained when a monomer liquid containing a polymerization initiator is introduced into the hollow portion of the short fiber without passing through a hole.

That is, according to the present invention, the hollow ratio is 10
~ 65%, fineness 0.5 ~ 50de and fiber length 10 ~
A hollow short fiber within a range of 150 mm is treated with a monomer solution containing a polymerization initiator, a monomer solution containing a polymerization initiator is introduced into the hollow portion, and then washed with a solvent capable of dissolving the monomer to remove the short fiber. A method for treating hollow short fibers, characterized in that the monomer in the hollow portion is polymerized simultaneously with or after the removal of the monomer attached to the surface.

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. Particularly preferred are polyester fibers.

As used herein, the polyester 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 and the like as a main glycol component. Polyester and the like. The polyester may 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, an inorganic particle agent, and the like, if necessary. . In addition, the hollow section fiber can be manufactured by a known method.
The method described in JP-A-79 can be arbitrarily adopted.

It is important that the short fiber having the hollow cross section has a hollow ratio of 10 to 65%.
More preferably, those in the range of 20 to 60% are exemplified. If the hollow ratio is less than 10%, it is difficult to introduce a sufficient amount of monomer into the hollow interior, and it is difficult to obtain the effects of the present invention. When the hollow ratio is larger than 65%, the thickness of the fiber wall becomes thin, causing splitting or the like, and depending on the application, not only is it difficult to use the polymer, but also the polymer formed in the hollow portion becomes easy. Therefore, the function-imparting agent is also easily dropped, and the effect of the present invention cannot be obtained.

The shape of the hollow cross section of the short fiber having a hollow cross section used in the present invention is not particularly limited, and may be a hollow fiber having a circular cross section, a triangle, a polygon, a quadrangle or the like. Those with a hollow part in the cross section are used,
In this case, the shape of the hollow portion itself may be the same as or different from the outer shape.

Further, the method for measuring the hollow ratio is as follows: In the cross section of the hollow fiber, when the cross-sectional area of a solid portion existing around the hollow portion is S ₁ and the cross-sectional area of the hollow portion is S ₂ , ｛S
₂ / (S ₁ + S ₂ )｝ × 100, which is obtained as an average value of 20 fibers from a photograph taken by enlarging the cross section of the hollow fiber by about 500 times.

Further, the short fibers used in the present invention need to have a fineness in the range of 0.5 to 50 de, preferably in the range of 1.0 to 20 de. If the fineness is less than 0.5 de, it is difficult to form a hollow section with high efficiency, which is not preferable. Further, those having a fineness of more than 50 degrees are not preferred because the texture becomes coarse and cannot be used for ordinary applications.

The short fiber has a fiber length of 10 to 150.
mm, preferably 20 to 15 mm
It is in the range of 0 mm. If the fiber length is out of this range, the handling of short fibers becomes poor, and the workability when processing into a nonwoven fabric or yarn becomes poor. Further, if the fiber length exceeds 150 mm, it becomes difficult to introduce the monomer liquid into the entire hollow portion of the short fiber, which is not preferable.

Next, the monomer liquid used in the present invention is prepared by dissolving a monomer and a polymerization initiator in a liquid such as an organic solvent or water.
It is preferably dispersed or emulsified, and has a viscosity as low as possible to facilitate introduction into the hollow fiber.

For this reason, 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. vinyl,
Examples include vinyl monomers such as (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.

The monomer liquid used in the present invention may contain a polymerization initiator.
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-azobisisothyronitrile And so on. In addition, a functionality imparting agent can be added to the monomer liquid as needed.

The function-imparting agent used in the method of the present invention includes:
It is made of a polymer or a compound that does not cause polymerization when polymerizing the above-mentioned monomer liquid, and can impart various functions to the fiber. Examples thereof include the following.

(1) Substances having medicinal properties and plant incense (plant extracts, plant proteins) aloe, aloe vera, ogun (goganebana), oubak (kihada), cuckoo (kudzu), chamomile, cucumber, kouka (safflower), wheat, Rice, sanshin (gardenia), shea, sicon, purple, peony, birch, senkyu, assembly, capsicum, daisy (jujube 9), dice, tea (tea, green tea), touki,
Chimpi (unsaturated mandarin), spruce (daidai), tomato, carrot, garlic, bakmonadou (janoge), hammerellis, loofah, hop, peach, yokuninin, adlay barley, lemon, logwood, altea, arnica, ginkgo, hypericum perforatum, kaisou, kiwi The solution or extract obtained by extracting, kujin (clara), soybean mulberry (mulberry), salvia, salamander, jiou (redwood), clove (clove), calendula officinalis, jujuya (kiyoki), bodaiju, vetch, jinjin, etc., is dried. Crushed one.

(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, beer yeast, whey, casein, etc.

(3) Electricity-imparting substances (ceramic fine particles) for conductors, magnetic substances, etc. Single particles made of metal oxides, carbides, nitrides, and silicides having an average primary particle size of 0.01 to 1 μm. One-component fine particles or mixed fine particles thereof. Specifically, titanium oxide, zinc oxide, colloidal silica, iron oxide, aluminum oxide, zirconium carbide, zeolite, spiolite, and the like.

(4) Compounds having antibacterial and deodorant properties Compounds having antifungal properties, antiseptic properties, resistance to bacteria, repellency against insects or mites, or compounds having deodorant properties and deodorant properties. Specifically, octacarboiron phthalocyanine, dimethyl phthalate, diethyl phthalate, methyl adipate, polyacrylonitrile copper sulfide complex (daidunite), organosilicon type 4
Sphere ammonium salt, 3,4,4-trichlorocarbanilide, organic nitrogen compound, antibacterial zeolite, aromatic halogen compound, α-sinamic aldehyde, 2- (4-thiazolyl) benzimidazole and the like.

(5) Compounds having aromaticity For example, FC5696 (rush), F.R.
C5698 (jasmine), FC5697 (rose),
FC1284 (lemon oil), rose flavor 32
8 (OS), Shoyaku flavor 3127 (OS),
3155 (OS), FC5700 (Hinoki), FC56
99 (Lavender), Forest Shower-N
O. 86, Muskmelon flavor 1406 (WS),
Jasmine flavor 122 (OS) and the like.

(6) Compound having water absorbency or moisture absorbency For example, a copolymer of polyethylene glycol and polyethylene terephthalate, a compound in which a group having a polyoxylene oxide chain is bonded to a polyalkylene polyamine skeleton, and HLB of 6. Etc. in the range of 0 to 16.0.

(7) Compound having water repellency For example, a substance represented by the following formula (1) is used as a main repeating unit, a fluorocarbon group such as perfluoroalkyl is used as a side chain, and a polyacrylate or methacrylic acid is used. Fluorine-containing polymers having an ester polymer or the like in the main chain, dimethylpolysiloxane or copolymer silicone resin.

[0030]

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In the present invention, the monomer and the function-imparting agent are introduced into short fibers having a hollow cross section. The method is as follows. (2) immersing the hollow short fibers in a liquid containing a monomer liquid and a function-imparting agent, and then squeezing them with a mangle or the like to air the hollow short fibers. And (3) placing the hollow short fibers in an airtight container and depressurizing to remove air from the short fibers having a hollow cross section.
A method of injecting a liquid containing a monomer liquid and a function-imparting agent into a container and introducing the monomer liquid and the function-imparting agent into the hollow portion can be exemplified. In this case, the short fibers having the hollow cross section can be treated in the form of raw short fibers (raw cotton), woven or knitted fabric, or non-woven fabric.

After introducing the monomer solution containing the polymerization initiator and the function-imparting agent into the hollow portion, the short fiber having the hollow cross section is immersed in a solvent capable of dissolving the monomer, or It is necessary to wash by a method such as applying a solvent capable of dissolving the monomer to the surface of the short fiber having the hollow cross section to dissolve and remove the monomer attached to the fiber surface.

The solvent used here is a solvent capable of dissolving the monomer introduced into the hollow portion, and does not inhibit the degree of polymerization of the monomer introduced into the hollow portion. Any agent can be used as long as it is not so permeable as to elute the monomer.

With respect to the above-mentioned monomers, water, acetone, dimethylformaldehyde, dimethylsulfoxide,
Benzene, toluene and the like are used. Water is particularly preferred because it is inexpensive and easy to handle.

Further, when a short fiber having a hollow cross section in which a monomer liquid or a function-imparting agent is introduced into the hollow portion is treated with the solvent, the temperature of the solvent is set to a temperature equal to or higher than the polymerization initiation temperature of the monomer. 50 to 50 in the case of the monomer shown in
By heating to 100 ° C., the monomer adhering to the fiber surface can be dissolved and removed, and the monomer introduced into the hollow can be simultaneously polymerized.

Further, it is preferable to add a polymerization inhibitor to the solvent, since polymerization of the monomer remaining on the fiber surface is suppressed, and the removal of the monomer is further facilitated. As the polymerization inhibitor, a stable radical can be generated, and diphenylpicrylhydrazyl, galvinoxyl,
Other examples include ferdasil, and oxygen, sulfur, benzoquinone derivatives, and nitro compounds that generate stable radicals by an addition reaction with a growing radical, or diphenylpicrylhydrazine, diphenylamine that generates a stable radical by a chain transfer reaction with a growing radical. Examples thereof include hydroquinone and tertiary butyl catechol.

When treating a short fiber having a hollow cross section into which a monomer solution and a function-imparting agent have been introduced with a solvent containing these polymerization inhibitors, the amount of the inhibitor in the solvent is limited by the polymerizability of the monomer in the hollow portion. Have a significant effect. That is,
If the amount of polymerization inhibitor present in the solvent is too large,
There is a risk that the polymerization inhibitor in an amount sufficient to inhibit the polymerization will enter the hollow portion, and the polymerization of the monomer not only on the fiber surface but also in the fiber (in the hollow portion) will be suppressed, and the polymer cannot be formed in the hollow portion. There is. Therefore, the amount of the polymerization inhibitor present in the solvent depends on the performance of the polymerization inhibitor, but can be limited to the minimum amount that can capture the reactive radical generated by heating from the monomer attached to the fiber surface. preferable.

Further, it is preferable to add a soaping agent to the above-mentioned 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, a nonionic surfactant generally used for fiber processing, and the like. The amount of the soaping agent added to the solvent is suitably from 0.1 to 5.0% by weight.

The method of washing the hollow short fibers with the solvent after introducing the monomer solution and the function-imparting agent into the hollow portion is particularly preferable if the monomer adhering to the fiber surface can be dissolved and removed as described above. Although it is not limited, a method of immersing the short fiber having the hollow fiber in the solvent and stirring the solvent is particularly preferably used.

In this way, after treating with a solvent to dissolve and remove the monomer adhering to the fiber surface, a heat treatment is performed at a temperature at which the monomer in the hollow portion of the short fiber having the hollow cross section can be polymerized. Is polymerized to fix the functionalizing agent introduced into the hollow portion. As described above, the solvent can be heated to a temperature at which the monomer can be polymerized, and the removal of the monomer from the surface of the short fiber and the polymerization of the monomer in the hollow portion can be simultaneously performed.

[0041]

As described above, according to the present invention, the monomer introduced into the hollow portion of the short fiber is polymerized and hardly falls off, and the function-imparting agent contained in the monomer solution is also fixed in the hollow portion. As a result, the falling-off resistance (durability) of the function-imparting agent is greatly improved.

That is, in the case of a continuous fiber (filament), a communicating hole communicating with the hollow portion was necessary to introduce the monomer into the hollow portion. In the present invention, a short fiber having a high hollow ratio was used. Therefore, the monomer containing the function-imparting agent is easily introduced into the hollow portion from the hollow cross section.

Further, in the case of fabrics using short fibers, it is common to not carry out a treatment such as alkali weight reduction after forming the fabric to give a sense of volume. You need to lose weight. According to the present invention, it is possible to solve the problem of the deterioration of the quality due to the alkali weight reduction.

[0044]

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. Further, the hygroscopicity (moisture absorption rate) and the washing durability in Examples were measured by the following methods.

(1) Moisture Absorption A sample was preliminarily dried at 50 ° C. for 2 hours and then completely dried at 105 ° C. for 2 hours (the weight at this time is W ₀ ). Next, the temperature 20
After placing in a desiccator at 90 ° C and 90% RH for 3 days,
The weight (W ₁ ) is measured, and the moisture absorption is calculated by the following equation.

[0046]

(Equation 1)

(2) Washing durability According to JIS L-1018-77 6.63, method H, washing was repeated 10 times, and the moisture absorption was measured by the method of (1). To evaluate.

Example 1 Short fibers having a hollow section having a hollow ratio of 40%, a denier of 20 de, and a fiber length of 50 mm were produced by a known method, and the short fibers having a hollow section were placed in a closed container. Into the container using a rotary pump.
The pressure was reduced to 004 mmHg, and then a monomer liquid composed of 30 parts by weight of PEG-dimethacrylate represented by the following formula (2), 0.1 part by weight of potassium persulfate, and 65.9 parts by weight of water was poured into the container.

[0049]

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After the injection, the reduced pressure was further maintained for 10 minutes using the rotary pump. At this time, the pressure in the container was 0.2 mmHg. Next, the hollow short fibers were immersed in hot water for 3 minutes with stirring, and then dried and heat-treated. The obtained hollow cross-section short fiber has a soft texture, and from the observation results by electron micrographs, there is almost no polymer remaining on the surface of the short fiber, and the weight change of the entire short fiber before and after processing. The calculated adhesion rate of the polymer is
It can be regarded as the polymer filling rate in the hollow cross-section short fiber (in the hollow portion). The obtained short fibers have a high moisture absorption and excellent washing durability as shown in Table 1.

Example 2 The operation was performed in the same manner as in Example 1 except that a short fiber having a hollow section of 60%, a medium cross section, a denier of 20 de and a fiber length of 50 mm was used. The obtained short fibers had soft texture, good hygroscopicity, and good durability. The evaluation results are shown in Table 1.

Example 3 The same operation as in Example 1 was carried out except that a short fiber having a hollow section of 20%, a medium cross section, a denier of 20 de and a fiber length of 50 mm was used. The obtained short fibers had soft texture, good hygroscopicity, and good durability. The evaluation results are shown in Table 1.

Example 4 An operation was performed in the same manner as in Example 1 except that a short fiber having a hollow section of a medium section of 40%, a denier of 20 de, and a fiber length of 100 mm was used.
The obtained short fibers had soft texture, good hygroscopicity, and good durability. The evaluation results are shown in Table 1.

Example 5 An operation was performed in the same manner as in Example 1 except that a short fiber having a medium section having a hollow ratio of 40%, a denier of 20 de, and a fiber length of 20 mm was used. The obtained short fibers had soft texture, good hygroscopicity, and good durability. The evaluation results are shown in Table 1.

Comparative Example 1 The same operation as in Example 1 was carried out except that a short fiber having a hollow section of 9%, a denier of 20 de, and a fiber length of 50 mm was used. The obtained short fiber had a soft hand, but had a low hollow ratio and a sufficient amount of polymer was not introduced into the hollow portion. As shown in Table 1, the hygroscopicity and the durability were higher than those of the examples. Was inferior.

Comparative Example 2 The same operation as in Example 1 was carried out except that a short fiber having a hollow cross section of 70%, a denier of 20 de, and a fiber length of 50 mm was used. Although the obtained short fibers had a soft texture, the hollow ratio was too high, causing the polymer to fall off. As shown in Table 1, the durability of the short fibers was inferior to those of the examples.

[0057]

[Table 1]

Claims (6)

[Claims] A hollow ratio of 10 to 65% and a fineness of 0.5 to 1.
A hollow short fiber having a length of 50 de and a fiber length in the range of 10 to 150 mm is treated with a monomer liquid containing a polymerization initiator, and after introducing the monomer liquid containing a polymerization initiator into the hollow portion, a solvent capable of dissolving the monomer is obtained. Or removing the monomer adhering to the surface of the short fiber by washing with the method described in (1) or after removing the monomer, polymerizing the monomer in the hollow portion. 2. The method according to claim 1, wherein the monomer liquid contains a function-imparting agent. 3. The method according to claim 1, wherein the solvent capable of dissolving the monomer is water. 4. The method for treating hollow short fibers according to claim 1, wherein the temperature of the solvent capable of dissolving the monomer is not lower than the polymerization initiation temperature of the monomer. 5. The method for treating hollow short fibers according to claim 1, wherein the solvent capable of dissolving the monomer contains a polymerization inhibitor. 6. The method according to claim 1, wherein the solvent capable of dissolving the monomer contains a soaping agent.