JPH1143818A - Moisture keeping fiber, production thereof and dyeing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a fiber having moisture keeping and protecting effects to a skin and an excellent softness and a touch feeling by immersing a fiber consisting of a polymer having reactive hydroxyl groups, etc., in a solution containing a specific compound and aminopolysaccharides under an acidic condition and treating at a specific temperature. SOLUTION: This method for producing a moisture keeping fiber is to immerse a fiber consisting of a polymer having reactive hydroxyl groups or amino groups into a solution containing a compound of the formula [R1 to R4 are each an alkyl or an alkylene by forming a ring with R1 and R2 , R3 and R4 ; R5 is H or an alkyl; (m) is 2-10], (e.g.; 1,1,6,6-tetramethoxyhexane) and aminopolysaccharides under an acidic condition of pH 2.0-5.0, and treat at 90-130 deg.C to obtain an objective fiber fixed with the aminopolysaccharides through the compound of the formula.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a fiber which, when used as a garment in direct contact with the skin, has a moisturizing and protective effect on the skin, maintains the health of the skin, and has excellent flexibility and texture. The present invention relates to a method for producing the fiber and a method for dyeing the fiber.

[0002]

2. Description of the Related Art Conventionally, softening agents such as silicone oil agents have been used to impart flexibility to spun yarns made of natural fibers, synthetic fibers, and the like, woven and knitted fabrics, and nonwoven fabrics.
It has been proposed to use anionic, nonionic, cationic, double-sided surfactants. JP-A-3-14674
Japanese Patent Application Publication No. JP-A-2003-115139 discloses a method of treating a natural fiber with a quaternary ammonium base and a cationic compound having a reactive group that reacts with a hydroxyl group of the fiber, and then softening the fiber with an anionic softener. However, since the treatment with a cationic compound aims at the reaction between the natural fiber and the cationic compound, the fact is that the type of fiber is limited.

[0003] In order to impart moisturizing properties to fibers,
It has been proposed to anchor proteins and chitosan to fibers. For example, JP-A-2-41473 discloses that a fiber having at least one functional group such as a hydroxyl group, an amino group, and a carboxyl group is immersed in an aqueous solution of chitin / chitosan and a derivative compound thereof, and then dried and dried. A method of performing a cross-linking reaction using a polyisocyanate compound in a system solvent is disclosed in Japanese Patent Application Laid-Open No. 9-3772, and a method of coating a protein on the surface of a fiber structure is disclosed in JP-A-9-3772.
JP-A-9-41270 and JP-A-9-4127
No. 1 proposes natural and synthetic fibers provided with antibacterial and deodorizing performance, the surfaces of which are coated with a polyion complex comprising chitosan and a polyanion.

However, the method of fixing chitosan to fibers using a polyisocyanate compound as a cross-linking agent (Japanese Patent Application Laid-Open No. 2-41473) is not only complicated, but also uses a polyisocyanate compound as a cross-linking agent. Therefore, there is a problem that the fiber itself or the fabric has a reduced whiteness, while impairing the inherent hygroscopicity and moisture releasing property of the fiber itself. Further, a method of coating a protein or chitosan on a fiber surface (Japanese Patent Application Laid-Open Nos.
In JP-A-41270 and JP-A-9-41271), even if protein or chitosan can be fixed to the surface of the fiber or the surface of the fibrous structure, it is an apparent bond, and the protein or chitosan is forcibly attached to the surface of the fiber or the fibrous structure. Alternatively, since the fibers or the fiber structure are physically fixed, the texture of the fibers or the fibrous structure becomes hard and the commercial value is low. Further, in order to bond the fiber with chitosan, it is conceivable to use a compound having an aldehyde group such as formaldehyde, glyoxal, glutaraldehyde, etc. instead of the polyisocyanate compound described in JP-A-2-41473. However, there is a problem that the human body, especially those with weak skin, is not necessarily hygienic.

[0005]

SUMMARY OF THE INVENTION The present invention has a moisturizing property without impairing the intrinsic properties of the fiber, for example, when used as clothing that comes in direct contact with the skin, it has a moisturizing property on the skin and a protective effect. Provided are a fiber, a fiber product, and a method for producing the fiber, which have high washing durability and maintain excellent performance such as excellent flexibility and texture.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, have reached the present invention. That is, the present invention provides a fiber comprising a polymer having a reactive hydroxyl group or an amino group, in which an aminopolysaccharide is mainly immobilized via a compound represented by the following formula (1), and a fiber mainly comprising the fiber. Product, its production method and its dyeing method.

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In the present invention, the fiber comprising a polymer having a reactive hydroxyl group or amino group refers to a fiber comprising a polymer having such a functional group, regardless of whether it is natural or synthetic. Specifically, natural fibers such as silk, cotton, wool, hemp, polyamide fibers, polyester fibers, polyvinyl alcohol-based fibers (including modified polyvinyl alcohol-based fibers), and ethylene-vinyl alcohol-based copolymer Synthetic fibers such as united fibers and regenerated fibers such as visco-rayon can be exemplified. The synthetic fiber includes a composite fiber of the above-mentioned polymer and another fiber-forming polymer.
The fiber products include spun yarns, woven and knitted fabrics, and nonwoven fabrics of single or mixed fibers composed of these fibers.

[0008] In particular, these textiles are used in lingerie, underwear, brassiere, bodice, which are worn directly on the skin.
Clothing, underwear for kimono, girdle, belly band, socks, gloves, sports goods, etc., as well as daily necessities such as curtains, carpets, etc., which are required to have dirt removal performance. It is suitable for.

Hereinafter, among the above-mentioned fibers, a fiber made of an ethylene-vinyl alcohol-based copolymer which is one of synthetic fibers will be described in detail. The ethylene-vinyl alcohol-based copolymer (hereinafter, sometimes simply referred to as a copolymer) that forms such fibers is a saponified ethylene-vinyl acetate-based copolymer. The amount of ethylene contained in the copolymer is preferably 25 to 70 mol%, more preferably 30 to 50 mol%. If the ethylene content of the copolymer is high, that is, if the content of the vinyl alcohol portion is low, the properties such as hydrophilicity are naturally lowered due to the reduction of hydroxyl groups, and the intended hydrophilicity, hygroscopicity, Effects such as water absorption tend to decrease. On the other hand, if the content of the vinyl alcohol portion is too high from the viewpoint of the yarn-making properties, the melt spinnability will be reduced, and the spinnability and elongation during fiberization will be deteriorated, and single yarn breakage and breakage will occur. This tends to be unsuitable for melt-spun fibers which are said to have excellent production rationality.

As will be described later, when a polymer having a high melting point such as polyester is used as a thermoplastic polymer during composite spinning of the copolymer and another thermoplastic polymer, the spinning temperature necessarily increases. The vinyl alcohol in the copolymer.
When there are many thread portions, melt spinning at high temperatures tends to be difficult.

The ethylene-vinyl alcohol-based copolymer is produced by saponifying an ethylene-vinyl acetate-based copolymer with sodium hydroxide.
It is preferably at least 5%. If the saponification degree is too low, not only the crystallinity of the copolymer is reduced and the fiber basic physical properties such as strength are reduced, but also the copolymer is easily softened, causing trouble in the processing step. In addition, the texture of the obtained fiber or fiber product may be deteriorated.

The copolymer can be produced by a known method. For example, ethylene and vinyl acetate are radically polymerized in a polymerization solvent such as methanol in the presence of a radical polymerization catalyst, then unreacted monomers are expelled, and a saponification reaction is caused by sodium hydroxide to produce ethylene-vinyl alcohol. After being made into a system copolymer, it is pelletized in water, washed with water and dried. In the process, an alkali metal or an alkaline earth metal is easily intervened in the copolymer, and its amount is several hundred ppm or more. When these metal ions are present, the copolymer is liable to be thermally decomposed. Therefore, it is necessary to reduce the amount to 100 ppm or less, particularly 50 ppm or less. As a method for reducing such metal ions, a method in which the wet pellets in the above-described production process are washed with a large amount of pure aqueous solution containing acetic acid, and further washed with only a large excess of pure water.

The amino polysaccharide used in the present invention is a polysaccharide having an amino group, and specific examples include chitosan. Chitosan is mainly obtained by removing chitin obtained by removing impurities such as calcium and protein from the shell of crustaceans such as crabs and shrimps by an acid and alkali treatment, and then subjecting the chitin to heat treatment with caustic soda. It is an acetylated basic polysaccharide having an amino group with a molecular weight of hundreds of thousands. The molecular weight of the chitosan used in the present invention is not particularly limited, but those having a relatively low molecular weight of 30,000 to 300,000 are preferable from the viewpoint of easy handling. The degree of deacetylation is preferably at least 70%, more preferably at least 80%, in consideration of the solubility in organic acids and inorganic acids.

In the present invention, as the protein to be used in combination with chitosan, any protein having an amino group can be used, as long as it is a vegetable protein or an animal protein. As the vegetable protein, defatted plant seeds and proteins separated therefrom, that is, soybean protein, wheat protein and the like can be used. Examples of animal proteins include milk proteins (casein, whey protein), collagen, gelatin, keratin, fibroin, sericin, wool powder and the like. Above all, it is preferable that the protein is a protein that is acid-resistant under the conditions for producing fibers described below, that is, under acidic conditions, and the molecular weight is preferably 30,000 or more.

Next, the above-mentioned amino polysaccharide and, if necessary, the main compound that fixes the amino polysaccharide and protein to the fiber will be described. In the present invention, "fixed" means that an aminopolysaccharide or, if necessary, a protein is chemically bonded to a reactive amino group or a hydroxyl group of a polymer via the compound. The compound is represented by the formula (1), and the compound will be described first.

[0016]

Embedded image In the formula, as the alkyl group represented by R _{1 to} R ₄ , a lower alkyl group having 1 to 4 carbon atoms is preferable, and among them, a methyl group is preferable in terms of ease of use. The alkyl group may be substituted with an alkyleneoxy group such as an ethyleneoxy group, and all of R _{1 to} R ₄ may be the same type of alkyl group or different. Further, as the alkylene group forming a ring, a lower alkylene group having 1 to 4 carbon atoms is preferable, but a 5- or 6-membered ring is preferable in consideration of the stability of the ring structure, and therefore, ethylene having 2 to 3 carbon atoms is preferable. And propylene groups are preferred. Any of these alkyl groups and alkylene groups may have a substituent. In the formula, m
Is a value calculated in consideration of the composition ratio when treating using a plurality of the compounds, and is not necessarily an integer.

In order to fix the above-mentioned amino polysaccharide and, if necessary, a protein together with the above-mentioned polymer, especially an ethylene-vinyl alcohol copolymer, the compound must have no branched chain. Preferably, R ₅ is hydrogen. However, the compound may be a mixture of a compound having a so-called branched chain in which R ₅ is a lower alkyl group having 1 to 4 carbon atoms, and a compound having no branched chain. It is preferable that the mixing ratio of the compound having no compound is high.

When R ₅ is an alkyl group, the number thereof may be up to m. However, in the present invention, it is not necessary that all m are alkyl groups. And the remainder is hydrogen, ie
This includes the case where the sum of the alkyl group and hydrogen is m. Further, the alkyl groups may be the same kind of group or different kinds of groups.

Specific examples of such compounds include 1,1,
6,6-tetramethoxyhexane, 1,1,6,6-tetraethoxyhexane, 1,1,7,7-tetramethoxyheptane, 1,1,7,7-tetraethoxyheptane, 1,1,8, 8-tetramethoxyoctane, 1,
1,8,8-tetraethoxyoctane, 1,1,9,9
-Tetramethoxynonane, 1,1,9,9-tetraethoxynonane, 1,1,9,9-bisethylenedioxynonane, 1,1,10,10-tetramethoxydecane,
1,1,10,10-tetraethoxydecane, 1,1,
11,11-tetramethoxyundecane, 1,1,1
1,11-tetraethoxyundecane and the like can be mentioned.

The compound is extremely stable because its terminal is blocked with an alkyl group or an alkylene group forming a ring, and is not oxidized even when contacted with oxygen such as air. When the compound is used as an aqueous solution since it is hardly soluble in water, an anionic surfactant such as sodium dodecylbenzenesulfonate or sodium oxyalkylene modified with polycyclic phenol is used. It can be used in an emulsified state. Alternatively, a mixed solvent of water and alcohol can be used.

In order to fix the aminopolysaccharide and, if necessary, the protein to the above-mentioned polymer, only the compound represented by the formula (1) may be used, but the compound represented by the following formula (2) may be used. They can be used together.

[0022]

Embedded image

The compound represented by the formula (2) is a dialdehyde compound. As the alkyl group represented by R ₆ , a lower alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group is particularly preferable in terms of ease of use. preferable. In the formula (2), n is preferably 3 or more, particularly preferably 7 or more, in view of the effect of increasing the melting point of the polymer to be treated. In order to immobilize the above-mentioned aminopolysaccharide and, if necessary, a protein, it is preferable that the compound does not have a branched chain similarly to the compound represented by the formula (1). May be used. In such a case, it is preferable that the mixing ratio of the compound having no branched chain is higher.

The compound represented by the formula (2) is generally liable to be oxidized by air, has poor stability over time, and has a poor yield in fixing an aminopolysaccharide and, if necessary, a protein to a fiber. Such a problem is suppressed when used in combination with the compound represented by (1). Therefore, when the compound represented by the formula (1) and the compound represented by the formula (2) are used in combination, it is preferable to increase the ratio of the former. A more preferable mixing ratio is the former: the latter = 70: 30-
90:10 (weight ratio). However, the effect of increasing the melting point of the fiber by immobilizing the aminopolysaccharide and protein by the compound represented by the formula (1) is larger than the effect of increasing the melting point of the fiber by the compound represented by the formula (2), and will be described later. When the dyeing treatment temperature is increased in a combined system with a dye, excessive shrinkage of fibers and sticking between fibers are likely to occur. Therefore, aminopolysaccharide and protein are fixed by the compound 100 represented by the formula (1).
% Is more preferable.

In immobilizing the aminopolysaccharide and, if necessary, the protein, the content of the above-mentioned compound in the treatment solution described below is determined in consideration of the iron shrinkage of the treated fiber or fiber product and the moisture retention of the product. Then, the content is preferably 5 to 20% by weight, particularly 7 to 15% by weight based on the fiber or the fiber product.

The conditions for immobilizing an aminopolysaccharide and, if necessary, a protein using the above-mentioned compound will be described. In order to impart moisture retention without impairing the intrinsic physical properties of the fiber, it is necessary to carry out an immobilization treatment of aminopolysaccharide, aminopolysaccharide and protein under appropriate acidity. PH of processing solution is 2.0
If it is less than 1, the degree of polymerization of aminopolysaccharide and protein is reduced, and the desired fiber cannot be produced. In addition, there are problems of coloring and yellowing of the obtained fiber, and when simultaneous dyeing described later is performed, problems of fading of the dyed material and poor light fastness arise. On the other hand, when the pH of the treatment liquid exceeds 5.0, the ethylene-vinyl alcohol-based compounds of the formulas (1) and (2) must be used unless the conditions such as the treatment temperature and the treatment time are severe. Cross-linking to the polymer, and thus, fixing of the aminopolysaccharide and protein to the fiber are difficult to proceed, and it is not possible to obtain a fiber having properties such as moisturizing properties without impairing the original fiber properties which is the initial purpose. . Aminopolysaccharide, the hydrolysis resistance and immobilization of proteins, the pH of the treatment solution is 2.5 or more in terms of the degree of crosslinking of the above compounds,
It is preferably 4.0 or less.

The acidity of the treatment liquid can be adjusted by a mineral acid such as hydrochloric acid and sulfuric acid; and an organic acid such as acetic acid, formic acid, maleic acid, tartaric acid, lactic acid, citric acid, malic acid and succinic acid. Among them, organic acids are preferred in view of the corrosion resistance of the processing apparatus. Solid acids such as activated clay and ion exchange resins may be used in addition to the water-soluble acids. Aminopolysaccharides are unnecessary in water and many organic solvents, but are more preferable because they can be dissolved in the above-mentioned organic acids and mineral acids.

It is desirable that the processing temperature is 90 ° C. or more and 130 ° C. or less, particularly 100 ° C. or more and 120 ° C. or less. In this case, in order to slow down the processing speed of the processing bath and perform processing with uniformity and reproducibility, it is desirable to reduce the temperature rising rate until the processing temperature reaches a substantial processing temperature. When the treatment temperature is lower than 90 ° C., even if the above-mentioned acidity is satisfied, the immobilization rate of aminopolysaccharides and proteins and, consequently, the cross-linking rate of the above-mentioned compound to the ethylene-vinyl alcohol copolymer are remarkable. Become slow. On the other hand, when the processing temperature is 1
If the temperature is higher than 30 ° C., excessive shrinkage of the fiber occurs, resulting in impaired feeling of the fabric containing the fiber.

In the above-mentioned processing temperature range, 100 ° C.
As described above, the treatment under a pressure of 130 ° C. or less is performed under a pressurized condition. Under the pressurized condition, a state in which an inert gas, for example, nitrogen, helium, or the like is sealed is included in addition to the reduced pressure state of the processing apparatus. Of course, even at a temperature of 90 ° C. or more and 100 ° C. or less, the treatment may be performed under an inert gas atmosphere or under reduced pressure.

The content of aminopolysaccharide and protein in the treatment solution is 0.1 to 0.1% based on the weight of the fiber or fiber product in consideration of the flexibility and moisture retention of the treated fiber or fiber product. It is preferably 10% by weight, particularly preferably 1.0 to 5.0% by weight, and the protein is preferably 0.1 to 5.0% by weight, particularly preferably 1.0 to 3.0% by weight. Since the protein is immobilized on the fiber in combination with the aminopolysaccharide, the ratio may be determined in consideration of the flexibility and moisture retention of the treated fiber or fiber product: aminopolysaccharide: protein = 2
0: 80-80: 20 (weight ratio), especially 30: 70-
It is preferably 70:30.

The cross-sectional shape of the fiber to which the aminopolysaccharide and, if necessary, the protein are immobilized as described above is not limited to a normal round cross-section, but may be an ellipse, a polygon such as a triangle to an octagon, or a polymorph such as a three- to eight-leaf. It may have an irregular cross section such as a leaf shape, a U shape, or a T shape.
Further, it may be a hollow fiber or a solid fiber. When it is a hollow fiber, it has a cross-sectional shape having at least one hollow portion communicating with the fiber axis direction, and the hollow ratio occupies 30% or more of the fiber cross-sectional area. It is preferable from the point of view. Such a hollow fiber may be manufactured by a conventionally known method, and the manufacturing method is not particularly limited. For example, a method in which a core component of a core-sheath composite fiber composed of two kinds of different polymers, or an island component of a sea-island composite fiber is subjected to a treatment such as alkali extraction treatment to form a hollow shape, and the spinning nozzle itself is made hollow. A method of directly spinning a fiber having a hollow cross section may be used.

In the present invention, as described above, fiberization may be performed using only the copolymer, or may be combined with another fiber-forming polymer according to the purpose. Such a fiber-forming polymer has a melting point of 15 in terms of heat resistance and dimensional stability.
A crystalline thermoplastic polymer of 0 ° C. or higher is preferable, and specific examples thereof include polyester, polyamide, and polypropylene. Examples of polyester include terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, phthalic acid, α, β- (4-carboxyphenoxy)
Aromatic dicarboxylic acids such as ethane, 4,4'-dicarboxydiphenyl and 5-sodium sulfoisophthalic acid; aliphatic dicarboxylic acids such as azelaic acid, adipic acid and sebacic acid and esters thereof; ethylene glyco-
, Diethylene glycol, 1,3-propanediol
1,4-butanediol, 1,6-hexanediol-
, Neopentyl glycol, cyclohexane-1,4
-Fiber-forming polyesters comprising diols such as dimethanol, polyethylene glycol and polytetramethylene glycol, wherein at least 80 mol% of the structural units are ethylene terephthalate units or butylene. Polyesters that are terephthalate units are preferred. The polyester may contain a small amount of additives such as a fluorescent whitening agent, a matting agent, a stabilizer, an ultraviolet absorber, a coloring agent, a flame retardant and the like. Examples of the polyamide include aliphatic polyamides containing nylon 6, nylon 66, and nylon 12 as main components, semi-aromatic polyamides, and the like. Polyamides containing a small amount of the third component may be used.
The polyamide also has a small amount of additives, such as an optical brightener,
Matting agents, stabilizers, ultraviolet absorbers, coloring agents, flame retardants and the like may be contained.

In the above-mentioned composite fiber, the composite ratio is ethylene-vinyl alcohol-based copolymer: other fiber-forming polymer (weight ratio) = 10: 90 to 90:10, particularly 3
The ratio of 0:70 to 70:30 is preferred from the viewpoint of spinnability. The composite form is not particularly limited as long as it is a conventionally known composite form, and examples thereof include an (eccentric) core-sheath type, a multilayer bonding type, a side-by-side type, and a random composite type. In order to make the ethylene-vinyl alcohol-based copolymer more hydrophilic and improve the feeling of the hand, at least a part of the cross-sectional circumference of the conjugate fiber, preferably 3
0% or more is preferably an ethylene-vinyl alcohol copolymer.

In the present invention, by immobilizing an aminopolysaccharide on a fiber using the above-mentioned compound, it is possible to impart flexibility and moisturizing property to the fiber or fiber product, and to use an ethylene-vinyl alcohol system. It becomes possible to dye the fiber made of the copolymer. Usually, fibers made of an ethylene-vinyl alcohol-based copolymer have a large exhaustion of the disperse dye, but on the other hand, since the dye is largely dropped off by reduction washing after dyeing, it is only slightly dyed when dyed with a disperse dye. there were. However, in the present invention, the immobilization of the aminopolysaccharide on the fiber made of the copolymer greatly enhances the affinity for the disperse dye. Thus, a fiber having high color development can be obtained.

For this reason, the dyeing can be carried out by adding a dye to a processing solution for fixing the aminopolysaccharide or protein to the fiber or textile using the above-mentioned compound. And staining can be performed simultaneously with the fixation of the protein. When only the compound represented by the formula (2) is used and immobilization of the aminopolysaccharide and the protein and simultaneous dyeing are carried out, the dye is severely decomposed and deep staining becomes impossible.
Further, immobilization and staining of aminopolysaccharide and protein can be performed in separate steps. In the case where the fixation and the dyeing are performed in different steps, the dye may be decomposed by the acid used at the time of the fixation. Therefore, it is preferable to perform the dyeing after the fixation. When dyeing ultrafine fibers having a single fiber fineness of 1.0 denier or less, especially 0.6 denier or less, a disperse dye is used for the simultaneous immobilization and dyeing described above, and after reduction washing, an acid dye or a metal complex salt is used. By re-dyeing with a dye, it becomes possible to dye ultra-fine fibers, which are difficult to darken, to a dark color.

Further, in the case of a fiber comprising only an ethylene-vinyl alcohol copolymer or a composite fiber comprising the copolymer as a component, the copolymer forming these fibers may be supplemented with an aminopolysaccharide or a protein. Before performing the fixing treatment, it is preferable to perform a dry heat treatment at a temperature equal to or lower than the melting point of the copolymer. By this dry heat treatment, a decrease in the hot water resistance of the fiber due to the immobilization of the aminopolysaccharide and the protein can be suppressed. In particular, it is preferable to perform the dry heat treatment at a temperature of (melting point -20) ° C or more and (melting point -5) ° C or less of the copolymer.
Although the reason for this is not clear, the crystallization of the copolymer in the fine fiber structure is promoted, and the introduction of a cross-linked structure by cross-linking the above-mentioned compound further restrains the molecular motion, thereby reducing the hot water resistance. It is presumed that a remarkable improvement is seen. Therefore, the aminopolysaccharide and the hot water that exceeds the decrease in the hot water resistance of the fiber due to the immobilization of the protein are imparted to the fiber, and the ironing at the time of sewing, the steam iron for ordinary households, and the like can prevent the fiber from sticking and softening the fiber. It can be prevented.

The immobilization of the aminopolysaccharide in the present invention, and thus the immobilization of the aminopolysaccharide and the protein, may be carried out in the form of fibers (including conjugated fibers). It may be performed in the form of a fiber product. From the viewpoint of operability, the above-mentioned fixing is preferably performed in the form of a textile such as a woven or knitted fabric or a nonwoven fabric.

In the present invention, fibers (including composite fibers)
The term "short fibers" includes not only short fibers but also long fibers. Examples of short fibers include clothing staples, dry nonwoven fabrics, wet nonwoven fabrics, and wet heat nonwoven fabrics. Of course, a non-woven fabric may be made by using cotton mixed with other fibers even if the fibers are 100% used. However, it goes without saying that the initial effect is not exhibited unless the fiber of the present invention is mixed in a certain ratio or more, especially in a product of 20% by weight or more. In addition, the fiber of the present invention can obtain a fiber having a good feeling such as flexibility and moisturizing property even with long fiber, clothing such as an inner, which is in direct contact with the skin, uniform (eg, golf wear), white robe, Ideal for outer garments. It is also ideal as a living material such as a carpet or carpet.

Further, the fibers of the present invention (including composite fibers)
Is deformed into a cross-sectional shape similar to a polygon such as a pentagon or hexagon by higher-order processing such as false twisting, or various types such as 3 to 8 leaves, T-shape, U-shape, etc. by a non-uniform cross-section nozzle during spinning The cross-sectional shape may be as follows.

[0040]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. In addition, each measured value in an Example is a value measured and calculated by the following method. (1) Fixation of aminopolysaccharide Undyed fiber or fiber product was colored under the following conditions, and the fixation was confirmed by the degree of coloring. Coloring conditions Kayanol Milling Blue GW 1% owf Ammonium acetate 5% owf acetic acid 2% owf Bath ratio 50: 1 Temperature 100 ° C. × 40 minutes Evaluation The amount of immobilization was evaluated by the exhaustion rate of the above acidic dye. For the exhaustion rate, the absorbance at the maximum absorption wavelength of the undiluted solution before dyeing and the dyed solution after dyeing were measured by a self-recording spectrophotometer. Exhaustion rate (%) = [(AB) / A] × 100 A: Absorbance at the maximum absorption wavelength in the stock solution before staining B: Absorbance at the maximum absorption wavelength in the stain solution after staining

(2) Fixation of Protein Undyed fibers or fiber products were colored under the following conditions, and the fixation was confirmed by the degree of coloring. Coloring conditions Rhodamine (CINo. Basic Violet10) 1% owf sodium acetate 0.5% owf acetic acid 1% owf Bath ratio 50: 1 Temperature 100 ° C × 40 minutes Evaluation (protein detection is evaluated by the degree of red coloration) ○ Protein Is present △ A little protein is present × No protein is present When the aminopolysaccharide and the protein are fixed together, the fibers are separately stained under the conditions (1) and (2), and The fixation of the substance was confirmed.

(3) Measurement of Area Ratio of Hollow Part of Hollow Fiber A cross section of the hollow fiber was taken by SEM photograph, and the area of the hollow part in the cross section was calculated to calculate the ratio to the fiber cross-sectional area. The value was shown as an average value of five samples. (4) Skin Water Content (Water Retention) Five female panelers in the 30-year-old were allowed to stay in a room at 20 ° C. and 60% RH for 2 hours, and the water content of the skin inside the upper arm was measured for the skin stratum corneum. Measured by a tester (IBS Co., Ltd.), and the displayed value of the meter was the average value of five persons before the test.
Then, each sample was wrapped around the inner skin of the upper arm in the same manner as in the above-mentioned test of each paneler, with a width of 10 cm, and after being in the room for 3 hours, each sample was removed and the water content of the site was removed. Was measured and shown as an average value.

(5) Washing test According to JIS L 0217-103, washing was repeated 30 times with a home washing machine. The water content of the skin after washing was measured by the above method (4). (6) Heat retention rate Measured by a heat retention tester prepared in accordance with ASTM D-1518-57T. (7) Moisture absorption rate (%) and moisture absorption / desorption difference (%) After adjusting the humidity for a certain period of time to reach a constant weight in an atmosphere of a temperature of 35 ° C., 65% RH and 85% RH, the sample is quickly transferred to a weighing bottle and weighed. Was done. Then, the sample was dried again in a hot air dryer at 105 ° C., weighed in the same manner, and the weight increase rate was calculated as the moisture absorption rate under humidity control of 65% RH.
The difference between the moisture absorption at 85% RH and the moisture absorption at 65% RH was calculated as the moisture absorption / release difference. The difference in moisture absorption and desorption was also performed on the sample after the washing test of (5).

(8) Water absorption (mm longitudinal direction) Method B (Bilec method) in accordance with JIS L 1096
The water absorption length was measured by the following method. The sample after the washing test of (5) was also measured. (9) Chargeability The sample was rubbed with a friction cloth (cotton: goldfish cloth) while rotating the sample according to JIS L 1094, and the generated charged voltage was measured. The sample after the washing test of (5) was also measured. (10) Stain Removal Property (SR Property) A test piece of YAKU 6 × 6 cm is placed horizontally on polyethylene sheet A, and 0.1 cc of the following contaminated liquid is dropped on the center of the test piece. Then, a polyethylene sheet B is placed on the contaminated portion, and a weight is placed thereon. After about 1 minute, the weight and the polyethylene sheet B are removed, and the mixture is left for about 1 hour. The test piece after standing was subjected to JIS L 0217-1.
No. 03 (centrifugal dehydration washing machine), and the degree of contamination after drying was determined as "grade" according to JIS L 0805. Contaminated liquid: Carbon black in dust motor oil.
1% by weight was added, and the mixture was stirred and mixed with a homomixer.

(11) Dark color of dyed material The tristimulus values (X, Y, Z) and chromaticity coordinates (x, y) of the dyed material were measured using a spectrophotometer C-2000S type color analyzer. Then, the L ^* value was calculated by the following relational expression. The smaller the value is, the better the darkness is. L ^* = 116 (Y / 100) ^1/3 −16 (12) Hand The hand of the sample before the fixing treatment and the sample after the fixing treatment were evaluated by five panelists. The evaluation criteria were as follows, and were shown by the average value of five persons. 5 points: The feeling of dryness is very large, or has a dry feeling and excellent softness. 4 points: Have a dry feeling or have a dry feeling and softness. 3 points: Slight dry feeling. 2 points: No dry feeling and slightly hard. 1 point: Hard and not practical.

Example 1 An ethylene-vinyl alcohol copolymer having an ethylene content of 44 mol% and a saponification degree of 99% (hereinafter referred to as Et /
Abbreviated as VA. Melting point 165 ° C.) and polyethylene terephthalate (hereinafter abbreviated as SIP-PET) containing 5.0 mol% of 5-sodium sulfoisophthalic acid in a mixed solvent of 30 weight% such as phenol / tetrachloroethane.
The intrinsic viscosity measured at 0.65 ° C. is 0.65) and Et / V
A composite fiber having a composite form in which A is a sea and SIP-PET is an island [composite ratio: Et / VA: SIP-PET = 50: 50 (weight ratio), 37 islands] is spun at a temperature of 270 ° C. Then, it was wound at a spinning speed of 1000 m / min. Then, the obtained undrawn yarn is drawn by bringing it into contact with a hot roller at 75 ° C. and a hot plate at 120 ° C., and is drawn at 75 denier / 24.
A drawn filament was obtained. The stretched yarn was used as a warp and a weft to prepare a taffeta fabric. The density of the greige was 96 yarns / inch and the density of 87 yarns / inch. The greige taffeta fabric is bathed in a solution containing 5 g / l of desizing agent (PAS-60, manufactured by Rakuto Kasei Kogyo) and 0.5 g / l of Actinol R-100 (manufactured by Matsumoto Yushi). It was immersed in a ratio of 50: 1 at a temperature of 90 ° C. for 1 hour to perform desizing. Then, a pre-set is performed, an alkali erosion treatment is performed under the following conditions, and SIP-PE which is an island component is formed.
T was dissolved and removed. A fiber made of Et / VA having a plurality of hollow portions communicating in the fiber axis direction was obtained.

Alkali erosion treatment conditions Sodium hydroxide 40 g / l Benzyl dimethyl dodecyl ammonium chloride 1 g / l Bath ratio 50: 1 Temperature 90 ° C. × 180 minutes Next, 1,1,9,9-bis Aminopolysaccharide (chitosan) was immobilized in the treatment solution shown below using ethylenedioxynonane. Immobilization treatment conditions Chitosan (molecular weight: 300,000, manufactured by Kimitsu Chemical Industry Co., Ltd.) 5% owf Immobilization treatment agent 15% owf emulsifier (labion, active ingredient is sodium decylbenzenesulfonate, manufactured by Matsumoto Yushi Co., Ltd.) 0.5 g / liter acetic acid 10 cc / liter pH adjuster (maleic acid) Bath ratio 50: 1 Treatment time 40 minutes The treatment liquid was prepared by dissolving chitosan in an acid solution. Table 1 shows various properties of the fiber after the immobilization treatment. It had moisturizing properties and was excellent in stain removal properties.

Examples 2 to 5 In Example 1, except that the pH adjusting agent was replaced with formic acid and the immobilization treatment was carried out in a solution having a pH of 2.5 (Example 2), the pH adjusting agent was changed to acetic acid. Instead, the immobilization treatment was performed in a solution using 10% owf of nonandial as a fixing agent except that the immobilization treatment was performed in a solution having a pH of 4.5 (Example 3). Except that the temperature of the immobilization treatment was 90 ° C. (Example 5), and that Et / having a plurality of hollow portions communicating in the fiber axis direction was similarly used.
Chitosan was immobilized on a fiber composed of VA.
Table 1 shows various properties of the fiber after the immobilization treatment. In the case where nonandial was used as the immobilizing agent, Example 1 was used.
Although the moisture retention was inferior to the fiber obtained in
The moisturizing property was not changed although it was low even after the first washing.
The durability of the moisture retention was excellent.

Comparative Examples 1 to 4 In Example 1, except that glyoxal was used at a concentration of 4% owf as a fixing agent (Comparative Example 1), formaldehyde was used as a fixing agent at a concentration of 2% owf. Except for using (Comparative Example 2), except that acetic acid was used as a pH adjuster and the immobilization treatment was performed in a solution having a pH of 5.5 (Comparative Example 3), the immobilization treatment temperature was 135 ° C. Except for (Comparative Example 4), chitosan was immobilized on a fiber made of Et / VA having a plurality of hollow portions communicating in the fiber axis direction. Table 1 shows various properties of the fiber after the immobilization treatment. When the immobilization agent and the immobilization conditions were different from those of the present invention, the immobilization rate of chitosan became poor, and thus the moisture retention of the fiber was greatly reduced, and the fiber became hard and lacked in practicality. . Further, the hollow fiber which had been immobilized with glyoxal and formaldehyde had a crushed hollow portion and did not have a satisfactory heat retaining property.

Comparative Example 5 In the same manner as in Example 2 except that the fixing temperature was changed to 135 ° C., immobilization of chitosan on a fiber made of Et / VA having a plurality of hollow portions communicating in the fiber axis direction was performed. Processing was performed. Table 1 shows various properties of the fiber after the immobilization treatment. When the temperature of the immobilization treatment was increased, the rate of immobilization of chitosan on the fiber was extremely low, resulting in poor moisture retention and only hard fibers.

Example 6 A polyethylene terephthalate having an intrinsic viscosity of 0.65 (hereinafter abbreviated as PET) was used as a core and an ethylene content of 44.
Core / sheath composite fiber having a sheath portion of Et / VA having a mole ratio of 99% and a saponification degree of 99% and a melting point of 165 ° C. [Composite ratio PET: Et / VA =
50/50 (weight ratio)] at a spinning temperature of 260 ° C and a spinning speed of 1000 m / min. 75 of the obtained undrawn yarn
A hot roll at 140 ° C. and a hot plate at 140 ° C. were drawn to give a drawn yarn of 50 denier / 24 filaments. This drawn yarn is used for warp and weft, 300 T / M twist is applied to the warp, Z twist of 2500 T / M and S twist of 2500 T / M are applied to the weft, and alternate weft is performed two by two. Woven satin crepe. The greige
5 g of desizing agent (PAS-60, manufactured by Rakuto Kasei Kogyo)
Liter and Actinol R-100 (manufactured by Matsumoto Yushi Co., Ltd.) in a solution containing 0.5 g / liter, a bath ratio of 50:
1. Dipping was performed by immersion at 80 ° C. for 1 hour. Then, it is pre-set at 150 ° C, and chitosan,
If necessary, staining was performed simultaneously with immobilization of the protein, and reduction washing was performed. Further, final setting was performed at 150 ° C. to obtain a dyed fabric.

Immobilization and staining conditions Chitosan (molecular weight 300,000, manufactured by Kimitsu Chemical Industry Co., Ltd.) 1% owf collagen (molecular weight 1.1 million, manufactured by Showa Denko KK) 2% owf immobilization agent (1,1,9) , 9-Tetramethoxynonane) Approximately 15% owf Emulsifier (Ravation, active ingredient is sodium decylbenzenesulfonate, manufactured by Matsumoto Yushi Co., Ltd.) 0.5 g / liter Acetic acid 10 cc / liter pH adjuster (maleic acid) Dye (Dianix Tuxedo Black) Hconc liquid) 15% owf Dye agglomeration / precipitation inhibitor (Meisanol CW, manufactured by Meisei Chemical Industry Co., Ltd.) 1% owf bath ratio 50: 1 treatment 115 ° C. × 40 minutes (heating rate from 70 to 115 ° C. is 1 ° C.) The processing solution was prepared by dissolving chitosan in an acid solution.

Reduction washing hydrosulfite 1 g / l Sodium hydroxide 1 g / l Amylazine D 1 g / l Bath ratio 50: 1 Treatment 80 ° C. × 20 minutes Table 2 shows various properties of the obtained dyed fabric. 30 moisture retention
It can be seen that there is no change even after the washing, the chargeability is low, and the dyeing is performed in a dark color.

Example 7 The same procedure as in Example 6 was carried out except that the green fabric satin crepe was subjected to a dry heat treatment at 150 ° C. without tension using a shrink surfer machine, followed by scouring and desizing. Then, fixation and staining were performed, and reduction washing was performed. Table 2 shows various properties of the obtained dyed fabric. By performing the dry heat treatment, the melting point of the fiber was improved, and the water absorption was also improved.

Example 8 A composite fiber was obtained in the same manner as in Example 6 except that collagen was not fixed to Et / VA, and immobilization / staining treatment and reduction washing were performed. Table 2 shows various properties of the obtained dyed fabric. Compared to the fixation of chitosan and collagen, the fixation of chitosan alone has a slightly lower moisture absorption / desorption property,
The charging voltage was also high.

Comparative Examples 6 and 7 In Example 7, except that glyoxal was used at a concentration of 3.5% owf as an immobilizing agent (Comparative Example 6).
Glutaraldehyde 6.0% ow as immobilization agent
Except for using at a concentration of f (Comparative Example 7), a composite fiber was obtained in the same manner, and was subjected to fixation / dyeing treatment and reduction washing. Table 2 shows various properties of the obtained dyed fabric. The fiber had a low moisture absorption rate and a small difference in moisture absorption / release. Inner
When used as, a feeling of stuffiness occurred.

Comparative Examples 8 to 9 In Example 7, sulfuric acid was used as a pH adjuster, and p
Fixing and staining were performed in a solution with H of 1.5 (Comparative Example 8). Fixation was not confirmed, probably because chitosan and collagen were hydrolyzed because the treatment was performed on the side where the hydrogen ion concentration was high. In addition, acetic acid was used as a pH adjuster, and immobilization and staining were performed in a solution having a pH of 5.5 (Comparative Example 9). Since the treatment was performed on the side where the hydrogen ion concentration was low, chitosan and collagen were not immobilized and did not have satisfactory performance.

Example 9 Et / VA having an ethylene content of 44 mol%, a saponification degree of 99% and a melting point of 165 ° C., and a polyethylene terephthalate containing 8 mol% of isophthalic acid (hereinafter abbreviated as IPA-PET) And the composite ratio is Et / VA: IPA-P
A conjugate fiber having an ET = 1/2 (weight ratio) vertically split 11-layer alternately laminated cross section (flat cross section; Et / VA: 5 layers) was wound at a spinning temperature of 270 ° C. and a spinning speed of 1000 m / min. The obtained undrawn yarn was heated with a hot roller at 75 ° C, 140
The film was drawn by contacting with a hot plate at a temperature of 75 ° C. to obtain a drawn yarn of 75 denier / 24 filaments. Using this drawn yarn, a 28-gauge circular knit smooth was knitted. Actinol R-100 (manufactured by Matsumoto Yushi Co., Ltd.) was added to this circular knitting machine using a 0.
In a solution containing 5 g / l, a bath ratio of 50: 1 and a temperature of 80
It was immersed at 30 ° C for 30 minutes to remove the size. Then, it is pre-set at 160 ° C., subjected to alkali reduction treatment at 20 g / l of sodium hydroxide at 85 ° C. for 40 minutes, and the above-mentioned conjugate fiber is made of Et / VA having a single fiber fineness of 0.2 denier.
IPA-PE with fiber and single yarn fineness of 0.15 denier
A circular knitted fabric consisting of T fibers was obtained. This knitted fabric had a good texture of microfiber, peach skin touch. The circular knitted fabric was fixed with chitosan under the following fixing and dyeing treatment conditions A, and at the same time, firstly, dyed with a disperse dye and subjected to reduction washing. Then, staining was performed again under the following staining conditions B, and a final set was performed at 150 ° C. When L ^* was measured after two times of dyeing, it was found that the dye was dyed dark.

A. Immobilization / staining treatment conditions Chitosan (molecular weight: 350,000, manufactured by Kimitsu Chemical Industry Co., Ltd.) 10% owf Immobilization treatment agent (1,1,9,9-tetramethoxynonane) 15% owf emulsifier (labion, active ingredient is decylbenzene) Sodium sulfonate, manufactured by Matsumoto Yushi Co., Ltd. 0.5 g / liter Acetic acid 10 cc / liter pH adjuster (maleic acid) Dye (Dianix Tuxedo Black Hconc liquid) 15% owf Dye coagulation and sedimentation inhibitor (Meisanol CW, Meisei Chemical Co., Ltd.) 1% owf bath ratio 50: 1 treatment 115 ° C. × 40 minutes (heating rate from 70 ° C. to 115 ° C. is 1 ° C./min) The treatment liquid was prepared by dissolving chitosan in an acid solution.

Reduction washing hydrosulfite 1 g / l Sodium hydroxide 1 g / l Amilazine D 1 g / l Bath ratio 50: 1 Treatment 80 ° C. × 20 minutes

B. Dyeing conditions Dye (Suminol Milling Black VLG: acid dye) 5% owf ammonium acetate 5% owf acetic acid 2% owf Bath ratio 50: 1 Temperature 100 ° C. × 40 minutes The various properties of the obtained dyed fabric are shown in Table 3. Table 3 shows various performances of the dyed circular knitted fabric.

Comparative Example 10 In Example 10, glyoxa was used as the immobilizing agent.
Immobilized in a solution with a concentration of 3.5% owf using
A conjugate fiber was obtained in the same manner as above except that the dyeing treatment was performed, alkali splitting treatment was performed, and chitosan was immobilized and dyed with a disperse dye. Subsequently, reduction washing was performed, and dyeing was performed again using an acid dye. Table 3 shows various performances of the dyed circular knitted fabric. Compared with the dyed product obtained in Example 10, it had lower moisture absorption / desorption property, the detachment of the disperse dye after reduction washing was large, and the effect of improving the deep color by the acid dye was not observed.

Comparative Examples 11 to 12 In Example 10, sulfuric acid was used as a pH adjuster,
Dyeing treatment with an immobilized / dispersed dye was performed in a solution having a pH of 1.5, reduction washing, and dyeing treatment with an acid dye were performed (Comparative Example 11). Since the treatment was performed on the side where the hydrogen ion concentration was high, no immobilization of chitosan was observed, and therefore no darkening effect was observed. In addition, acetic acid was used as a pH adjuster, dyeing treatment was performed with a fixed / dispersed dye in a solution having a pH of 5.5, and reduction washing and dyeing treatment with an acid dye were performed (Comparative Example 12). Since the treatment was performed on the side where the hydrogen ion concentration was low, no immobilization of chitosan was observed, and thus no darkening effect was observed.

Comparative Example 13 A composite fiber was obtained in the same manner as in Example 10 except that chitosan was not fixed, subjected to an alkali splitting treatment, a dyeing treatment with a disperse dye and an acid dye, and subjected to reduction washing. Since the chitosan was not fixed, the hygroscopicity and the hygroscopicity were very low, and the dye was almost dropped off by the reduction washing, and the dyeing did not seem to be performed. Also, there was no fixation of chitosan in the staining with the acid dye after the reduction washing, and therefore, there was no staining.

Example 10 In Example 9, 1,1,9,9 was used as the immobilizing agent.
-Bisethylenedioxynonane and nonanediol,
A composite fiber was obtained in the same manner as above except that each was used at a concentration of 12% owf and a concentration of 3% owf, subjected to an alkali splitting treatment and a dyeing treatment, and subjected to reduction washing and re-dyeing treatment. p
Under the acidity of H of 3.0, nonandial was decomposed during dyeing, and chitosan was fixed only with 1,1,9,9-bisethylenedioxynonane. The knitting yield was poor, and the darkness was inferior to the knitted fabric obtained in Example 10, but compared to the knitted fabric obtained in Comparative Example 13, it was dyed darker. .

[0066]

[Table 1]

[0067]

[Table 2]

[0068]

[Table 3]

[0069]

The fiber of the present invention is a polymer constituting the fiber.
Since the aminopolysaccharide and, if necessary, the protein are immobilized thereon, it has excellent moisturizing properties, hygroscopic properties, and hygroscopic properties, and is very suitable as a material directly in contact with the skin. In addition, the immobilization of the aminopolysaccharide and the protein and the staining are performed at the same time, which leads to simplification of the processability. Further, when an ethylene-vinyl alcohol copolymer is used as a polymer for immobilizing aminopolysaccharides and proteins, not only the above-mentioned properties are provided, but also the dye has good exhaustion properties and is dyed in a dark color. As a result, fibers having excellent coloring properties can be obtained. Moreover, it consists of an ethylene-vinyl alcohol-based copolymer,
Ultrafine fibers, for which it was difficult to darken, can be easily darkened by fixing the aminopolysaccharide and dyeing with a disperse dye and then re-staining with an acidic dye.

Claims (22)

[Claims] 1. A fiber comprising a polymer having a reactive hydroxyl group or amino group, wherein an aminopolysaccharide is mainly immobilized via a compound represented by the following formula (1). Embedded image 2. A fiber comprising a polymer having a reactive hydroxyl group or amino group, wherein an aminopolysaccharide and a protein are immobilized mainly via a compound represented by the following formula (1). Embedded image 3. The fiber according to claim 1, wherein the polymer is an ethylene-vinyl alcohol copolymer. 4. A fiber comprising an ethylene-vinyl alcohol copolymer in which an amino polysaccharide is mainly fixed via a compound represented by the following formula (1) and another fiber-forming polymer. Embedded image 5. A fiber comprising an ethylene-vinyl alcohol copolymer in which an aminopolysaccharide and a protein are immobilized mainly via a compound represented by the following formula (1), and another fiber-forming polymer. Embedded image 6. The fiber according to claim 1, wherein the fiber has at least one hollow portion communicating in the fiber axis direction. 7. The ratio of the hollow portion to the fiber cross-sectional area is 30%.
7. The fiber according to claim 6, wherein: 8. A fiber product comprising the fiber according to claim 1 as a main fiber. 9. A fiber consisting of a polymer having a reactive hydroxyl group or amino group is prepared by subjecting a fiber mainly comprising a compound represented by the following formula (1) and an aminopolysaccharide to an acid having a pH of 2.0 to 5.0. Immerse in the solution containing, 90 ° C or more, 130 ° C
A method for producing a fiber, comprising treating at the following temperature. Embedded image 10. A fiber comprising a polymer having a reactive hydroxyl group or an amino group is obtained by mixing a compound represented by the following formula (1) with an aminopolysaccharide under acidity at a pH of 2.0 to 5.0. A method for producing a fiber, comprising immersing in a solution containing a protein and treating at a temperature of 90 ° C to 130 ° C. Embedded image 11. The polymer according to claim 9, wherein the polymer is an ethylene-vinyl alcohol copolymer.
A method for producing the fiber according to the above. 12. A fiber comprising an ethylene-vinyl alcohol-based copolymer and another fiber-forming polymer is mainly represented by the following formula (1) under an acidic condition of pH 2.0 to 5.0. A method for producing a fiber, comprising immersing in a solution containing a compound to be prepared and an aminopolysaccharide and treating at a temperature of 90 ° C or more and 130 ° C or less. Embedded image 13. A fiber comprising an ethylene-vinyl alcohol-based copolymer and another fiber-forming polymer, which is mainly represented by the following formula (1) under acidic conditions having a pH of 2.0 to 5.0. A method for producing a fiber, comprising immersing in a solution containing a compound, an aminopolysaccharide and a protein to be treated and treating at a temperature of 90 ° C or more and 130 ° C or less. Embedded image 14. A fiber comprising an ethylene-vinyl alcohol-based copolymer is prepared by subjecting a fiber mainly composed of a compound represented by the following formula (1), an aminopolysaccharide and a dye to an acid having a pH of 2.0 to 5.0. Immerse in the solution containing, 90 ° C or more, 130 ° C
A method for dyeing a fiber, comprising treating at the following temperature. Embedded image 15. A fiber comprising an ethylene-vinyl alcohol-based copolymer and a compound represented by the following formula (1), an aminopolysaccharide and a protein, under acidic conditions of pH 2.0 to 5.0. Immersed in a solution containing the dye, 90 ° C or higher,
A method for dyeing a fiber, comprising treating at a temperature of 130 ° C. or lower. Embedded image 16. A fiber comprising an ethylene-vinyl alcohol-based copolymer and another fiber-forming polymer, which is mainly represented by the following formula (1) under an acidic condition of pH 2.0 to 5.0. A method for dyeing a fiber, comprising immersing in a solution containing a compound, an aminopolysaccharide and a dye to be treated at a temperature of 90 ° C or more and 130 ° C or less. Embedded image 17. A fiber comprising an ethylene-vinyl alcohol-based copolymer and another fiber-forming polymer, which is mainly represented by the following formula (1) under acidic conditions having a pH of 2.0 to 5.0. A method for dyeing a fiber, comprising immersing in a solution containing a compound, an aminopolysaccharide, a protein and a dye to be treated and treating at a temperature of 90 ° C. or more and 130 ° C. or less. Embedded image 18. A fiber comprising an ethylene-vinyl alcohol copolymer and another fiber-forming polymer in a solution containing a compound represented by the following formula (1), an aminopolysaccharide and a disperse dye. And dyeing by dipping in a solution containing an acid dye or a metal complex dye. Embedded image 19. A fiber comprising an ethylene-vinyl alcohol-based copolymer and another fiber-forming polymer, mainly comprising a compound represented by the following formula (1), an aminopolysaccharide, a protein and a disperse dye. A method for dyeing a fiber, comprising immersing in a solution for dyeing, and then immersing in a solution containing an acid dye or a metal complex dye for dyeing. Embedded image 20. The method for producing fibers according to claim 11, wherein a dry heat treatment is performed at a temperature lower than the melting point of the ethylene-vinyl alcohol copolymer as a pretreatment. 21. The fiber dyeing method according to claim 14, wherein the pretreatment is a dry heat treatment at a temperature not higher than the melting point of the ethylene-vinyl alcohol copolymer. 22. An agent for immobilizing an aminopolysaccharide and a protein on a fiber comprising a polymer having a reactive hydroxyl group or amino group, comprising a compound represented by the following formula (1) as an essential component.