JPH0625911A - Modified ethylene-vinyl alcohol-based copolymer yarn - Google Patents

Abstract

(57) [Summary] [Structure] The basic skeleton is composed of an ethylene-vinyl alcohol copolymer, and the alcoholic hydroxyl group in the copolymer is represented by the following formula (I); (In the formula, M is a metal atom capable of forming a chelate, R is an alkyl group, and X ₁ , X ₂ , X ₃ and X ₄ are groups selected from a halogen atom and a hydroxyl group, which may be the same or different. Fibers comprising an ethylene-vinyl alcohol copolymer modified with at least one compound represented by the formula (1), a composite fiber, a textile product such as a cloth, and a production method thereof. [Effect] It has very good hot water resistance and does not cause sticking, adhesion, shrinkage, etc. even if it is dyed or treated with hot water such as steam ironing. It is possible to obtain a product having an extremely high commercial value, which has a good texture, gloss, and appearance similar to those of fibers and has a deep deep shade.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a modified ethylene-vinyl alcohol-based copolymer excellent in hot water resistance which does not cause sticking or adhesion due to the ethylene-vinyl alcohol-based copolymer when treated with hot water. The present invention relates to fibrous products such as the following fibers, yarns and cloths, a method for producing the same, and a method for producing the dyed product. More specifically, the present invention is to improve hot water resistance by modifying ethylene-vinyl alcohol copolymer fiber, yarn or a fiber product made of the same with a specific chelate compound. According to the method of the present invention, the chelate compound can be rapidly diffused and permeated into the fiber, and further, the shrinkage and deterioration at the time of dyeing are prevented,
It is possible to obtain a dyed product having good gloss, texture, and appearance.

[0002]

2. Description of the Related Art Synthetic fibers made of polyester or polyamide are widely used as synthetic fibers. A cloth made of such synthetic fibers is more hydrophilic than a cloth made of natural fibers such as cotton and hemp. It is inferior in antifouling property, antistatic property, etc., and has a feeling that the texture is monotonous and glossy and has a cold feeling. Further, when dyed, there are drawbacks in that the color tone is inferior in sharpness as compared with natural fibers such as wool and silk, and it is difficult to obtain depth of color.

Fibers made of ethylene-vinyl alcohol-based copolymers have been developed to cover such drawbacks of conventional synthetic fibers. Ethylene-vinyl alcohol copolymer fibers have a hydroxyl group in the molecule and thus have the advantages that hydrophilicity, antifouling property, antistatic property, dyeability, etc. are superior to polyester fibers and polyamide fibers. is doing.

However, since the ethylene-vinyl alcohol copolymer fiber has a low melting point and a low softening point, it is inferior in heat resistance and hot water resistance, and is particularly vulnerable to a treatment using hot water or steam at a high temperature. For example, a cloth made of ethylene-vinyl alcohol-based copolymer fiber is used.
When dyed at a temperature of 0 ° C or higher, or when a steam iron is used for sewing press or ordinary ironing, the ethylene-vinyl alcohol copolymer is softened or glued to make the fabric feel hard. In addition, there is a drawback that the appearance is deteriorated.

In order to improve the above-mentioned drawbacks of the ethylene-vinyl alcohol copolymer fiber, the ethylene-vinyl alcohol copolymer is a polyester having a heat resistance higher than that of the ethylene-vinyl alcohol copolymer, It has been proposed to manufacture a composite fiber by compounding with another thermoplastic resin such as polyamide or polypropylene (Japanese Patent Publication No. Sho 5).
6-5846, Japanese Patent Publication No. 55-1327, etc.). However, also in this case, when treated with a high-temperature dyeing bath or a high-temperature steam iron, the ethylene-vinyl alcohol-based copolymer exposed on the surface of the composite fiber is partially softened or stuck, and the wind It causes deterioration of quality, such as a hardened joint, a loss of gloss, and a deteriorated appearance.

In order to dye a fabric made of a composite fiber containing an ethylene-vinyl alcohol copolymer component without causing the above problems, the dyeing temperature is set to soften the ethylene-vinyl alcohol copolymer. It is necessary to maintain a low temperature of 90 ° C or lower that does not cause sticking or sticking, but other thermoplastic resins such as polyester and polyamide used for the composite are 90 ° C.
If the temperature is lower than 0 ° C, dyeing is not sufficiently performed, uneven dyeing occurs on the composite fiber, and a good dyed product cannot be obtained.

[0007]

The object of the present invention is to prevent the ethylene-vinyl alcohol-based copolymer fibers from sticking or adhering even when they are subjected to high-temperature dyeing or high-temperature steam ironing, and the resulting texture. Curing, deterioration of appearance, no loss of gloss, etc., excellent heat and water stability, swelling, firmness, fiber made of ethylene-vinyl alcohol copolymer capable of maintaining good texture with elasticity, It is an object of the present invention to provide a fiber product such as a composite fiber, a yarn and a cloth made of the same. Further, an object of the present invention is to provide a dyed product of a fiber or a fiber product of an ethylene-vinyl alcohol copolymer dyed in a clear and deep good color while maintaining such good quality. Is. Further, the present invention is to provide a method capable of rapidly and continuously producing a fiber, a fiber product or a dyed product comprising the ethylene-vinyl alcohol-based copolymer having the above excellent properties.

[0008]

[Means for Solving the Problems] The present inventors have continued research to solve the above problems. As a result, when a fiber or yarn or a fiber product made of an ethylene-vinyl alcohol copolymer is subjected to a modification treatment with a specific chelate compound, the hot water resistance of the ethylene-vinyl alcohol copolymer is improved and the above-mentioned problems are caused. I found that can be solved.

Furthermore, the inventors of the present invention, when the modification treatment with the chelate compound is carried out in combination with a neutralizing agent and / or a specific auxiliary agent, the diffusion and penetration of the chelate compound into the fiber are promoted, It has been found that the treatment can be carried out quickly and continuous operation is possible. Furthermore, when the present inventors dye the modified ethylene-vinyl alcohol-based copolymer fibers, yarns, and fiber products thus obtained using a specific dyeing bath, they will not feel hard and It has been found that a good dyed product which has no loss of gloss, swelling, flexibility, firmness, stiffness, etc., and has a clear and deep color can be obtained.

That is, in the present invention, the basic skeleton is made of an ethylene-vinyl alcohol copolymer, and the alcoholic hydroxyl group in the copolymer is represented by the following formula (I);

[0011]

[Chemical 4] (In the formula, M is a metal atom capable of forming a chelate, R is an alkyl group, and X ₁ , X ₂ , X ₃ and X ₄ are groups selected from a halogen atom and a hydroxyl group, which may be the same or different. The modified fiber is composed of a modified ethylene-vinyl alcohol-based copolymer, which is modified with at least one compound represented by

Further, the present invention is a composite fiber comprising the above-mentioned modified ethylene-vinyl alcohol copolymer and another thermoplastic polymer, and a yarn and a fiber product containing at least one of the fiber and the composite fiber as a constituent component. Includes.

The present invention provides a fiber of an ethylene-vinyl alcohol copolymer, a conjugate fiber, or a yarn and a fiber product containing at least one of the fibers as a constituent component, represented by the above formula (I). Fiber treated with a treating agent containing at least one of the compounds described above, and then heat-treated at a temperature lower than the melting point of the ethylene-vinyl alcohol copolymer to form a fiber or composite fiber composed of the modified ethylene-vinyl alcohol copolymer. , A method of manufacturing yarns and textiles.

In the present invention, the modification treatment with the compound represented by the above formula (I) is further performed, and (a) a neutralizing agent and / or (b) glycerin, ethylene glycol, polyethylene glycol and isopropyl alcohol The method includes adding at least one hydroxyl group-containing compound to the treatment agent.

Further, according to the present invention, before the above-mentioned treatment, the fiber, the composite fiber, the yarn and the fiber made of the ethylene-vinyl alcohol copolymer at a high temperature lower than the melting point of the ethylene-vinyl alcohol copolymer. Including heat treating the product.

In the present invention, after the modification treatment with the compound represented by the above formula (I), it is further dyed in a dyeing bath containing boric acid or a salt of boric acid and a strong acid / strong base. Methods of making modified and dyed fibers, bicomponent fibers, yarns and textiles are included.

Ethylene which is the basic skeleton of the fiber of the present invention
The vinyl alcohol-based copolymer (hereinafter referred to as “Et / VA-based copolymer”) has a repeating unit ratio of ethylene of 30 to 70 mol%, with the balance being vinyl alcohol alone or vinyl alcohol and other vinyl. Those composed of repeating units of a system monomer are preferable.

The proportion of ethylene units in the copolymer is 3
When it is less than 0 mol%, that is, when the proportion of vinyl alcohol units is more than 70 mol%, the spinnability at the time of fiber formation becomes poor, and the number of single yarn breaks and yarn breaks during spinning or drawing increases, Moreover, it becomes inflexible. Also, E
In a conjugate fiber composed of a t / VA-based copolymer and another thermoplastic polymer, when a high melting point polymer such as polyethylene terephthalate is used as the other thermoplastic polymer, high spinning of usually 250 ° C. or higher is performed. Although temperature is used, if the proportion of ethylene units is less than 30 mol% in that case, the heat resistance of the Et / VA copolymer becomes insufficient, and good composite fibers cannot be obtained, which is disadvantageous.

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 the hydrophilicity of the fibers is lowered, so that a natural fiber-like feel cannot be obtained. . At the same time, the compound represented by the above formula (I) [hereinafter referred to as "chelate compound (I)"
That is, the ratio of modification due to [1] is reduced, and it becomes impossible to obtain a desired fiber or fiber product having excellent hot water resistance and a swelling and good texture. From the standpoint of obtaining fibers having hot water resistance and a good texture with swelling, Et
The proportion of vinyl alcohol units in the / VA copolymer is particularly preferably 40 to 70 mol%.

Here, the Et / VA copolymer forming the basic skeleton may be a chain which is not crosslinked or may be crosslinked by an appropriate method.
When crosslinked, monoaldehyde as a crosslinking agent,
Although dialdehyde, diamine, etc. can be mentioned, 1,9-nonanedial which is a dialdehyde is preferable from the viewpoint of crosslinking reactivity. The cross-linking agent is preferably added to the reaction system from the viewpoint of production efficiency when the chelate compound (I) is added. This Et / VA copolymer can be obtained by saponifying the vinyl acetate portion of an ethylene / vinyl acetate copolymer, and the saponification degree in that case is about 95%.
It should be above. When the degree of saponification is low, not only the crystallinity of the copolymer is lowered and physical properties such as strength are lowered,
It is not preferable because the copolymer is apt to be softened, a trouble occurs in the fiberizing process, and the obtained fiber has a poor texture.

The Et / VA copolymer usually has a number average molecular weight of 5,000 to 25,000, particularly 8,000 to 2
It is better to use the one of 0000. Et / VA copolymer are, for example, Ltd. under the trade name EVAL ^R from Kuraray and Nippon Synthetic Chemical Industry Co., Ltd. is commercially available under the trade name Soarnol ^R from readily available. However, a commercially available copolymer of ethylene and vinyl acetate is purchased and saponified, or an ethylene / vinyl acetate copolymer is produced from ethylene and vinyl acetate by radical polymerization or the like and saponified and used. You may.

In any case, if the Et / VA copolymer contains alkali metal ions such as sodium ions and potassium ions or alkaline earth metal ions such as calcium and magnesium, the main chain is cleaved in the copolymer. , Side chain desorption, excessive cross-linking, etc., reduce the thermal stability of the copolymer, breakage of the fiber during spinning due to gelation of the copolymer, clogging of the spinning filter, and accompanying spin pack pressure. Since it causes a sudden rise and a shortening of the nozzle life, it is preferable to minimize the content of these ions (usually about 100 ppm or less, preferably 50 ppm or less).

In the fiber, yarn and fiber product of the present invention, the alcoholic hydroxyl group in the Et / VA copolymer must be modified with at least one of the chelate compounds (I). Et / VA copolymer has 1
It may be modified with only one kind of chelate compound (I) or may be modified with two or more kinds of chelate compound (I).

In the chelate compound (I), the alkyl group represented by the group R is preferably an alkyl group having 5 to 20 carbon atoms, particularly preferably a pentyl group or a stearyl group. In addition, a metal atom M having a chelate-forming ability
Examples of the metal atom include chromium, iron, zirconium, cobalt, nickel, titanium, aluminum, tin, and the like. In the case of chromium, the chelate compound (I) has excellent stability, and in the case of aluminum, Is suitable for a fiber dyed in a light color because the resulting fiber has almost no coloring. Of course, even when the metal atom is chromium, it can be dyed in a light color, but it is slightly inferior to aluminum in that it causes coloring unique to chromium.

Further, X ₁ , X ₂ , X ₃ and X ₄ are groups selected from a halogen atom and a hydroxyl group, and they may be the same or different from each other. Therefore, in the chelate compound (I), when all of X _{1 to} X ₄ are the same halogen atom, when they are two or more kinds of halogen atoms, _{1 to 3} of X _{1 to} X ₄ are optional. Of the halogen atoms of X and the rest of them are hydroxyl groups, X ₁
There is a case where all of to X ₄ are hydroxyl groups, and any of them may be used. When all or some of X _{1 to} X ₄ are halogen atoms, they are selected from chlorine, iodine, bromine or fluorine, and chlorine is particularly preferable. Specific preferred examples of the chelate compound (I) include the following formula (Ia);

[0026]

[Chemical 5] A compound represented by [hereinafter referred to as "compound (Ia)"] or the following formula (Ib);

[0027]

[Chemical 6] The compound represented by the following [hereinafter referred to as “compound (Ib)”] can be mentioned, and among these compounds, the compound (Ia)
On the other hand, it is available as "Zebran CR-N" (trade name) manufactured by Yatsusha Oil and Fats.

Although the reaction mechanism in the case where the Et / VA type copolymer fiber is modified with the chelate compound (I) is not clear, for example, when X _{1 to} X ₄ are chlorine, a dehydrochlorination reaction occurs. A bond is formed between the alcoholic hydroxyl group in the Et / VA copolymer and at least one of the four chlorine atoms bonded to the metal atom in the chelate compound (I), and the alcohol Via the oxygen atom of the hydroxyl group
Formula (II) below;

[0029]

[Chemical 7] It is judged that the Et / VA copolymer is modified by the group represented by the formula (wherein R and M are the same as above, and ~ represents the remaining bond).

In the group represented by the above formula (II), the remaining bonds (1) to (4) are bonded to another alcoholic hydroxyl group in the Et / VA copolymer through an oxygen atom, When it is a hydroxyl group, it may be bound to any one of the other bonding hands of the chelate compound (I) adjacent to it to form a chelate compound (I) polymer, or may be a mixture thereof. To be In either case,
The chelate compound (I) is chemically bonded to the Et / VA-based copolymer and is strongly bound and contained in the Et / VA-based copolymer, so that the Et / VA-based copolymer can be treated even after washing or dyeing. Does not easily leave the polymer. And chelate compound (I)
Is bonded to the alcoholic hydroxyl group in the Et / VA copolymer and at the same time forms a polymer of the chelate compound (I) by the remaining bond, the fiber of the Et / VA copolymer is obtained. A film of the chelate compound (I) is formed on the surface of the.

The modification ratio of the Et / VA copolymer fiber with the chelate compound (I) is 0.02 to 2.0 mol% based on the number of moles of vinyl alcohol units in the copolymer. Good, and particularly preferably 0.1 to 1.0 mol%. The number of moles of vinyl alcohol unit as used herein means a saponified vinyl alcohol unit, an unsaponified vinyl acetate unit, and a vinyl alcohol unit having a hydroxyl group such as an acetal group when it becomes an ether group or the like. Is the total number of moles of.

The rate of modification with the chelate compound (I) is 0.
If it is less than 02 mol%, good hot water resistance cannot be imparted to the fiber composed of the Et / VA copolymer, and, for example, when the temperature at the time of dyeing is 95 ° C. or higher, the fiber shrinks or sticks. Becomes large, and it is difficult to obtain a good texture, gloss, and appearance. On the other hand, when the modification ratio by the chelate compound (I) exceeds 2.0 mol%, the fiber made of the Et / VA copolymer becomes coarse and hard, and the dyeability is deteriorated to deteriorate the texture and appearance.

The modification with the chelate compound (I) is carried out by Et /
A fiber or a composite fiber is produced from a VA-based copolymer by melt spinning, and a fiber product such as a yarn or a fabric is further formed from these fibers, if necessary, or commercially available Et /
It is carried out by using VA type copolymer fibers, yarns, fiber products and the like and treating them with a treating agent containing the chelate compound (I). Usually, the treating agent is preferably in the form of an aqueous solution, an alcohol solution, an emulsion or the like, and when used as an aqueous solution, the concentration of the chelate compound (I) is about 0.3-.
It is preferable to set it in the range of 3% from the viewpoint of feeling and appearance.

In that case, the chelating compound is contained in the treating agent.
In the case of producing hydrochloric acid or the like by the reaction of (I) or the chelate compound (I) with water, in order to neutralize it or prevent corrosion of the metal processing container by the produced hydrochloric acid. The inclusion of a neutralizing agent is desirable because it increases the stability of the treating agent. Examples of the neutralizing agent include hexamethylenetetramine, sodium hydroxide, sodium carbonate and the like, and hexamethylenetetramine is preferable from the viewpoint of heating stability. The amount of the neutralizing agent used is preferably 2 to 10% by weight, particularly 4 to 6% by weight based on the weight of the chelate compound (I).

The treatment operation for modifying the fiber, composite fiber, yarn or fiber product comprising the Et / VA copolymer with the chelate compound (I) is not limited, and the modification of the Et / VA copolymer is not limited. Any method can be used as long as it can be performed smoothly. Among them, the pad mangle squeezing method is preferably used. In the case of this method, a fiber, a composite fiber, a yarn or a fiber product made of an Et / VA copolymer is treated with a treatment agent containing a chelate compound (I) (treatment). Bath /) at a temperature of 40 ° C or lower for a predetermined time while being immersed in Et /
When the VA-based copolymer is swollen to uniformly disperse the treatment agent in the fiber, and then the pad mangle drawing method is performed, a swelling feeling can be given.

At the time of the above dipping treatment at a temperature of 40 ° C. or lower, at least one hydroxyl group-containing compound selected from glycerin, ethylene glycol, polyethylene glycol and isopropyl alcohol is added to the chelating compound (I) in the treatment bath in an amount of 10%. If added in an amount of less than or equal to wt%, E
The swelling of the t / VA-based copolymer and the diffusion / permeation of the chelate compound (I) into the Et / VA-based copolymer can be promoted, and as a result, the processing time can be shortened and the chelate compound can be obtained.
The modification ratio due to (I) can be improved, and good fibers and fiber products having a bulging feeling can be obtained in a short time. Use ratio of the above hydroxyl group-containing compound is 10% by weight
If it exceeds, the hot water resistance of the obtained fiber or fiber product is decreased, which is not preferable.

E modified with chelate compound (I)
The fiber, the conjugate fiber, the yarn and the fiber product made of the t / VA copolymer are then usually dried at a temperature of 100 ° C. or lower to evaporate water and the like. Next, at 100 ° C or higher and Et /
The heat treatment is performed at a temperature lower than the melting point of the VA-based copolymer to complete the modification treatment.

In the present invention, the chelate compound is added to the Et / VA copolymer fiber, the composite fiber, the yarn or the fiber product.
After imparting (I), at a high temperature lower than the melting point of the Et / VA copolymer, preferably at a temperature of 100 ° C. or higher and 5 to 10 ° C. lower than the melting point of the Et / VA copolymer. Modification is performed by further heat treatment. If the heat treatment temperature is less than 100 ° C, the crosslinking reaction is insufficient. Also,
It is preferable to perform heat treatment (pre-heat treatment) before applying the chelate compound (I) because the heat resistance thereof is further improved. The heat treatment and the pre-heat treatment can be performed by dry heat treatment (infrared heating, hot air heating that does not include moisture, etc.), heating steam treatment, high-pressure steamer treatment, high-frequency heating in the presence of steam, etc. It is desirable from the viewpoint that the effect of improving hot water resistance and the reactivity between the chelate compound (I) and the Et / VA copolymer can be maintained well.

When heat treatment is applied to the fibers, composite fibers, yarns and cloths made of the Et / VA type copolymer, if they are carried out without tension, the appearance of crimps in the fibers and the yarns and the cloths are formed. Bulking of the constituent yarns can be brought about, and the woven wave can be increased to give a bulged product.

Further, the chelate compound (I) is applied, and then the fiber product of the present invention, such as the fiber of the present invention, the composite fiber and the cloth, which has been modified by heat treatment at a high temperature, and further under a high temperature before modification is carried out. As described above, the fiber product of the present invention that has been heat-treated at, the fiber product such as the composite fiber and the cloth has excellent hot water resistance and can withstand the dyeing treatment under high temperature.
When dyeing them, if a dyeing bath containing boric acid or a salt of strong acid / strong base and boric acid is used, the bath temperature is 9
Even if dyeing is performed using a dyeing bath at 5 ° C or higher, Et / V
No sticking, shrinkage, deterioration, etc. of the A-type copolymer fiber occur, dyeing of the dye becomes extremely good, and a dyed product with good texture, color tone and appearance can be obtained.

At this time, when only boric acid is added to the dyeing bath, the concentration of boric acid is preferably 2 g / liter or more.
It is more preferably g / liter or more. When both boric acid and a salt of strong acid / strong base are added, it is preferable that the concentration of boric acid is 1 g / liter or more and the concentration of the salt of strong acid / strong base is 1 g / liter or more. If the concentration is lower than the above, E
When the t / VA-based copolymer fiber is dyed at a temperature of 110 ° C. or higher at a high temperature and a high pressure, the fiber is likely to cause sticking, shrinkage, deterioration and the like. Examples of the strong acid / strong base salt used in combination with boric acid include sodium sulfate, potassium sulfate, sodium chloride, potassium chloride and the like, and sodium sulfate is preferable.

The dyeing method using the above dyeing bath is Et /
It is particularly effective for a composite fiber composed of a VA-based copolymer and another thermoplastic resin such as polyester that requires high temperature dyeing. For example, a high dyeing temperature is adopted for ordinary polyester single fibers, and even in the case of a composite fiber composed of an Et / VA copolymer and polyester, in order to perform good dyeing on the polyester side, Temperature 11
It is said that the temperature should be 0 ° C or higher, preferably 120 ° C or higher.

The composite fiber of the present invention composed of the Et / VA copolymer and polyester, which has been modified with the chelate compound (I) and subjected to the above-mentioned high temperature heat treatment, or a cloth made of the same, is treated with boric acid or boric acid and a strong acid. By dyeing at a high temperature of 110 ° C or higher using a dyeing bath containing a salt of a strong base, dyeing of Et / VA-based copolymer and polyester is very good and a clear color tone is obtained. Since it does not cause sticking, shrinkage, deterioration, etc. at the Et / VA-based copolymer portion constituting the conjugate fiber, the whitening phenomenon, curing, etc. at the time of dyeing disappears, and the gloss, texture and appearance It is possible to obtain a good dyed product.

When the fiber of the present invention is a composite fiber, the composite ratio of modified Et / VA copolymer: other thermoplastic polymer is 10:90 to 90:10 by weight. Is desirable. If it is out of this range, the composite ratio becomes unbalanced and the spinnability is likely 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 higher from the viewpoint of heat resistance and dimensional stability. Polyester, polyamide, polyolefin, polyvinyl chloride and the like can be mentioned.

As the polyester, terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, phthalic acid, α, β- (4-carboxyphenoxy) ethane, 4,
Aromatic dicarboxylic acids such as 4'-dicarboxydiphenyl, 5-sodium sulfoisophthalic acid, adipic acid,
Aliphatic dicarboxylic acids such as sebacic acid or their esters, and ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanedio-
Le, neopentyl glycol, cyclohexane-1,4
-A fiber-forming polyester synthesized from a diol compound such as dimethanol, polyethylene glycol or polytetramethylene glycol may be used, and 80 mol% or more, particularly 90 mol% or more of the constituent units are ethylene terephthalate units. Polyesters consisting of and / or butylene terephthalate units are preferred. As the polyamide, nylon 4, nylon 6, nylon 66, nylon 12 or the like can be used, and as the polyolefin, polypropylene, ethylene / propylene copolymer or the like can be used.

The composite form of the composite fiber can be any form such as a core-sheath type, a sea-island type, a laminating type, and a mixed type thereof. In the case of the core-sheath type, either a two-layer core-sheath type or 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 some of the islands may be exposed on the fiber surface. Furthermore, in the case of the bonding type, in the fiber cross section perpendicular to the length direction of the fiber, the bonding surface may be in a linear shape, an arc shape or any other randomly curved shape, and The plurality of bonded portions may be parallel to each other, may be radial, or may have any other shape.

In the conjugate fiber of the present invention, modified Et /
The other thermoplastic polymer to be compounded with the VA-based copolymer is 1
It may be one kind or two or more kinds. Then, the method of the present invention uses Et on part or all of the fiber surface.
It is particularly effective for the conjugate fiber in which the / VA-based copolymer is exposed and its hot water resistance is reduced.

The cross-sectional shape of the fiber and the conjugate fiber of the present invention may be any shape, and may be circular or irregular. In the case of a modified cross section, for example, a flat shape, an elliptical shape, a rectangular shape such as a triangle to an octagon, a T shape,
It may have any shape such as a multi-leaf shape such as a 3 to 8 leaf shape, a hollow shape, or the like. Further, the fiber and the conjugate fiber of the present invention may optionally contain an optional additive such as a fluorescent whitening agent, a stabilizer, a flame retardant and a colorant which are usually used in the fiber-forming polymer. it can.

The fibers and yarns of the present invention include long fibers such as monofilaments, short fibers such as staples, filament yarns, spun yarns, blends of the fibers of the present invention with natural fibers, semi-synthetic fibers and other synthetic fibers. Any of a yarn, a mixed yarn, a plied yarn, etc. may be used. Further, the fiber of the present invention may be subjected to any treatment such as false twist crimping and entanglement treatment. Further, the fiber product of the present invention may be any of knitted fabrics, non-woven fabrics, final garments, fiber products such as towels, which are made of those fibers and threads.

The fiber and the composite fiber of the present invention are made of cotton, silk,
When mixed-spun or interwoven with natural fibers such as hemp and wool, the presence of these natural fibers inhibits the modification of the Et / VA copolymer by the chelate compound (I) and improves hot water resistance. The effect may be difficult to exert.
In that case, before mixing or interwoven with natural fibers,
First, a chelate compound (I) is prepared by using a fiber or a composite fiber made of an Et / VA copolymer in the form of threads such as crepe, thread, and cheese.
It is possible to improve the hot water resistance by denaturing the resin with a natural fiber and then blending or knitting with natural fibers.

A fiber product such as a cloth having a soft texture can be obtained from the fiber composed of the modified Et / VA type copolymer of the present invention and the composite fiber itself. The fiber or the composite fiber of the present invention is circular knitted. Chelate compound (I) in the form
By denaturing and then heat treatment at high temperature to give crimps,
After that, the circular knit is unwound to obtain a crimped yarn, and the crimped yarn is woven or knitted alone or is knitted and woven with a natural fiber to obtain a stretchable fabric having a better soft feeling and a good texture. Obtainable.

[0052]

EXAMPLES The present invention will be specifically described below with reference to Examples and the like. In the following Examples and Comparative Examples, the compound (Ia) represented by the above formula (Ia) was used as the chelate compound (I). Further, in the following Examples and Comparative Examples, the evaluation of hot water resistance was carried out by the presence or absence of gloss before and after dyeing of the cloth obtained in each Example and the texture, and after steam ironing with a patch cloth. This was done by examining the texture of the fabric. Further, the modification ratio of the alcoholic hydroxyl group in the Et / VA copolymer by the compound (Ia), the dyeing rate of the dye and the shrinkage rate of the cloth after dyeing were measured by the following methods.

By the compound (Ia) of alcoholic hydroxyl group
Measurement of modification ratio : The value obtained by subtracting the polymerization ratio (mol%) of the ethylene unit from the Et / VA copolymer is regarded as a vinyl alcohol unit, and the ratio of the vinyl alcohol unit modified by the compound (Ia) above. [That is, the modification ratio (mol%) with respect to 100 mol% of vinyl alcohol] was calculated from the value of the chromium content in the Et / VA copolymer after the modification treatment, which was detected by atomic absorption spectrometry.

Measurement of dyeing ratio : The dye solution before and after dyeing was diluted with a mixed solvent of acetone / water (volume ratio 1: 1),
The absorbance of the diluted solution was measured, and the dyeing rate was calculated by the following mathematical formula 1.

[0055]

## EQU1 ## Dyeing rate (%) = {(A−B) / A} × 100 where A: absorbance at the maximum absorption wavelength of the dye solution before dyeing B: absorbance at the maximum absorption wavelength of the dye solution after dyeing

Measurement of shrinkage of the cloth after dyeing : The warp density before and after dyeing was measured with a decimator, and it was determined by the following mathematical formula 2.

[0057]

[Equation 2] Shrinkage (%) = {(ED) / E} × 100 where D: warp density before dyeing (pieces / dimensions) E: warp density after dyeing (pieces / dimensions)

Example 1 Using methanol as a polymerization solvent and azobis-4-methyloxy-2,4-dimethylvaleronitrile as a polymerization initiator, 60
Ethylene and vinyl acetate were radically polymerized at a temperature of 50 ° C. under pressure to produce an ethylene / vinyl acetate random copolymer having an ethylene content of 44 mol% (number average degree of polymerization: about 350). Next, this ethylene / vinyl acetate random copolymer (hereinafter referred to as "Et / VAc copolymer") is saponified in a methanol solution containing caustic soda to obtain 99 mol% or more of vinyl acetate units in the copolymer. A saponified wet Et / VA copolymer was prepared. The Et / VA-based copolymer was repeatedly washed with a large excess of pure water to which a small amount of acetic acid was added, and then washed with a large excess of pure water to obtain alkali metal ions in the copolymer. And the content of alkaline earth metal ions each less than about 10 ppm,
Then, after separating water from the copolymer by a dehydrator, 1
Dry thoroughly by vacuum drying at a temperature below 00 ° C and
/ VA copolymer (85% hydrous phenol solvent, 30 ° C
Intrinsic viscosity [η] = 1.05dl / g when measured by
Got

The Et / VA copolymer obtained above was melt-spun at a spinneret temperature of 260 ° C. and wound at a spinning speed of 1000 m / min to obtain 50 denier / 24 filament Et / VA.
A copolymer multifilament was obtained. The fiberizing process described above was good and no trouble occurred. A taffeta fabric was produced using the multifilament obtained above as a warp and a weft. The above-mentioned raw taffeta fabric was treated with sodium hydroxide at 1 g / liter and Actinol R-10.
0 (surfactant: Matsumoto Yushi Co., Ltd.) was treated with an aqueous solution containing 0.5 g / liter at 80 ° C. for 30 minutes to desizing, and then the following treatment bath in which the concentration of compound (Ia) was changed. The composition was placed in each of the treatment baths and impregnated at room temperature for 10 seconds.

Treatment bath composition Compound (Ia) (Zebran CR-N; purity 25%); concentration (%) shown in Table 1 hexamethylenetetramine; {concentration of compound (Ia)} ×
0.05 (%)

Then, the taffeta fabric was taken out of the treatment bath and was squeezed with a mangle to have an impregnation rate of 60%. This was pre-dried at 70 ° C. and then heat-treated at 150 ° C. for 1 minute. The taffeta fabric obtained above was dipped in a dyeing solution having the dyeing composition shown below and dyed at 100 ° C. for 40 minutes.

Dyeing liquid Compositional dye: Sumikaron Blue SE-RPD (Sumitomo Chemical Co., Ltd.) 2% owf Dispersant: Nikkasan Salt (Nikka Chemical Co., Ltd.) 0.5 g / liter pH adjuster Ammonium sulfate 1 g / liter Acetic acid (48%) 1 cc / liter Bath ratio 50: 1

The dyed product obtained above is dried to obtain a modification ratio of the alcoholic hydroxyl group in the Et / VA copolymer fiber constituting the cloth with the compound (Ia), a dyeing ratio and a shrinkage ratio of the cloth after dyeing. Was measured by the method described above. Further, the hot water resistance of the obtained dyed product was evaluated by the presence or absence of gloss before and after the dyeing and the feel, and the presence or absence of hardening of the cloth after the patch cloth was steam ironed. The results are shown in Table 1 below.

[0064]

[Table 1]

From the results shown in Table 1 above, the modification ratio with the compound (Ia) is in the above-mentioned range of 0.05 to 2 mol% based on the number of moles of the alcoholic hydroxyl group in the Et / VA copolymer. And the hot water resistance of the fabric composed of the Et / VA copolymer fiber are improved, and the high-temperature hot water (steam) treatment during dyeing and steam ironing does not cause shrinkage or sticking of the fabric, resulting in gloss and texture. Is kept good,
Moreover, it can be seen that the dyeing rate of the dye is good and the dyeing is performed in a clear color.

Comparative Example 1 An Et / VAc copolymer having an ethylene content of 44 mol% (number average degree of polymerization: about 350) prepared in Example 1 was melt-spun without saponification to obtain 50 denier. A taffeta woven fabric was produced using / 24 filament filament yarns as warp and weft yarns. After desizing the taffeta fabric in the same manner as in Example 1, the taffeta fabric was placed in a treatment bath having a compound (Ia) concentration of 10% and a hexamethylenetetramine concentration of 0.05%, and impregnated at room temperature for 10 seconds. I went. Then, after predrying, heat treatment and dyeing treatment were performed in the same manner as in Example 1 to produce a dyed Et / VAc copolymer fiber taffeta fabric. The modification ratio with the compound (Ia), the dyeing ratio, and the shrinkage ratio of the cloth after dyeing in this taffeta fabric were measured by the methods described above, and the hot water resistance thereof was evaluated in the same manner as in Example 1. The results are shown in Table 2 below.

Comparative Example 2 50 manufactured by a wet method
Dental / 24 filament polyvinyl alcohol (hereinafter "PVA") filament yarns were used as warp and weft to produce taffeta fabrics. 1 g / liter of sodium hydroxide and Actinol R-100 (surfactant: manufactured by Matsumoto Yushi Co., Ltd.) were used for this raw taffeta fabric.
In an aqueous solution containing 0.5 g / liter of water at 50 ° C.
After demineralization by treating for 30 minutes with a compound (Ia), it was placed in a treatment bath having a concentration of compound (Ia) of 10% and a concentration of hexamethylenetetramine of 0.05%, and impregnated at room temperature for 10 seconds. Then, the taffeta fabric was taken out of the treatment bath, squeezed with a mangle to a 60% impregnation rate, and then pre-dried at 70 ° C.
Dry heat treatment was performed at 50 ° C. for 1 minute. The taffeta fabric obtained above is dipped in a dyeing solution having the dyeing composition shown below for 100
It was dyed at 40 ° C. for 40 minutes.

[0068] liquor group formed dye fee: Copper Blue 2B (manufactured by Nippon Kayaku Co., Ltd.) 2% owf accelerants: 10% sodium sulfate owf bath ratio 50: 1

The rate of modification by the compound (Ia) in this taffeta fabric, the dyeing rate and the shrinkage rate of the cloth after dyeing were measured by the methods described above, and the hot water resistance thereof was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0070]

[Table 2]

From the results in Table 2 above, a cloth made of Et / VAc copolymer fiber in which vinyl acetate units are not saponified and PV in which the vinyl acetate units are completely saponified
In the case of a fabric composed of A fibers, the rate of modification with the compound (Ia) is significantly reduced after dyeing, the hot water resistance thereof is greatly impaired, shrinkage and sticking occur during dyeing, and the gloss and feel of the fabric deteriorate. Change

Example 2 Using each of the Et / VA copolymers in which the ethylene copolymerization ratio is the value shown in Table 3 below and the saponification degree of the vinyl acetate unit is 99%, , Melt spinning at a spinneret temperature of 260 ° C., spinning speed of 1000
It was wound at m / min to obtain each Et / VA copolymer multifilament of 75 denier / 36 filament. A taffeta woven fabric was produced by using each of the multifilaments obtained above as a warp and a weft. This taffeta fabric was subjected to modification treatment with the compound (Ia) in the same manner as in Example 1, followed by heat treatment and dyeing treatment. In this Example 2, the concentration of the compound (Ia) in the treatment bath was 10%.
And When the same evaluation as in Example 1 was performed, the results were as shown in Table 3 below.

[0073]

[Table 3]

From the results shown in Table 3 above, if the ethylene copolymerization ratio in the Et / VA copolymer is too low, the fiberizing processability deteriorates and spinning becomes impossible. On the other hand, if the ethylene copolymerization ratio is too high, the woven fabric becomes Compound (Ia) with reduced texture
It can be seen that the modification ratio due to is small and the hot water resistance is poor.

Example 3 Each Et / VA copolymer having an ethylene copolymerization ratio shown in Table 4 below and polyethylene terephthalate (PET) (in an equal amount mixed solvent of phenol and tetrachloroethane, at 30 ° C.). [Η] 0.67 dl / g) when measured and subjected to composite spinning / stretching at the weight ratios shown in Table 4 so that the cross-sectional shape is a perfect circle and E
50 denier / 2 consisting of a two-layer concentric core-sheath type composite fiber in which the t / VA copolymer constitutes the sheath part and PET constitutes the core part
A 4-filament composite filament yarn was produced.

Plain fabrics were prepared using the drawn composite yarn obtained above as warp and weft. After desizing in the same manner as in Example 1, each plain fabric was subjected to modification treatment with the compound (Ia) in the same manner as in Example 1.
In this example, the compound (I
The concentration of a) was set to 5%. The plain woven fabric obtained above was dipped in a dyeing solution having the dyeing composition shown below and dyed at 115 ° C. for 40 minutes.

Dyeing liquid Compositional dye: Sumikaron Blue SE-RPD 2% owf Dispersant: Nikkasan salt 0.5 g / l pH adjuster Ammonium sulfate 1 g / l Acetic acid (48%) 1 cc / l Bath ratio 50: 1

The dyed product obtained above was dried to give the modification ratio of the alcoholic hydroxyl group in the Et / VA copolymer fiber constituting the cloth with the compound (Ia) and the hot water resistance of the obtained dyed product. It was evaluated by the presence or absence of gloss before and after dyeing and the texture. The results are shown in Table 4 below.

[0079]

[Table 4]

From the results shown in Table 4 above, the woven fabric of the present invention comprising the composite fiber modified with the compound (Ia) has excellent hot water resistance, and the gloss and the texture of the fabric can be improved even by the high temperature treatment under the water during dyeing. It can be seen that there is no decrease. Furthermore, from the results in Table 4, in order to improve the fiberizing processability, Et / VA
It can be seen that it is necessary to adjust the copolymerization ratio of ethylene in the copolymer and the ratio of the Et / VA copolymer and the polyester in the composite fiber.

Example 4 An Et / VA copolymer having an saponification degree of 99% and an ethylene content of 44 mol% (intrinsic viscosity [η] = 1.10 dl / g) and 8 mol% of isophthalic acid were used. Polymerized polyethylene terephthalate (hereinafter “PE
"T copolymer") (intrinsic viscosity during spinning [η] = 0.
65 dl / g) is spun in a weight ratio of 1: 1 so that the cross-sectional shape is a perfect circle, the Et / VA copolymer constitutes the sheath portion, and the PET copolymer constitutes the core portion. The layer concentric core-sheath type composite fiber is spun at a temperature of 265 ° C. and the spinning speed is 100
A composite filament yarn was produced by melt spinning at 0 m / min.

The composite yarn obtained above was brought into contact with a heat roller at 75 ° C. and a heat plate at 120 ° C. by an ordinary roller plate drawing machine and drawn at a draw ratio of 4.1 times to 50.
A denier / 24 filament composite drawn yarn was produced.
This composite drawn yarn is used as a warp and a weft, a Z twist of 300 T / M is used for the warp, and a Z twist of 2500 T / M is used for the weft.
A satin crepe in which two M and S twist 2500 T / M strong twist yarns were alternately wefted was woven. The greige density was 164 warps / dimension and 97 wefts / dimension.

The raw satin crepe obtained above was tension-free with a Shrink Suffer machine.
A dry heat treatment at 50 ° C. was performed. Next, 1 g / liter of sodium hydroxide and 0.5 g of actinol R-100
After performing a scouring desizing treatment at 80 ° C. for 30 minutes using a liquid containing 1 / liter of the liquid, a treatment bath having the following treatment bath composition containing the compound (Ia) was impregnated at room temperature.

Treatment bath composition Compound (Ia) (Zebran CR-N; Purity 25%) 5% Glycerin 2% Hexamethylenetetramine 0.25%

The fabric was then removed from the treatment bath and squeezed with a mangle to 60% impregnation. This was pre-dried at 70 ° C. and then heat-treated at 150 ° C. for 1 minute. The woven fabric obtained above is dipped in a dyeing solution having the following dyeing solution composition, and 1
It was dyed at 20 ° C. for 40 minutes.

Dyeing liquid Compositional dye: Miketon Polyester Navy Blue GLSF conc. 5% owf (manufactured by Mitsui Toatsu Dyes Co., Ltd.) Dispersant: Nikkasan Salt 0.5 g / l pH adjuster Ammonium sulfate 1 g / l acetic acid (48 %) 1 cc / liter Bath ratio 50: 1

Next, after taking out from the dyeing bath, washing treatment was performed with warm water of 80 ° C. for 30 minutes, and then final heat treatment was performed at 140 ° C. for 1 minute. Modification ratio of the alcoholic hydroxyl group of the Et / VA copolymer fiber constituting the woven fabric with the compound (Ia),
The hot water resistance of the obtained dyed fabric was evaluated by the gloss and the feel before and after dyeing as described above. The results are shown in Table 5 below.

<Embodiment 5> No tension state before desizing, 1
Satin crepe production, dyeing treatment and final heat treatment were carried out in the same manner as in Example 4 except that dry heat treatment at 50 ° C. was not carried out. The compound (I
The modification ratio according to a) and the hot water resistance of the obtained dyed fabric were examined in the same manner as in Example 4. The results are shown in Table 5 below.

Comparative Example 3 A satin crepe was produced and dyed in the same manner as in Example 4 except that the denaturing treatment with the compound (Ia) was not carried out, and the dyeing treatment was carried out by jet high temperature dyeing at 120 ° C. Treatment and final heat treatment were performed. The modification ratio of compound (Ia) in the obtained dyed fabric and the hot water resistance of the obtained dyed fabric were examined in the same manner as in Example 4.
The results are shown in Table 5 below.

[0090]

[Table 5]

From the results shown in Table 5 above, the woven fabrics of Examples 4 and 5 treated with the compound (Ia) have good hot water resistance, and even if they are dyed at a high temperature, the shine and the texture of the woven fabric are good. It is possible to maintain good quality without deterioration, and the compound (I
It can be seen that in Example 4 in which the dry heat treatment is performed at a high temperature before the treatment according to a), the hot water resistance of the fabric is further improved and the quality of the fabric is further excellent. In contrast, the compound (I
In Comparative Example 3 in which the treatment according to a) is not performed, the hot water resistance of the woven fabric is not improved, and sticking occurs due to heating during dyeing.

Example 6 A greige satin crepe was produced in the same manner as in Example 5, and was subjected to a dry heat treatment at 150 ° C. and a scouring desizing treatment in the same manner as in Example 5 without tension. It was Then, the woven fabric was wound into a lantern and impregnated with a treatment bath having the following treatment bath composition containing the compound (Ia) at 30 ° C. for 3 hours.

Treatment bath composition Compound (Ia) (Zebran CR-N; Purity 25%) 5% Hexamethylenetetramine 0.25%

The fabric was then removed from the treatment bath and squeezed with a mangle to 60% impregnation. This was pre-dried at 70 ° C. and then heat-treated at 140 ° C. for 1 minute. The modification ratio with the textile compound (Ia) at this time was 0.6 mol%. The woven fabric obtained above was dipped in a dyeing solution having the dyeing solution composition shown below and dyed at 135 ° C. for 40 minutes.

[0095] liquor group formed dye fee: Kayalon Polyester Black G-SF (manufactured by Nippon Kayaku Co., Ltd.) 5% owf dispersant: Tohosolt TD (manufactured by Toho Chemical Co., Ltd.) 0.5 g / l pH regulating agents: Ultra mt- N ₂ (manufactured by Daiwa Chemical Industry Co., Ltd.) 0.7 g / liter Boric acid Concentration: As shown in Table 6 below Sodium sulfate concentration: As shown in Table 6 below Bath ratio 50: 1

Then, it was taken out of the dyeing bath and subjected to usual reduction washing at 70 ° C. The shrinkage ratio (width shrinkage ratio) of the dyed fabric obtained as a result of high-temperature dyeing at 135 ° C. was measured by the above-mentioned method, and the texture and appearance were evaluated to examine the hot water resistance. The results are shown in Table 6 below.

[0097]

[Table 6]

From the results shown in Table 6 above, when boric acid or boric acid and sodium sulfate were added to the dyeing bath, it was possible to prevent the shrinkage of the fabric despite the dyeing at a high temperature of 135 ° C. To obtain a highly commercial dyed product having excellent texture, appearance and color tone.

Example 7 A satin crepe was produced in the same manner as in Example 4 and subjected to scouring desizing treatment, and then the compound
A treatment bath having the following treatment bath composition containing (Ib) was impregnated at room temperature.

Treatment bath composition Compound (Ib) (aluminum octanoate chloride; purity 20%) 5% 1,9-nonanedial 0.8% isopropyl alcohol 3% hexamethylenetetramine 0.25%

The fabric was then removed from the treatment bath and squeezed with a mangle to 60% impregnation. This was wound around a beam, wrapped in a polyethylene film in a hermetically sealed state, and left at room temperature for 24 hours while opening the store. After unwinding the beam winding, preliminary drying was performed at 70 ° C., and then dry heat treatment was performed at 150 ° C. for 1 minute. The woven fabric obtained above was dipped in a dyeing solution having the dyeing composition shown below and dyed at 120 ° C. for 40 minutes.

[0102] liquor group formed dye fee: Sumikaron Blue SE-RPD (manufactured by Sumitomo Chemical Co., Ltd.) 2% owf Dispersant: Nikkan San Salt 0.5 g / l pH regulating agent: Ammonium sulfate 1 g / l acetic acid (48%) 1 cc / Liter Sodium sulfate: 20 g / liter Boric acid 20 g / liter Bath ratio 50: 1

Next, the product was taken out of the dyeing bath, washed with warm water of 80 ° C. for 30 minutes, and finally heat-treated at 130 ° C. for 1 minute. The modification ratio of the alcoholic hydroxyl group of the Et / VA copolymer fiber constituting the woven fabric with the compound (Ib) and the hot water resistance of the obtained dyed woven fabric were examined in the same manner as in Example 4. The results are shown in Table 7 below.

Comparative Example 4 A salen crepe was produced in the same manner as in Example 7 except that the denaturing treatment with the compound (Ib) was not carried out, and the dyeing treatment was carried out by jet high temperature dyeing at 120 ° C. And a final heat treatment was performed. The hot water resistance of the obtained dyed fabric was examined in the same manner as in Example 4. The results are shown in Table 7 below.

[0105]

[Table 7]

From the results shown in Table 7 above, the chelate compound (I)
In the compound (I) in which the metal atom M is aluminum.
It can be seen that also in the case of b), a good gloss and texture can be obtained.

[0107]

EFFECTS OF THE INVENTION The fibers, yarns and fiber products of the present invention have extremely good hot water resistance, and even during dyeing or treatment with hot water or high temperature steam such as steam iron treatment,
To obtain a product with a very high commercial value that does not cause sticking, adhesion, shrinkage, etc., has a good texture, luster, appearance similar to natural fibers that is soft and has a high sense of bulkiness, and has a deep deep shade. You can Further, in the present invention, high-temperature heat treatment can be performed before or after dyeing to further improve the hot water resistance.

In the present invention, boric acid,
Alternatively, by adding boric acid and a salt of a strong acid or a strong base, smooth high temperature dyeing becomes possible, and a composite fiber of a thermoplastic polymer and an Et / VA copolymer, such as polyester, which requires high temperature dyeing, Dyeing of yarns and textiles can be carried out extremely well, without impairing the texture and appearance.

Further, in the case of the method of the present invention, the copolymerization ratio of ethylene in the Et / VA copolymer, the modification ratio with the group (I) and / or the group (II), depending on the respective circumstances,
By adjusting the composite ratio of the Et / VA-based copolymer and other thermoplastic polymer, the strength of the fiber is not lowered, and troubles and undesired coloring in the polymer design and the fiber forming process are caused. It is possible to easily obtain fibers, yarns and fiber products having excellent hot water resistance, without causing

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location D01F 8/10 C 7199-3B 8/14 Z 7199-3B D02G 3/02 D03D 15/00 A 7199 −3B D06M 13/184 (72) Inventor Kazuhiko Tanaka 1621 Sakazu, Kurashiki, Okayama Prefecture Kuraray Co., Ltd. (72) Inventor Masao Kawamoto 1621 Sakata, Kurashiki City, Okayama (72) Inventor Tanaka Takaaki 12-13 Umeda, Kita-ku, Osaka

Claims (7)

[Claims] 1. The basic skeleton comprises an ethylene-vinyl alcohol copolymer, and the alcoholic hydroxyl group in the copolymer is represented by the following formula (I); (In the formula, M is a metal atom capable of forming a chelate, R is an alkyl group, and X ₁ , X ₂ , X ₃ and X ₄ are groups selected from a halogen atom and a hydroxyl group, which may be the same or different. The modified fiber is composed of a modified ethylene-vinyl alcohol-based copolymer, which is modified with at least one compound represented by 2. The basic skeleton is composed of an ethylene-vinyl alcohol-based copolymer, and the alcoholic hydroxyl group in the copolymer is represented by the following formula (I): (In the formula, M is a metal atom capable of forming a chelate, R is an alkyl group, and X ₁ , X ₂ , X ₃ and X ₄ are groups selected from a halogen atom and a hydroxyl group, which may be the same or different. Optionally)), a composite fiber comprising a modified ethylene-vinyl alcohol copolymer modified with at least one compound represented by the formula (3) and another thermoplastic polymer. 3. A yarn and a fiber product containing at least one of the fibers according to claim 1 and claim 2 as a constituent component. 4. A fiber composed of an ethylene-vinyl alcohol copolymer, a composite fiber composed of an ethylene-vinyl alcohol copolymer and another thermoplastic polymer, or a yarn containing at least one of those fibers as a constituent component. And a textile product having the following formula (I): (In the formula, M is a metal atom capable of forming a chelate, R is an alkyl group, and X ₁ , X ₂ , X ₃ and X ₄ are groups selected from a halogen atom and a hydroxyl group, which may be the same or different. Optionally treated with) a treatment agent containing at least one compound represented by the formula (1), and then heat-treated at a temperature lower than the melting point of the ethylene-vinyl alcohol copolymer. A method for producing the fiber, the conjugate fiber, the yarn, and the fiber product according to any one of items. 5. The treating agent is, in addition to the compound represented by the above formula (I), (a) a neutralizing agent; and / or (b) at least one of glycerin, ethylene glycol, polyethylene glycol and isopropyl alcohol. The method according to claim 4, further comprising one kind of hydroxyl group-containing compound. 6. A fiber, a composite fiber, a yarn and a fiber comprising an ethylene-vinyl alcohol copolymer at a high temperature lower than the melting point of the ethylene-vinyl alcohol copolymer before the treatment according to claim 4 or 5. Heat treating the product.
Or the manufacturing method of 5. 7. The method according to any one of claims 4 to 6, further followed by dyeing in a dyeing bath containing boric acid or a salt of boric acid and a strong acid / strong base. Process for producing fibers, composite fibers, yarns and textiles modified and dyed with a compound of formula (I).