JP2007217855A - Ethylene-vinyl alcohol-based fiber having deodorizing property and antimicrobial property and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a modified ethylene-vinyl alcohol fiber having deodorizing property and antimicrobial property, having good washing durability, particularly solving deodorizing property and antimicrobial property, etc., in repeated washing at 60°C and further excellent in production stability. <P>SOLUTION: An ethylene-vinyl alcohol-based copolymer is melt-spun and fiberized and then, the fiber is impregnated into a water solution in which either one of titanium ion or copper ion exists or the titanium ion is mixed with the copper ion to form the fiber in which nano microparticles of titanium or copper exist through the interior of the fiber. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention comprises an ethylene-vinyl alcohol copolymer in which titanium fine particles or copper fine particles are dispersed in ethylene-vinyl alcohol and have practically durable performance such as deodorization and antibacterial properties. The present invention relates to a composite fiber comprising the ethylene-vinyl alcohol copolymer as a component, and a method for producing these fibers.

  As the heat-meltable fiber, a fiber made of polyester, polyamide, polyolefin, or the like is widely used. However, in the case of most general-purpose synthetic fibers obtained by melt spinning such as polyester fibers, polyamide fibers, polyolefin fibers, etc., antibacterial properties and antibacterial properties can be obtained by attaching a deodorant, antibacterial agent, etc. to the fiber surface. Although it is possible to impart odor, the attached antibacterial agent and deodorant are only physically present on the surface, and stagnation and washing of the fabric, especially at a high temperature of about 60 ° C. It is very difficult to make these antibacterial agents and deodorizers easily fall off by repeated washing, and to make the antibacterial properties and deodorizing properties durable.

  Further, as functional polymers, ethylene-vinyl alcohol fibers having excellent hygroscopicity due to having a hydroxyl group have been disclosed (Japanese Patent Laid-Open No. 5-51813), but in addition to these functionalities, deodorization and antibacterial properties are disclosed. In order to produce an ethylene-vinyl alcohol fiber for the purpose of a composite function with added functionality, it is desired to knead the functional substance into a polymer at the spinning stage. In practice, kneading is impossible due to the restriction of heat resistance during spinning and the like. For example, even if it becomes possible to perform spinning by using a thermal decomposition inhibitor / stabilizer, yarn breakage is severe during spinning, and the practicality is poor. Therefore, in reality, it is very difficult to complete a composite product having the functionality. The same applies to most general-purpose synthetic fibers obtained by melt spinning such as the above-described polyester fibers, polyamide fibers, and polyolefin fibers.

  The present invention solves the above-mentioned drawbacks. In particular, the object of the present invention is to provide a deodorant having good washing durability, especially even after repeated washing at about 60 ° C. It aims to prevent the antibacterial agent from falling off, and further provides an ethylene-vinyl alcohol fiber having deodorant and antibacterial properties excellent in production stability.

  As a result of intensive studies to obtain the above-described ethylene-vinyl alcohol fibers, the present inventors do not need specially expensive equipment for ethylene-vinyl alcohol copolymers (hereinafter abbreviated as EVOH). After the melt spinning, the EVOH is impregnated with an aqueous solution containing a single compound of titanium ion or copper ion or a mixture of the compounds in a normal manufacturing process by post-processing. It was found that titanium ions, copper ions, or both ions were mixed and bonded to each other, and as a result, it was possible to form titanium and copper nanoparticles, and the fibers thus obtained were highly advanced. It was found to be EVOH fiber that has excellent durability, deodorant properties, and antibacterial properties.

  Further, it has been found that in the treatment step for improving the hot water resistance by crosslinking the EVOH fibers described above, it is possible to simultaneously form titanium and copper nanoparticles at the same time as providing the hot water resistance.

That is, the present invention is an EVOH fiber comprising fine particles having an average particle diameter of 200 nm or less and having a melting point of 160 ° C. or higher and satisfying any of the following (1) to (3).
(1) The fine particles are made of titanium, and the content thereof is 0.1% by weight or more based on EVOH.
(2) The fine particles are made of copper, and the content thereof is 0.1% by weight or more based on EVOH;
(3) The fine particles are made of copper and titanium are mixed in the fiber, and the total content of the fine particles is 0.1% by weight or more with respect to EVOH;

Further, the present invention comprises EVOH containing fine particles having an average particle diameter of 200 nm or less and a melting point of 160 ° C. or higher and other thermoplastic polymers, and the EVOH occupies most of the fiber surface. EVOH type composite fiber satisfying any one of 1) to (3).
(1) The fine particles are made of titanium, and the content thereof is 0.1% by weight or more based on EVOH.
(2) The fine particles are made of copper and the content thereof is 0.1% by weight or more based on EVOH.
(3) The fine particles are made of copper and titanium are mixed in the fiber, and the total content of the fine particles is 0.1% by weight or more with respect to EVOH,

The present invention also relates to a yarn or fiber product containing the EVOH fiber or EVOH composite fiber.
Furthermore, the present invention provides an EVOH fiber or EVOH composite fiber characterized by treating a fiber comprising EVOH or a composite fiber comprising EVOH and another thermoplastic polymer with an aqueous solution of the following (A) or (B): Is the method.
(A) an aqueous solution containing a compound capable of coordinating titanium element or copper element to the hydroxyl group of EVOH, and an aqueous solution heated to 50 ° C. to 105 ° C. when the EVOH is non-crosslinked,
(B) An aqueous solution containing a compound having the property that a titanium element or a copper element can coordinately bond to the hydroxyl group of EVOH, and when the EVOH is crosslinked, an aqueous solution heated to 106 ° C to 140 ° C ,

  Further, the present invention provides a fiber comprising EVOH or a composite fiber comprising EVOH and another thermoplastic polymer, a titanium compound having a property that a titanium element can coordinately bond to a hydroxyl group of the EVOH, or a copper element to the hydroxyl group of the EVOH. Is an aqueous solution containing a copper compound having the property of being capable of coordinating and a compound capable of forming a crosslinked acetal bond at the hydroxyl group in the EVOH, the pH of which is 2.0 to 4.5, and 80 ° C. A process for producing EVOH fibers having deodorizing and antibacterial properties, characterized by treating with an aqueous solution heated to ˜140 ° C. to crosslink EVOH.

  In addition, the titanium fine particles and the copper fine particles referred to in the present invention are not only those made of titanium metal or copper metal, but also those made of titanium compounds or copper compounds that are unnecessary for water, or metals and compounds of these metals. In the mixed state, the substance is made of a substance that is substantially unnecessary for water.

That is, the present invention impregnates EVOH fibers in an aqueous solution containing titanium atoms or copper atoms and insolubilizes them to form nanoparticles formed from the atoms inside the fibers. It was found that EVOH fiber having both deodorant and antibacterial properties can be obtained. This utilizes the fact that EVOH fibers have a large number of hydroxyl groups and have a special property that hot water easily penetrates into the fibers.
In particular, when the above-described cross-linking acetalization and coordination bonding with a titanium atom or a copper atom are performed by the same treatment, the manufacturing process can be simplified.

  EVOH used in the present invention preferably has a repeating unit composed of ethylene of 25 to 70 mol%, and the remainder is preferably composed of a vinyl alcohol unit alone or a repeating unit of vinyl alcohol and other vinyl monomers. .

When the proportion of ethylene units in EVOH is less than 25 mol%, that is, the proportion of vinyl alcohol is more than 75 mol%, the spinnability at the time of fiberization becomes poor, and single yarn breakage or yarn breakage during spinning There will be more cuts and less flexibility.
When a high melting point polymer such as polyethylene terephthalate is used as the other thermoplastic polymer in a composite fiber composed of the above EVOH and another thermoplastic polymer, a spinning temperature of 250 ° C. or higher is usually used. However, in that case, if the proportion of the ethylene unit is less than 25 mol%, the heat resistance of EVOH becomes insufficient, and a good composite fiber cannot be obtained, which is inconvenient.

  On the other hand, when the proportion of ethylene units exceeds 70 mol%, the proportion of vinyl alcohol units, that is, hydroxyl groups, inevitably decreases, and is contained in the above-mentioned EVOH by a compound containing titanium, copper, or a cross-linking acetalizing agent. The amount of bonds to the hydroxyl group is reduced, and the desired deodorant and antibacterial heat-resistant fibers cannot be obtained. Preferably, the proportion of vinyl alcohol units in EVOH ranges from 30 mol% to 70 mol%, more preferably from 40 mol% to 60 mol%.

  Here, EVOH constituting the basic skeleton may be a chain that is not crosslinked, or may be crosslinked by an appropriate method. When not cross-linked, it is also possible to cause the titanium atom or the copper atom to exist together with the cross-linking agent, and to carry out the cross-linking and the coordination bond by the same treatment. Examples of the crosslinking agent herein include aldehyde compounds such as monoaldehyde and dialdehyde, but dialdehyde compounds are preferred from the viewpoint of crosslinking reaction between molecular chains. Of these, bisethylenedioxynonane, which is an acetalized product of 1,9-nonanedial and ethylene glycol, which is an alcohol component, is most preferable.

  When the crosslinking agent is introduced, the titanium-containing compound, the copper-containing compound, before the treatment with the mixture of the titanium-containing compound and the copper-containing compound or the like, or the crosslinking agent is used together with each of these compounds. It is more preferable in terms of simplification. In general, aldehyde substances are easily oxidized in the air. Therefore, in order to increase the stability during storage, the aldehyde group of the aldehyde compound is blocked with an alcoholic hydroxyl group and acetalized. Is preferred.

  A compound containing a sulfonic acid group salt may be added to the treatment bath as a crosslinking acetalization accelerator. Preferable examples of the compound include paratoluene sulfonate and dodecylbenzene sulfonate. The degree of crosslinking is preferably about 20 mol% in terms of improving hot water resistance.

  EVOH can be obtained by saponifying the vinyl acetate portion of the ethylene / vinyl acetate copolymer, and the degree of saponification is preferably about 95 mol% or more. When the degree of saponification is lowered, not only the crystallinity of the copolymer is lowered and physical properties such as strength are lowered, but also the copolymer is easily softened, trouble occurs in the fiberizing process, and the fiber obtained The texture becomes inferior, which is not preferable. More preferably, the saponification degree is 99 mol% or more and 100 mol% or less.

  As EVOH, it is usually preferable to use those having a number average molecular weight of 5000 to 25000, particularly 8000 to 20000. The number average molecular weight of EVOH here is a value measured by GPC method. EVOH is commercially available, for example, under the trade name Eval from Kuraray Co., Ltd. and under the trade name Soarnol from Nippon Synthetic Chemical Industry Co., Ltd., and is easily available. However, an ethylene / vinyl acetate copolymer may be produced from commercially available ethylene and vinyl acetate by radical polymerization or the like and saponified.

  In the present invention, the melting point of EVOH constituting the EVOH fiber is required to be 160 ° C. or higher. When the temperature is lower than 160 ° C., there arises a problem of softening and sticking in hot water at 100 ° C. Preferably it is the range of 165 degreeC-180 degreeC. The melting point of EVOH referred to in the present invention is that treated with a titanium compound, a copper compound, or a mixture of a titanium compound and a copper compound, or one in which a crosslink is introduced into EVOH and the nanoparticle material is contained. Mean melting point. In EVOH, in order to increase the melting point, the copolymerization ratio of vinyl acetate and the degree of saponification should be increased.

  In any case, when an alkali metal ion such as sodium ion or potassium ion or an alkaline earth metal ion such as calcium or magnesium is present in EVOH, main chain cleavage, side chain elimination, excessive crosslinking, etc. are present in EVOH. This causes a decrease in the thermal stability of EVOH, breakage during spinning due to gelation of EVOH, clogging of the spinning filter, a concomitant increase in the pressure of the spinning pack, and a shortening of the nozzle life. It is preferable to reduce the content as much as possible (usually 100 ppm or less, preferably 50 ppm or less).

  And in order to obtain the fiber of this invention, a textile product, etc., it is necessary to use the compound which has the property which can be coordinate-bonded by the hydroxyl group of EVOH, and either a titanium atom or a copper atom. Specifically, in the present invention, a titanium compound, a copper compound, a compound having both a titanium atom and a copper atom, or a mixture of both a titanium compound and a copper compound may be used. Further, two or more compounds may be used in combination as the titanium compound and the copper compound.

  In the present invention, the compound having the property that each of the titanium atom and the copper atom can be coordinated is a substance having solubility in water in the case of a compound containing a titanium atom. It means a compound having the property that a titanium atom can be coordinated to a hydroxyl group contained in EVOH, and preferred examples include titanium sulfate, titanium lactate, and diisopropoxytitanium bis (triethanolaminate). . In particular, those having very low hydrolyzability capable of withstanding the conditions in the aqueous solution under the heating conditions used in the present invention are preferable, and in this respect, titanium lactate is most preferable. What is marketed by Matsumoto Pharmaceutical Co., Ltd. by the brand name of ORGATICS TC-310 is mentioned.

  In the case of a compound containing copper element, similarly, a substance having high solubility in water is preferable. Specific examples of the compound include copper sulfate and copper nitrate. Among them, copper nitrate having particularly high solubility is used. More preferably, it is used.

  As the treatment temperature, when EVOH is in a non-crosslinked state, a temperature within a range of 50 ° C. to 105 ° C. is used. When the temperature exceeds 105 ° C., problems such as shrinkage, softening and sticking occur. On the other hand, when the temperature is lower than 50 ° C., satisfactory introduction of titanium particles, copper particles, mixed particles of titanium and copper, and the like cannot be obtained. Particularly preferably, it is 80 ° C. or higher from the viewpoint of easy formation of coordinate bonds of these atoms to the hydroxyl group in EVOH, and 100 ° C. from the viewpoint of suppression of shrinkage, softening and sticking of fibers made of EVOH. It is as follows. And more preferably, there is a suitable range for the rate of temperature rise until the processing temperature to be coordinated is reached, that is, in order to uniformly bond, it is preferable to start from a low temperature, more preferably In the case of starting from the range of 30 ° C. to 70 ° C., particularly in order to impart deodorant and antibacterial properties which are the object of the present invention with good reproducibility, it is particularly preferable to start from 40 ° C. or more and 50 ° C. or less. preferable. Further, the rate of temperature rise is preferably 1 ° C./min or less from the viewpoints of softening the fibers made of EVOH and suppressing sticking. The treatment time after reaching a predetermined temperature is preferably in the range of 30 to 90 minutes.

  On the other hand, when the EVOH fiber is subjected to the above crosslinking treatment (acetalization treatment) in advance, the treatment temperature is 106 ° C to 140 ° C. When the temperature exceeds 140 ° C., the fiber frequently shrinks. On the other hand, when the temperature is less than 106 ° C., it is difficult to introduce both titanium and copper into EVOH. In order to efficiently provide coordinate bonding and deodorant and antibacterial properties with good reproducibility, 110 ° C. or higher and 130 ° C. or lower are preferable. Also in this case, in order to bond uniformly, it is preferable to start from a low temperature first, more preferably from the range of 50 ° C. to 80 ° C., and the deodorization that is the object of the present invention with particularly good reproducibility. It is particularly preferable to start from 60 ° C. or higher and 75 ° C. or lower in order to impart properties and antibacterial properties. Further, the rate of temperature rise is preferably 2 ° C./min or less from the viewpoints of softening the fibers made of EVOH and suppressing sticking. The treatment time after reaching the predetermined temperature is preferably in the range of 30 to 90 minutes.

When the above-mentioned titanium or copper is introduced into the EVOH simultaneously with the crosslinking treatment (acetalization treatment) on the EVOH fiber, 1.8 to 4.5 is used as the PH range of the treatment bath. If it exceeds 4.5, the amount of cross-linked acetal bond decreases, and the hot water resistance of the resulting fiber is insufficient. On the other hand, when the pH is less than 1.8, it is difficult to coordinate bond the hydroxyl group of the element to EVOH.
As processing temperature, 80-140 degreeC is generally used. When the temperature exceeds 140 ° C., the fiber frequently shrinks. On the other hand, when the temperature is less than 80 ° C., it is difficult to introduce titanium or copper into EVOH. 90 ° C. or more and 120 ° C. or less are preferable in order to form a coordination bond efficiently, to provide deodorant and antibacterial properties with good reproducibility, and to have good hot water resistance. Also in this case, in order to bond uniformly, it is preferable to start from a low temperature first, more preferably from 50 ° C. to 80 ° C., and the deodorizing property which is the object of the present invention with particularly good reproducibility. In order to obtain EVOH fibers that impart antibacterial properties and have good hot water resistance, it is particularly preferable to start at 60 ° C. or higher and 75 ° C. or lower. The heating rate is preferably 2 ° C./min or less, more preferably 1 ° C./min, from the viewpoints of slow crosslinking with the hydroxyl group in the EVOH fiber and softening of the fiber and suppression of sticking. It is. The treatment time after reaching the predetermined temperature is preferably in the range of 30 to 90 minutes.

As the concentration of the above-mentioned treatment aqueous solution, in the case of containing either titanium or copper, it is preferably in an aqueous solution of 0.1% by mass or more and 5% by mass or less in terms of titanium / copper metal based on EVOH. If the treatment concentration is less than 0.1% by mass, EVOH fibers having satisfactory deodorant and antibacterial properties cannot be obtained. If it exceeds 5% by mass, physical adsorption only by the titanium or copper-containing compound is generated on the fiber surface, and the treated fiber becomes hard and the texture is deteriorated. In particular, a range of 0.3% by mass or more and 3% by mass or less is preferable from the reproducibility of effects on performance such as deodorant property and antibacterial property.
And when it contains what mixed titanium and copper, it is 0.1 mass% or more and 6 mass% or less in terms of the metal of titanium and copper by the total amount of both elements with respect to EVOH, You may use arbitrarily the combination of content.

  The treatment may be performed in a fiber state or after forming a false twisted yarn, a woven or knitted fabric, a nonwoven fabric or the like. Especially when processing in the form of yarn, the method of using a cheese dyeing machine in the form of a false twisted package that has been subjected to bulk processing is preferable because the processing liquid can easily penetrate into the cheese package and can be uniformly performed. It is.

As described above, titanium or copper coordinated to the hydroxyl group of EVOH can be insolubilized by a treatment such as reduction to form fine particles. Although the specific method is not particularly limited, for example, in the case of copper ions, copper sulfide nanoparticles can be formed by sulfidation reduction treatment. That is, following the copper ion impregnation treatment described above, by passing through a bath in which a compound containing sulfide ions having sulfidation reduction ability is dissolved, the coordination of EVOH and copper ions is removed, and thereby the copper sulfide nanoparticles are made into fibers. It can be formed even inside.
In addition, simply immersing EVOH fiber in warm water containing titanium ions and copper ions, titanium ions and copper ions are coordinated to the hydroxyl groups of EVOH, and titanium and copper are around the coordinated titanium and copper. Since it precipitates, it exists in the form of fine particles without performing the reduction treatment as described above. Therefore, in the present invention, processing such as reduction may be performed, or processing such as reduction may not be performed.

The EVOH fiber obtained by such treatment contains either titanium nanoparticles, copper nanoparticles, or coexistence of both titanium nanoparticles and copper nanoparticles. That is, titanium nanoparticles having an average particle diameter of 200 nm or less, copper nanoparticles having an average particle diameter of 200 nm or less, or both nanoparticles are finely dispersed inside the fiber.
In the present invention, the content of the titanium fine particles or the copper fine particles must be 0.1% by mass or more / EVOH, and the titanium fine particles and the copper fine particles exist in the EVOH. When it is, it is essential that the total content of the fine particles is 0.1% by mass or more / EVOH. When the content of the fine particles is less than 0.1% by mass, there arises a problem that performance such as deodorizing property and antibacterial property cannot be obtained satisfactorily. Preferably it is the range of 0.12-1.5 mass%. When titanium fine particles and copper fine particles are mixed, if the content of any fine particles is less than 0.05% by mass, high deodorant and antibacterial performances can be obtained satisfactorily. The problem that there is not. Preferably, in either case, the range is 0.12 to 3% by mass.

  On the other hand, when the average particle diameter exceeds 200 nm, there arises a problem that the dispersion is not uniform due to the aggregation of the fine particles, and the performance such as deodorization and antibacterial is not reproducible, and the performance varies. Preferably it is the range of 5-100 nm.

  In the case of a fiber with titanium particles or copper particles adhering only to the fiber surface, or inside the fiber, there are many large particles of 1 μm or more that can be confirmed visually or with a stereomicroscope level. When the average particle size as defined in the invention is hardly observed, the intended deodorizing performance, antibacterial performance and the like are not exhibited. In the fiber of the present invention, the presence form of fine particles can be confirmed for the first time by a transmission electron microscope (TEM). In addition, the average particle diameter as used in the field of this invention is the value measured with the high magnification photograph of TEM. A specific method will be described later.

  In the present invention, modification of EVOH fiber with a titanium-containing compound, a copper-containing compound, a mixture thereof, and the like is performed by manufacturing fibers from EVOH by melt spinning, and if necessary, false twisted yarn or fabric from these fibers. Then, they are treated in an aqueous solution state of the titanium-containing compound, copper-containing compound, mixed product of titanium-containing compound and copper-containing compound, or a crosslinking agent to EVOH is allowed to coexist. It is preferable to perform the treatment in the state of an aqueous solution in the specified pH range, and it is more preferable to add a very small amount of alcohol, for example, isopropyl alcohol, to the treatment liquid because it is easily denatured.

  When the fiber of the present invention is a composite fiber, it is desirable that the composite ratio of EVOH: other thermoplastic polymer is 10:90 to 90:10 in terms of polymerization ratio. Outside this range, the composite ratio becomes unbalanced and the spinnability tends to be poor. As the other thermoplastic polymer used for the composite fiber, it is preferable to use a crystalline thermoplastic polymer having a melting point of 150 ° C. or more from the viewpoint of heat resistance and dimensional stability, and a typical example thereof is fiber forming property. Polyester, polyamide, polyolefin, polyvinyl chloride, and the like. Particularly preferred is the case where the composite ratio of EVOH: other thermoplastic polymer is set in the range of 30:70 to 70:30 by weight, and polyester is used as the other thermoplastic polymer.

  Examples of the polyester include terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, phthalic acid, aliphatic dicarboxylic acid such as 5-sodiumsulfoisophthalic acid, aliphatic dicarboxylic acid such as adipic acid and sebacic acid, or these Synthesized from esters and diol compounds such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexane-1,4dimethanol, polyethylene glycol, polytetramethylene glycol A fiber-forming polyester can be used. Among them, a polyester in which 80 mol% or more, particularly 90 mol% or more of the structural units are composed of ethylene terephthalate units and / or butylene terephthalate units is preferable.

As the polyamide, nylon 4, nylon-6, nylon-66, nylon-12, nylon-610 and the like can be used.
Furthermore, polypropylene or ethylene / propylene copolymer can be used as the polyolefin.

As a composite form in the composite fiber, a core-sheath type, particularly a core-sheath type structure in which a core component has a large number of protrusions (for example, 10 or more protrusions), a sea-island type, a bonded type, a mixed type thereof, etc. Any form is mentioned. In the case of the core-sheath type, any of a two-layer core-sheath type including a protrusion shape of the core component and a multilayer core-sheath type having three or more layers may be used. In the case of the sea-island type, the shape, number, and dispersion state of the islands can be arbitrarily selected, and part of the islands may be exposed on the fiber surface. Furthermore, in the case of a bonding type, the bonding surface may be in a linear shape, an arc shape, or any other random curved shape in a fiber cross section perpendicular to the fiber length direction, The plurality of bonded portions may be parallel, radial, or any other shape. In any composite shape, it is necessary for the EVOH component to be exposed on the fiber surface for impregnation with titanium atoms or copper atoms, and it is preferable that EVOH covers 50% or more of the fiber surface, More preferably, EVOH covers the entire fiber surface. The most preferable case is a core-sheath type composite fiber in which EVOH is a sheath component and another thermoplastic resin is a core component.
In the conjugate fiber of the present invention, the other thermoplastic polymer to be complexed with EVOH may be one type or two or more types.

And the cross-sectional external shape of the fiber of this invention and a composite fiber may be what kind of thing, and can be made into a round shape or an unusual shape. In the case of an irregular cross section, for example, a flat shape, an oval shape, a square shape such as a triangle to an octagon, a multi-leaf shape such as a T shape, a V shape, a 3 to 8 leaf shape, and a hollow shape can be used. .
Furthermore, the fibers and composite fibers of the present invention are fluorescent whitening agents, stabilizers, flame retardants, colorants, other substances for enhancing deodorizing properties and antibacterial properties that are commonly used in fiber-forming polymers. Any additive such as can be contained as needed. The thickness of the single fiber of the present invention is preferably in the range of 0.1 to 5 dtex from the standpoint of yarn production.

  The fibers and yarns of the present invention include long fibers such as monofilaments, short fibers such as staples, multifilament yarns, spun yarns, blended yarns of fibers of the present invention and natural fibers, semi-synthetic fibers, and other synthetic fibers. Or a blended yarn, a twisted yarn or the like. The fiber of the present invention may be subjected to any treatment such as false twist crimping or entanglement treatment. Further, the textile product of the present invention may be any of textile products such as a knitted fabric, a nonwoven fabric, a final garment, and a towel made of those fibers and yarns.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, this invention is not limited to these Examples.

[Measurement of titanium and copper content in EVOH fiber]
It was determined by analysis such as fluorescent X-ray spectrum and atomic absorption.
[Measurement of average particle diameter of titanium and copper in EVOH fiber]
This was performed using a Hitachi H-800NA transmission electron microscope (TEM). 100 titanium fine particles and copper fine particles were arbitrarily selected from the photograph of the fiber cross section, their sizes were measured, and the average value was taken as the average particle size.

[Melting point of EVOH]
It measured on the following conditions with the differential scanning calorimeter (DSC), and read by the endothermic peak temperature.
Measurement conditions: The sample was allowed to stand at 30 ° C. for 3 minutes, and then heated to 220 ° C. at a rate of 10 ° C./min. When the sample was a composite fiber, the peak on the low temperature side was taken as the melting point of EVOH.
[Measurement of deodorization]
Deodorant component (gas): ammonia 40ppm, acetic acid 100ppm, formalin 40ppm
Adsorbability: Put 3.0 g of sample to be measured in a 5 L tetra bag, inject 3 L of measurement target gas adjusted to a predetermined concentration, measure the gas concentration after 2 hours with a detector tube, and obtain the residual ratio. The deodorizing property was evaluated in terms of size.

[Evaluation of antibacterial properties]
Based on JIS-L-1902, the bacteriostatic activity value of 2.2 or more was judged to be antibacterial by the bacterial solution absorption method using the test bacteria and Staphylococcus aureus.
[Deodorant and antibacterial washing durability]
In accordance with JIS-L-1072, the above deodorization and antibacterial properties were evaluated after repeated washing at 60 ° C. for 30 times (described as “after 30HL” in the table described below).

Examples 1-3 and Comparative Examples 1-5
Using methanol as a polymerization solvent and azobis-4-methyloxy-2,4-dimethylvaleronitrile as a polymerization initiator, radical polymerization of ethylene and vinyl acetate under pressure at 60 ° C. gave an ethylene content of 44 mol. % Ethylene / vinyl acetate random copolymer (number average degree of polymerization, about 350), and then the ethylene / vinyl acetate random copolymer (hereinafter referred to as “Et / VAc copolymer”) is methanol containing caustic soda. Saponification treatment was performed in the liquid to produce wet EVOH in which 99 mol% or more of vinyl acetate units in the copolymer were saponified. The EVOH was repeatedly washed with a large excess of pure water to which a small amount of acetic acid was added, and then further washed with a large excess of pure water to obtain alkali metal ions and alkaline earth metals in the copolymer. Each of the ion content was adjusted to about 10 ppm or less, and then water was separated from the copolymer by a dehydrator, and then sufficiently dried by vacuum drying at a temperature of 100 ° C. or less to obtain EVOH (in 85% hydrous phenol solvent, An intrinsic viscosity of 1.05 dl / g when measured at 30 ° C. was obtained.

  This polymer was used as a sheath component of a core / sheath type composite fiber. On the other hand, polyethylene terephthalate having intrinsic viscosity = 0.60 is used as a core component, and a sheath / core structure (composite ratio of sheath component to core component = 50/50 (volume ratio), cross-sectional shape of the core component by a biaxial extruder. Has 30 protrusions, and the fiber surface is 100% covered with a sheath component.) The melt is discharged from a circular spinning nozzle, and the length of 1. is set at a position 1.2 m below the spinneret. Introduced into a tube heater (inner wall temperature 200 ° C) with an inlet diameter of 8 mm and an inner diameter of 30 mmφ, oil was applied to the thread that came out of the tube heater with a crow opening oiling (gear pump oiling method), and two take-up rollers And a multifilament of 85 dtex / 24f was obtained. The obtained multifilaments were used to produce a 28-gauge tengu circular knitted fabric without any problem in spinnability.

  This circular knitted fabric is scoured at 80 ° C. for 20 minutes in a treatment bath having a concentration of 1 g / l of actinol R-100 (manufactured by Matsumoto Yushi Co., Ltd.) as a deoiling agent, and preset 150 ° C. for 1 minute. A dry heat treatment was performed. EVOH fibers constituting the obtained knitted fabric are not crosslinked. The knitted fabric was subjected to a heating treatment in an aqueous solution containing titanium lactate [trade name ORGATICS TC-310 (manufactured by Matsumoto Pharmaceutical Co., Ltd.)] which is a titanium-containing compound under the conditions shown in Table 1. The processing time at the processing temperature is 40 minutes. The aqueous solution of titanium lactate compound contains 40% (volume%) of isopropyl alcohol. The performance of the obtained circular knitted fabric is shown in Table 1.

  In the case of a treatment temperature outside the specified range of the present invention (Comparative Example 4.5), the initial deodorizing property, washing durability (Comparative Example 3) (deodorizing property, ammonia 55%, acetic acid 52%), etc. Became inferior. On the other hand, in the case of Examples 1 to 3, the deodorizing property after washing 30 times was excellent, such as 1.0% for the ammonia component and 3.5% for the acetic acid component. The average particle diameter of titanium in the fiber was 200 nm or less (Example 1: 10 nm, Example 2: 100 nm, Example 3: 150 nm) in the case of the examples. On the other hand, in Comparative Examples 2 to 5, all were 300 nm. And in the case of the Example, it confirmed with the electron microscope that these microparticles | fine-particles existed in the fiber.

Examples 4-6 and Comparative Examples 6-10
Using the same spinning yarn as in Example 1, an SZ false twisted yarn was obtained by a conventional method. The false twisting in this case was a belt false twist using a Murata machine Mach with a draw ratio of 1.06, a heater temperature of 120 ° C. in the first stage, 110 ° C. in the second stage, and a yarn speed of 500 m / min. The fineness was 87T / 24f. The cheese was subjected to a crosslinking treatment at the following bath composition, treatment temperature, time and the like. The degree of crosslinking of the EVOH fiber after crosslinking was 20 mol%.

<Bath composition for crosslinking treatment>
Cross-linking agent (bisethylenedioxynonane) Trade name: Meister TM21 14% omf (manufactured by Meisei Chemical Co., Ltd.)
Acetalization accelerator (main component sodium sodium dodecylbenzenesulfonate) Meister SA-2 0.6 g / l (manufactured by Meisei Chemical Co., Ltd.)
Catalyst Maleic acid 1g / l
Bath ratio 1:10 Treatment heating rate and time: Temperature was increased from 40 ° C. to 90 ° C. at 1 ° C./min.
Keeping treatment temperature and time: 90 ° C. × 40 minutes After the above treatment, washing with hot water at 100 ° C. for 20 minutes was performed, followed by oiling in a bath and drying. A knitted fabric was obtained in the same manner as in Example 1 using this crosslinked yarn.
The knitted fabric was heated with an aqueous solution of a titanium-containing compound under the conditions shown in Table 2. The processing time at the heating processing temperature is 40 minutes. The aqueous solution of titanium lactate compound contains iso 40% (volume%) isopropyl alcohol.
In the case of the examples, the average particle diameter of titanium in the fibers was 200 nm or less (Example 4: 50 nm, Example 5: 100 nm, Example 6: 30 nm). And in the case of the Example, it confirmed with the electron microscope that these microparticles | fine-particles existed in the fiber.

Examples 7-9 and Comparative Examples 11-15
The same spinning yarn as in Example 1 was used, and the same circular knitted fabric, deoiling, dry heat treatment and the like were performed. The EVOH fiber in this case is not subjected to crosslinking treatment. This knitted fabric was heated in the aqueous solution using copper nitrate trihydrate, which is a copper-containing compound, under the conditions shown in Table 3.

  In the case of a treatment temperature outside the scope of the present invention (Comparative Example 14.15), the initial deodorizing property, washing durability (Comparative Example 13) (deodorizing property, ammonia 60% acetic acid 55%), etc. It became. On the other hand, in Examples 7 to 9, the deodorizing property after repeated washing 30 times was excellent, such as 4.5% for the ammonia component and 6.0% for the acetic acid component. In addition, the average particle diameter of the copper in a fiber is 200 nm or less in the case of an Example (Example 7: 20 nm, Example 8: 150 nm, Example 9: 10 nm). On the other hand, in Comparative Examples 12 to 15, all were 300 nm. And in the case of the Example, it confirmed with the electron microscope that these microparticles | fine-particles existed in the fiber.

Examples 10-12 and Comparative Examples 16-20
The same cross-linking treatment as in Example 4 was performed, and knitted fabrics having the same specifications for EVOH fibers having the same cross-linking degree were subjected to the same scouring and dry heat treatment. This knitted fabric was subjected to a heating treatment with the aqueous solution using copper nitrate trihydrate which is a copper-containing compound under the conditions shown in Table 4. The processing time at the processing temperature is 40 minutes. In the case of the examples, the average particle diameter of the copper fine particles existing in the fiber is 200 nm or less in any of the examples (Example 10: 50 nm, Example 11: 110 nm, Example 12: 10 nm). Further, in these examples, it was confirmed with an electron microscope that copper fine particles were present in the fiber.

Examples 13 to 15 and Comparative Examples 21 to 26
The same spinning yarn as in Example 1 was used, and the same circular knitted fabric, deoiling, dry heat treatment and the like were performed. The EVOH fiber in this case is not subjected to crosslinking treatment. For each of the conditions shown in Table 5 for this knitted fabric, an aqueous solution containing a titanium-containing compound, trade name ORGATIXX TC-310 (manufactured by Matsumoto Pharmaceutical Co., Ltd.) and copper-containing compound copper nitrate trihydrate The mixture was heated with an aqueous solution.

In the case of the processing temperature outside the range of the present invention (Comparative Examples 25 and 26), and in the case of the contents of titanium and copper outside the range, the initial deodorizing property and washing durability (Comparative Examples 21, 23, 23) 24) (deodorant, formalin 90%, ammonia 65% acetic acid 58%) and the like. On the other hand, in Examples 13 to 15, the deodorizing property after repeated washing 30 times is excellent, such as 2.1% for the formalin component, 2.7% for the ammonia component, and 1.5% for the acetic acid component). The antibacterial bacteriostatic activity value was 2.2 or higher.
In addition, the average particle diameter of titanium and copper in the fiber is 200 nm or less in the case of Example (Example 13: Titanium 8 nm, Copper 10 nm, Example 14: Titanium 50 nm, Copper 40 nm, Example 15: Titanium 80, Copper 75 nm) Met. On the other hand, in the case of Comparative Examples 21 to 26, both titanium and copper were 300 nm or less. And in the case of the Example, it confirmed with the electron microscope that these microparticles | fine-particles existed in the fiber.

Examples 16-18 and Comparative Examples 27-32
The same cross-linking treatment as in Example 4 was performed, and knitted fabrics having the same specifications for EVOH fibers having the same degree of cross-linking were subjected to the same scouring and dry heat treatment. With respect to this knitted fabric under the conditions shown in Table 6, an aqueous solution containing a titanium-containing compound, trade name ORGATIXX TC-310 (manufactured by Matsumoto Pharmaceutical Co., Ltd.) and copper-containing compound copper nitrate trihydrate A heating treatment with the aqueous solution was carried out using. The processing time at each processing temperature is 40 minutes.

  In addition, the average particle diameter of titanium and copper in the fiber was 200 nm or less in the examples. And in the case of the Example, it confirmed with the electron microscope that these microparticles | fine-particles existed in the fiber.

Examples 19 to 25 and Comparative Examples 33 to 39
The same EVOH polymer as in Example 1 was used as the sheath component of the core / sheath type composite fiber. On the other hand, a polyethylene terephthalate polymer having an intrinsic viscosity = 0.62 is used as a core component, and a sheath / core structure (composite ratio of the sheath component and the core component = 50/50, the cross-sectional shape of the core component is projected by a biaxial extruder. Tube heater (inner wall temperature 200 ° C) with a length of 1.0m, inlet diameter 8mm, inner diameter 30mmφ installed at a position 1.2m below the spinneret. Is applied to the yarn coming out from the tube heater by a crow mouth oiling (gear pump oiling system) and wound up at a take-up speed of 3700 m / min via two take-up rollers to obtain a multifilament of 85 dtex / 24f. It was. There was no problem with spinnability.

  Using the above-mentioned spinning yarn, an SZ false twisted yarn was obtained by an ordinary method. The false twisting in this case was a belt false twist using a Murata machine Mach with a draw ratio of 1.06, a heater temperature of 120 ° C. in the first stage, 110 ° C. in the second stage, and a yarn speed of 500 m / min. The fineness was 87 dtex / 24f. This yarn was rolled up for a cheese dyeing machine, and the aqueous solution containing titanium-containing compound and trade name ORGATICS TC-310 were dissolved at the respective treatment temperatures shown in Table 7 in the bath composition shown below for the rolled cheese. The treatment was carried out under the pH of each treatment bath shown in Table 7 together with the composition and a composition solution containing a crosslinking agent shown in the following bath composition. The processing time is 40 minutes.

<Bath composition excluding titanium-containing compounds>
Cross-linking agent (bisethylenedioxynonane) Trade name: Meister TM21 14% omf (manufactured by Meisei Chemical Co., Ltd.)
Acetalization accelerator (main component: sodium sodium dodecylbenzenesulfonate) Meister SA-2 0.6 g / l
Catalyst (Acids) Adjusted to each PH value shown in Table 7 with sulfuric acid, maleic acid, acetic acid and the like.
Bath ratio 1:10
Treatment temperature increase rate and time: The temperature was increased from 40 ° C. to each treatment temperature shown in Table 7 at 1 ° C./min. Keeping time: 40 minutes After the above treatment, washing with hot water at 100 ° C. for 20 minutes was performed, followed by oiling in the bath and drying.
These treated yarns were made into the same knitted fabric as in Example 1, and scouring and presetting were performed as in Example 4.

  If the pH of the treatment bath outside the specified range of the present invention is less than 2.0 (Comparative Example 37), the initial deodorizing property (deodorizing property, ammonia component 70%, acetic acid component 65%) is inferior. When the pH is higher than 4.5 (Comparative Example 38), the melting point of EVOH is lower than 160 ° C, the fiber softens and sticks in 120 ° C hot water, the hot water resistance is poor, and the washing durability (dissipation) Odorous ammonia component 58%, acetic acid component 60%). And at the processing temperature outside the specified range (Comparative Examples 36 and 39), the initial deodorizing property (deodorizing property, ammonia component 65%, acetic acid component 73%) was inferior. On the other hand, in Examples 19 to 21, 23, and 24, the deodorizing property after 30 times of washing was excellent, such as 3.2% for the ammonia component and 4.5% for the acetic acid component. The average particle diameter of titanium in the fibers was 200 nm or less in the case of the examples. (Example 19: 8.5 nm, Example 20: 75 nm, Example 21: 145 nm). On the other hand, in the case of Comparative Examples 34 to 39, all were 300 nm. And in the case of the Example, it confirmed with the electron microscope that these microparticles | fine-particles existed in the fiber.

Examples 26 to 32 and Comparative Examples 40 to 45
Using the same spinning yarn as in Example 19, the same false twisting as in Example 4 was performed, and using the rolled cheese (for cheese dyeing), the bath composition shown below is shown in Table 8, respectively. The treatment is carried out under the pH of each treatment bath shown in Table 8 together with an aqueous solution in which copper nitrate trihydrate, which is a copper-containing compound, is dissolved at a treatment temperature and a solution containing a crosslinking agent shown in the following bath composition. went. The processing time is 40 minutes.

<Bath composition excluding copper-containing compound>
Cross-linking agent (bisethylenedioxynonane) Trade name: Meister TM21 14% omf (manufactured by Meisei Chemical Co., Ltd.)
Acetalization accelerator (main component sodium sodium dodecylbenzenesulfonate) Meister SA-2 0.6 g / l
Catalysts (Acids) Adjusted bath ratio to 10:10 with each pH by sulfuric acid, maleic acid, acetic acid, etc.
Process temperature increase rate and time: The temperature is increased from 40 ° C. to each process temperature shown in Table 8 at 1 ° C./min. Keeping time: 40 minutes After the above treatment, washing with hot water at 100 ° C. for 20 minutes was performed, followed by oiling in the bath and drying.
These treated yarns were made into the same knitted fabric as in Example 1, and scouring and presetting were performed as in Example 4.

  The obtained knitted fabric was evaluated for deodorizing property, antibacterial property, texture and the like. The results are shown in Table 8. As for the knitted fabrics of these examples, as a result of testing the deodorant property and antibacterial property after 30 times of washing, the formalin residual rate, the ammonia residual rate, and the acetic acid residual rate were slightly increased, and the performance decreased. It was in a state that can hardly be said. In the examples, the average particle diameter of titanium in the fibers was 200 nm or less. And in the case of the Example, it confirmed with the electron microscope that these microparticles | fine-particles existed in the fiber.

Examples 33 to 39 and Comparative Examples 46 to 51
Performing the same false twisting as in Example 4 using the same spinning yarn as in Example 19, and using the rolled cheese (for cheese dyeing machine) shown in Table 9 in the bath composition shown below, An aqueous solution containing a titanium-containing compound at each processing temperature, an aqueous solution obtained by mixing a trade name ORGATIXX TC-310 (manufactured by Matsumoto Pharmaceutical Co., Ltd.) and copper-containing compound copper nitrate / trihydrate, The heating treatment was performed under the pH of each treatment bath shown in Table 9 to which a composition solution containing the following crosslinking agent was added and at each treatment temperature. The processing time is 40 minutes.

<Bath composition excluding mixing of titanium-containing compound and copper-containing compound>
Cross-linking agent (bisethylenedioxynonane) Trade name: Meister TM21 14% omf (manufactured by Meisei Chemical Co., Ltd.)
Acetalization accelerator (main component sodium sodium dodecylbenzenesulfonate) Meister SA-2 0.6 g / l
Catalyst (Acids) Adjusted to each pH value shown in Table 9 with sulfuric acid, maleic acid, acetic acid and the like.
Bath ratio 1:10
Process heating rate and time: Temperature was increased from 40 ° C. to each processing temperature shown in Table 10 at 1 ° C./min. Keeping time: 40 minutes After the above treatment, washing with hot water at 100 ° C. for 20 minutes was performed, followed by oiling in the bath and drying.
These treated yarns were made into the same knitted fabric as in Example 1, and scouring and presetting were performed as in Example 4.

When the pH of the treatment bath outside the specified range of the present invention is less than 2.0 (Comparative Example 46), the initial deodorizing property (deodorizing property, ammonia component 68%, acetic acid component 78%, formalin component 78). %) And PH is greater than 4.5 (Comparative Example 47), the melting point of EVOH is less than 160 ° C, the fibers soften and stick in 100 ° C hot water, the hot water resistance is poor, and the laundry The durability was inferior (deodorant ammonia component 76%, acetic acid component 85%, formalin component 81%). When the temperature of the treatment bath is out of the range, when the temperature is lower than 80 ° C. (Comparative Example 48), the titanium content decreases to 0.05% by mass or less, and the initial deodorizing property (ammonia component 76%, acetic acid component 81). %, Formalin component 85%). When the temperature is higher than 140 ° C. (Comparative Example 49), the average particle size of titanium and copper greatly exceeds 200 nm (Comparative Example 49: 350 nm). Initial deodorization (ammonia component 74%, acetic acid component 83%, Formalin component 83%) is inferior. On the other hand, in the case of Examples 33 to 39, the deodorizing property after repeated washing 30 times is 1.5% to 3.0% for the ammonia component, 1.5% to 3.7% for the acetic acid component, The formalin component was excellent at 0.8% to 3.2%) and the like, and the antibacterial bacteriostatic activity value was at least 2.2. In these examples, the average particle diameters of titanium, copper, etc. in the fibers were 200 nm or less (for example, Example 33: Titanium 17 nm, Copper 23 nm, Example 37: Titanium 8 nm, Copper 19 nm, Example 38: titanium 113 nm, copper 105 nm). And in the case of the Example, it confirmed with the electron microscope that these microparticles | fine-particles existed in the fiber.

Claims (5)

An ethylene-vinyl alcohol copolymer comprising fine particles having an average particle diameter of 200 nm or less and having an melting point of 160 ° C. or more and satisfying any of the following (1) to (3): Polymer fiber.
(1) The fine particles are made of titanium, and the content thereof is 0.1% by weight or more based on the ethylene-vinyl alcohol copolymer,
(2) The fine particles are made of copper, and the content thereof is 0.1% by weight or more based on the ethylene-vinyl alcohol copolymer,
(3) The fine particles are made of copper and titanium are mixed in the fiber, and the total content of the fine particles is 0.1% by weight or more based on the ethylene-vinyl alcohol copolymer. , It consists of an ethylene-vinyl alcohol copolymer having a mean particle size of 200 nm or less and a melting point of 160 ° C. or more and another thermoplastic polymer, and the ethylene-vinyl alcohol copolymer is formed on the fiber surface. An ethylene-vinyl alcohol copolymer composite fiber that occupies the majority and further satisfies any of the following (1) to (3).
(1) The fine particles are made of titanium, and the content thereof is 0.1% by weight or more based on the ethylene-vinyl alcohol copolymer,
(2) The fine particles are made of copper, and the content thereof is 0.1% by weight or more based on the ethylene-vinyl alcohol copolymer,
(3) The fine particles are made of copper and titanium are mixed in the fiber, and the total content of the fine particles is 0.1% by weight or more based on the ethylene-vinyl alcohol copolymer. ,   A yarn or fiber product containing the fiber according to claim 1 or 2. The fiber comprising an ethylene-vinyl alcohol copolymer or a composite fiber comprising an ethylene-vinyl alcohol copolymer and another thermoplastic polymer is treated with an aqueous solution of the following (1) or (2). A method for producing an ethylene-vinyl alcohol copolymer fiber or an ethylene-vinyl alcohol copolymer composite fiber.
(1) An aqueous solution containing a compound having a property that a titanium element or a copper element can coordinately bond to a hydroxyl group of an ethylene-vinyl alcohol copolymer, and the ethylene-vinyl alcohol copolymer is non-crosslinked In the case of an aqueous solution heated to 50 ° C. to 105 ° C.,
(2) An aqueous solution containing a compound having a property that a titanium element or a copper element can coordinately bond to a hydroxyl group of an ethylene-vinyl alcohol copolymer, and the ethylene-vinyl alcohol copolymer is crosslinked. In the case of an aqueous solution heated to 106-140 ° C., A fiber made of an ethylene-vinyl alcohol copolymer or a composite fiber made of an ethylene-vinyl alcohol copolymer and another thermoplastic polymer is mixed with a titanium element at the hydroxyl group in the ethylene-vinyl alcohol copolymer. A titanium compound having the property of being capable of coordinate bonding or a copper compound having the property of being capable of coordinating copper element to the hydroxyl group, and a compound capable of forming a crosslinked acetal bond at the hydroxyl group in the ethylene-vinyl alcohol copolymer A cross-linking treatment of the ethylene-vinyl alcohol copolymer by treatment with an aqueous solution containing PH of 2.0 to 4.5 and heated to 80 ° C. to 140 ° C. A method for producing an ethylene-vinyl alcohol fiber, which is characterized.