JPH06101177A - Dyeing of modified ethylene-vinyl alcohol-based copolymer fiber, yarn or textile good - Google Patents

Abstract

PURPOSE:To produce a dyed material exhibiting a dark color excellent in rich feeling, etc., by dyeing a fiber composed of a modified ethylene-vinyl alcohol copolymer modified with a specified component in an acidic dye bath containing boric acid, etc., a specified sulfonic acid salt and a specified compound. CONSTITUTION:A fiber (or a composite fiber, etc.) composed of a modified ethylene-vinyl alcohol-based copolymer having a basic skeleton composed of an ethylene-vinyl alcohol-based copolymer in which alcoholic hydroxyl groups are modified with a chelate compound represented by the formula (M is a metal atom capable of chelate formation; R' is an alkyl; X is a halogen) is dyed in a dye bath containing boric acid or boric acid and a strong acid, a salt selected from a salt of a strong base, a naphthalenesulfonic acid salt or its condensate and a lignin sulfonic acid salt and a zirconium compound and exhibiting <=pH 5 at >=90 deg.C, thus affording the objective dyed material excellent in drapeability, stiffness and rigidity and exhibiting a dark color without occurrence of coagulation or adhesion between the fibers. If a heat treatment is carried out at a high temperature of <the melting point before dyeing, the fiber can be more effectively dyed.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a dyeing of an ethylene-vinyl alcohol copolymer fiber or a fiber product which is excellent in hot water resistance and has a good color tone and luster with deepness, an excellent feeling and appearance. The present invention relates to a dyeing method for obtaining a product. More specifically, the present invention relates to a modified ethylene-vinyl alcohol copolymer fiber having improved hot water resistance by a modification treatment with a specific chelate compound, a yarn or a fiber product made of the same, and a dyeing bath containing a predetermined compound. The present invention relates to a dyeing method for obtaining a dyed product which is more excellent in hot water resistance, color tone, gloss, texture, appearance and the like while preventing shrinkage and deterioration at the time of dyeing.

[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 monotonous feeling of texture, gloss, etc. and 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]

SUMMARY OF THE INVENTION Under the above circumstances, the present inventors have
Even when subjected to high-temperature dyeing or high-temperature steam iron treatment, there is no sticking or adhesion of the ethylene-vinyl alcohol copolymer fiber, hardening of the texture associated therewith, deterioration of appearance, loss of gloss, etc. Research aimed at obtaining fibers, composite fibers, yarns made of ethylene-vinyl alcohol copolymers and yarns and cloths made of them, which are excellent in stability and can maintain a good feeling with swelling, firmness and elasticity. I went. Furthermore, the inventors of the present invention are to obtain a dyed product of a fiber or a fiber product of an ethylene-vinyl alcohol copolymer dyed in a clear and deep good color tone while maintaining such good quality. Has also been conducting research and development for many years.

As a result, a fiber or yarn or a fiber product made of an ethylene-vinyl alcohol copolymer is represented by the following formula:
(I);

[0009]

[Chemical 2] (Wherein, M is a metal atom having a chelate-forming ability, R ¹ is an alkyl group, and X is a halogen atom), and a modification treatment is performed with a specific chelate compound. The hot water resistance of the combined product is improved, and further, the modified ethylene-vinyl alcohol copolymer fiber, yarn or fiber product thus obtained is subjected to a dyeing bath containing boric acid or boric acid and a salt of a strong acid or a strong base. It has been found that when dyed using, it is possible to obtain a good dyed product having clear and deep color tone without swelling, softness, firmness, elasticity, etc. without hardening of texture and loss of gloss. (Japanese Patent Application No. 4-60919).

Further, the inventors of the present invention continued to study, to obtain fibers, yarns or fiber products of ethylene-vinyl alcohol copolymer modified with the compound of formula (I).
In dyeing using a dyeing bath containing boric acid or a salt of boric acid and a strong acid or a strong base, the dyeing bath further contains a specific sulfonate or sulfate ester-based compound, and the pH of the dyeing bath is adjusted. Dyeing to 5 or less can prevent sticking, adhesion, shrinkage, deterioration and the like of dyeing fibers and textile products even when dyeing at high temperature, and is further excellent in color tone, gloss, texture and appearance. The present invention has been completed by finding that products can be obtained quickly and efficiently.

That is, in the present invention, 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);

[0012]

[Chemical 3] (Wherein M represents a metal atom having a chelate-forming ability, R ¹ represents an alkyl group, and X represents a halogen atom), and is a modified ethylene-vinyl alcohol copolymer copolymer modified with at least one compound represented by Fibers made of coalescing,
(I) boric acid, or a salt of boric acid and a strong acid / strong base; and (ii) (a) naphthalene sulfonate or its formalin, or a composite fiber, or a yarn or a fiber product containing at least one of these fibers as a constituent component. In a dyeing bath containing at least one compound selected from a condensate, (b) an alkyl (poly) oxyalkylene sulfate ester-based compound, and (c) a lignin sulfonate-based compound, an acidic region having a pH of 5 or less. A method for dyeing a fiber, a composite fiber, a yarn or a fiber product made of a modified ethylene-vinyl alcohol copolymer, which is characterized by dyeing with.

In the above dyeing treatment, a better result can be obtained by further containing a zirconium compound in the dyeing bath, and before the above dyeing treatment is performed, a modified ethylene-vinyl compound is used. When the fiber, the composite fiber, the yarn or the fiber product made of the alcohol-based copolymer is heat-treated at a high temperature lower than its melting point, a better result can be obtained, and the modified ethylene-vinyl alcohol-based copolymer In obtaining a fiber, a conjugate fiber, a yarn or a fiber product composed of a coalescence, a neutralizing agent together with the compound represented by the above formula (I); and / or glycerin,
It has been found to be more desirable to use a treating agent which further contains at least one hydroxyl group-containing compound selected from ethylene glycol, polyethylene glycol and isopropyl alcohol.

Therefore, the present invention further provides: The above dyeing treatment, boric acid, or a salt of boric acid and a strong acid / strong base; at least one of the above compounds (a) to (c).
Seed; and a method of using a dyeing bath containing a zirconium compound and having a pH of 5 or less, The modified ethylene-vinyl alcohol copolymer fiber, composite fiber, yarn or fiber product is heat-treated at a high temperature below the melting point. A dyeing method in which the above dyeing treatment is subsequently carried out; and a modified ethylene-vinyl alcohol copolymer fiber, a composite fiber, a yarn or a fiber product, in addition to the compound of the formula (I), a neutralizing agent; and / or It also includes the above-mentioned dyeing method, which uses one treated with a treating agent further containing at least one hydroxyl group-containing compound selected from glycerin, ethylene glycol, polyethylene glycol and isopropyl alcohol.

An ethylene-vinyl alcohol copolymer (hereinafter referred to as "E" which constitutes the basic skeleton of the fiber targeted by the present invention.
The term "t / VA-based copolymer") has a repeating unit ratio of ethylene of 30 to 70 mol% and a balance of vinyl alcohol alone or a repeating unit of vinyl alcohol and another vinyl-based monomer. 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. . Along with that, the above formula
The modification ratio by the compound represented by (I) [hereinafter referred to as "chelate compound (I)"] is reduced, and the target fiber or fiber product having excellent hot water resistance and good texture with swelling is obtained. I will not be able to. From the viewpoint of obtaining fibers having hot water resistance and good texture with swelling, Et /
The proportion of vinyl alcohol units in the VA-based copolymer is particularly preferably 40 to 70 mol%.

Here, the Et / VA-based copolymer forming the basic skeleton may be a chain which is not crosslinked or may be crosslinked by a suitable method.
This Et / VA copolymer can be obtained by saponifying the vinyl acetate portion of the ethylene / vinyl acetate copolymer, and the saponification degree in that case is preferably about 95% or more. When the saponification degree becomes low, not only the crystallinity of the copolymer is lowered and physical properties such as strength are lowered, but also the copolymer is easily softened, troubles occur in the fiberizing step, and It is not preferable because the texture becomes inferior.

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. The Et / VA copolymer is commercially available, for example, from Kuraray Co., Ltd. under the trade name of EVAL ^R and from Nippon Synthetic Chemical Industry Co., Ltd. under the trade name of Soarnol ^R , and is easily 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, when an Et / VA-based copolymer contains alkali metal ions such as sodium ions and potassium ions and 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 about 50 ppm or less).

The fibers, yarns and fiber products of the present invention are characterized in that the alcoholic hydroxyl group in the Et / VA copolymer is at least one of the above chelate compounds (I).
Must be modified by the species. The Et / VA-based copolymer may be modified by only one kind of chelate compound (I), or may be two or more kinds of chelate compounds.
It may be modified by (I).

In the chelate compound (I), the alkyl group represented by the group R ¹ is preferably a higher alkyl group having 10 to 20 carbon atoms, and particularly preferably a stearyl group. Examples of the metal atom M having a chelate-forming ability include metal atoms such as chromium, iron, zirconium, cobalt, nickel, titanium, aluminum and tin. In the case of chromium, the chelate compound (I) is thermally stable. It has excellent properties. The halogen atom X is chlorine, iodine, bromine or fluorine, with chlorine being preferred. Specific preferred examples of the chelate compound (I) include compounds represented by the following formula (I
a);

[0023]

[Chemical 4] [Compound (Ia)] represented by the following formula can be given, and this compound (Ia) is available as “Zebran CR-N” (trade name) manufactured by Yushisha Co., Ltd.

When the Et / VA copolymer fiber is modified with the chelate compound (I), a dehydrochlorination reaction occurs. Therefore, in the modified fiber, yarn and fiber product, the Et / VA copolymer fiber is used. A bond is formed between the alcoholic hydroxyl group in the copolymer and at least one of the four halogen atoms X bonded to the metal atom in the chelate compound (I), whereby oxygen of the alcoholic hydroxyl group is formed. Via the atom, the following formula (II);

[0025]

[Chemical 5] It is judged that the Et / VA copolymer is modified by the group represented by the formula (wherein R ¹ 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 any 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. It does not easily separate from the Et / VA copolymer. And chelate compound (I)
Binds 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 bonds, Et / VA
A film of the chelate compound (I) is formed on the surface of the fiber of the system copolymer.

The modification ratio of the Et / VA copolymer fiber with the chelate compound (I) is preferably 0.05 to 2 mol% based on the number of moles of vinyl alcohol units in the copolymer, In particular, it is preferable to set it to 0.2 to 0.8 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 05 mol%, good hot water resistance cannot be imparted to the fiber composed of the Et / VA copolymer, and, for example, when the dyeing temperature 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 mol%, the fiber made of the Et / VA copolymer becomes coarse and hard, and the dyeing property is deteriorated, resulting in poor 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. When the treating agent is used as an aqueous solution, it is preferable that the concentration of the chelate compound (I) is in the range of about 0.3 to 5%. It is preferable in terms of appearance.

In that case, a chelating compound is added to the treating agent.
In order to neutralize (I) or hydrochloric acid or the like produced by the reaction of the chelate compound (I) with water, or to prevent corrosion of a metal processing container by the produced hydrochloric acid, a neutralizing agent is added. This 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 made of 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, pad mangle squeezing method or cold batch method is preferable. In the case of the pad mangle drawing method, a fiber, a composite fiber, a yarn or a fiber product made of an Et / VA copolymer is predetermined in a treatment agent (treatment bath) containing a chelate compound (I) at a temperature of 40 ° C. or lower. When the Et / VA copolymer is swollen in advance while giving time vibration to swell the Et / VA-based copolymer so that the treatment agent is uniformly dispersed in the fiber, and then pad mangled drawing is performed, a swelling feeling can be given. Further, in the case of the cold batch method, the fibers, the composite fibers, the yarns or the fiber products squeezed by performing the pad mangle squeezing with the above-mentioned immersion liquid are used so that the treatment liquid remaining adhered thereto does not evaporate. 40 ° C in a closed atmosphere
When left at the temperature below, a swelling feeling can be similarly 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 that case, before the modification treatment with the chelate compound (I), the Et / VA copolymer fiber, the composite fiber, the yarn or the fiber product is treated at a high temperature below the melting point of the Et / VA copolymer. Below, preferably above 100 ° C and Et / V
Further heat treatment at a temperature of 5 to 10 ° C. lower than the melting point of the A-based copolymer further improves the hot water resistance thereof, which is preferable. When the heat treatment temperature is lower than 100 ° C, the effect of improving the hot water resistance by the heat treatment is small. The heat treatment at that time can be performed by dry heat treatment (infrared heating, hot air heating without 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-treating fibers, composite fibers, yarns and cloths made of an Et / VA type copolymer, when they are subjected to no tension, the appearance of crimps in fibers and yarns and the construction of cloths. The yarn can be bulked and the woven wave can be enhanced to give a bulged product.

In the present invention, the chelate compound (I)
(I) boric acid or a salt of boric acid and a strong acid / strong base; and a modified Et / VA-based copolymer fiber, composite fiber, yarn or fiber product which has been modified by (ii) (a) naphthalene sulfonate or its formalin condensate [hereinafter referred to as "compound (a)"],
(b) an alkyl (poly) oxyalkylene sulfate ester-based compound [hereinafter referred to as "compound (b)"], and (c) a lignin sulfonate-based compound [hereinafter referred to as "compound (c)"] Dyeing is carried out in an acidic region having a pH of 5 or less in a dyeing bath containing at least one kind.

By using the above specific dyeing bath, even if the dyeing treatment is carried out at a bath temperature of 95 ° C. or higher, for example, it is possible to prevent the sticking and adhesion of the fibers, the excessive shrinkage, the deterioration and the like. In addition, it is possible to obtain a dyed product having a deep and good color tone and gloss, and having an extremely excellent feeling and appearance. In particular, in the case of a yarn having a large number of twists or a fiber product such as a cloth using the same, the fibers are largely converged due to the large number of twists, and therefore the excessive adhesion between the fibers due to the high temperature during dyeing. However, in the case of the present invention using the above specific dyeing bath, such excessive adhesion or gluing between fibers can be prevented, and the untwisting force can be expressed, and there is a bulging feeling. It is possible to further improve the dyeing rate of the dye with a good texture,
It is possible to obtain a dyed product which is more excellent in the feeling, appearance and the like.

At this time, when boric acid is added to the dyeing bath alone, the concentration of boric acid is preferably 2 g / liter or more,
It is more preferably 5 g / liter or more. Boric acid and strong acid
If both strong base salts are added, the concentration of boric acid should be 1 g /
It is preferable that the concentration of the salt of a strong acid or a strong base is 1 liter / liter or more. If the concentration is lower than the above,
When the Et / VA-based copolymer fiber is dyed at a temperature of 110 ° C. or higher at high temperature and high pressure, the fiber is apt to cause sticking, shrinkage, deterioration and the like. Examples of strong acid / strong base salts that can be used in combination with boric acid include sodium sulfate, potassium sulfate, sodium chloride, potassium chloride and the like, with sodium sulfate being preferred.

Further, as a preferred example of the compound (a) in which boric acid or a salt of boric acid and a strong acid or a strong base coexists, the following formula (III);

[0040]

[Chemical 6] (In the formula, R ² is hydrogen or an alkyl group, Z is an alkali metal, m is 0 or a number of 1 or more), and a naphthalene sulfonate or a formalin condensate thereof can be mentioned.

In the compound (a) represented by the formula (III),
R ² is hydrogen or an alkyl group having 1 to 5 carbon atoms, Z is sodium or potassium, m is 1 to 10, and preferably 1 to 5. Specific examples of the compound (a) represented by the formula (III) include a formalin condensate of sodium β-naphthalenesulfonate and a formalin condensate of sodium alkylnaphthalenesulfonate.

Preferred examples of the compound (b) include the following formula (IV);

[0043]

[Chemical 7] (In the formula, R ³ is an alkyl group or an alkoxyl group, Z is an alkali metal, p is 0 or a number of 1 or more, and q is a number of 1 or more). Compounds are preferred.

In the compound (c) represented by the formula (IV), R
³ is an alkyl or alkoxyl group having 1 to 20 carbon atoms, Z is sodium or potassium, p is 1 to 25, q
Is preferably a number from 10 to 30. Specific examples of the compound (c) represented by the formula (IV) include sodium methyl polyoxyethylene polyoxypropylene sulfate, sodium methoxypolyoxyethylene polyoxypropylene sulfate, and sodium dodecyl polyoxyethylene sulfate. be able to.

The compound (c) (lignin sulfonate) has been conventionally known as a surfactant or a dispersant, and is mainly produced from a pulp manufacturing waste liquid as a raw material. In the present invention, the compound (c) is Any such lignin sulfonate can be used.

The dyebath may contain only one type of the compounds (a) to (c), or may contain two or more types. Compound (a) to compound in dyeing bath
The concentration of (c) is preferably such that it is about 0.1% by weight or more based on the weight of the fiber, yarn or fiber product to be dyed introduced into the dyeing bath. It is better to make it more than weight%. At that time, it is necessary to set the pH of the dyeing bath to 5 or less, and it is more preferable to set the pH to 4.5 or less.

Compound (a), compound (b), in the dye bath
The concentration of the compound (c) is lower than 0.1% by weight described above,
If the pH of the dyeing bath is higher than 5, the chelate compound
When the fibers, yarns or fiber products of the Et / VA copolymer modified by (I) are dyed especially at high temperature and high pressure of 130 ° C. or higher, the fibers are apt to stick, shrink, deteriorate, etc. It becomes difficult to obtain a dyed product having a perfect appearance.

If the modification ratio of the Et / VA copolymer fiber, yarn or fiber product with the chelate compound (I) is low, for example, about 0.2 to 0.5 mol%, Together with the compound (a) to the compound (c)
Further, when a zirconium compound is contained in the dyeing bath, even when dyeing is performed at a high temperature of 120 ° C. or higher, the fibers are prevented from sticking, shrinking and deteriorating, and the texture, color tone and appearance are very good. It is possible to obtain various dyed products. In that case, the zirconium compound is preferably an inorganic zirconium compound such as zirconium oxychloride; a zirconium salt of an organic acid such as zirconium acetate. The concentration of the zirconium compound in the dyeing bath is based on the weight of the dyed fiber, yarn or fiber product introduced into the dyeing bath,
It is preferably about 1% by weight or more, more preferably 5% by weight or more.

In the dyeing method of the present invention, the dyeing bath temperature is 90 ° C. or more, but the dyeing method is not limited thereto. The dyeing can be carried out in a short time, and the fiber is dyed. The dyeing bath temperature is preferably 11 because the dyeing rate is high and a dyed product having a deep and good color tone is obtained.
It is particularly preferable to keep the temperature at about 0 to 110 ° C.

Furthermore, before the dyeing treatment described above, the formula (I) is used.
A fiber, a composite fiber, a yarn or a fiber product comprising an ethylene-vinyl alcohol copolymer modified with the compound of
Heat treatment at a high temperature below the melting point is more desirable because it can further prevent sticking, shrinkage and deterioration of the fiber, yarn or fiber product during dyeing.

The dyeing method of the present invention is also very effective for a conjugate fiber composed of an Et / VA copolymer and another thermoplastic resin such as polyester which 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, It is said that the temperature should be 110 ° C or higher, preferably 120 ° C or higher.

The conjugate fiber of the present invention comprising the Et / VA copolymer and polyester, which has been modified with the chelate compound (I) and optionally subjected to the above-mentioned high temperature heat treatment, or a fabric comprising the same, is treated with boric acid or boric acid. Strong acid / base salts,
Etching is carried out at a high temperature of 110 ° C. or higher using a dyeing bath having a pH of 5 or less, which contains at least one compound selected from the compounds (a) to (c), and optionally a zirconium compound. Dyeing to the / VA type copolymer and polyester is further improved, and a clear color tone can be obtained. At the same time, no sticking, shrinkage, deterioration or the like occurs in the Et / VA copolymer portion constituting the conjugate fiber, so that the whitening phenomenon, curing, etc. at the time of dyeing is eliminated, and the gloss, texture and appearance are good. A dyed product can be obtained.

In the present invention, when the composite fiber of the modified Et / VA copolymer and another thermoplastic resin is used, the ratio of the modified Et / VA copolymer: the other thermoplastic polymer is: It is desirable to use a weight ratio of 10:90 to 90:10. 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,
Examples thereof include polyvinyl chloride.

As the polyester, terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, phthalic acid, α, β- (4-carboxyphenoxy) ethane,
Aromatic dicarboxylic acids such as 4,4′-dicarboxydiphenyl and 5-sodium sulfoisophthalic acid, aliphatic dicarboxylic acids such as adipic acid and sebacic acid, or their esters with ethylene glycol, diethylene glycol, 1 , 4-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexane-
A fiber-forming polyester synthesized from a diol compound such as 1,4-dimethanol, polyethylene glycol or polytetramethylene glycol can be used, and 80 mol% or more, particularly 90 mol% or more of the constituent units can be used. Polyesters consisting of ethylene terephthalate units 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 /
A 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 above-mentioned composite fiber, 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 dyeing method of the present invention is particularly effective for the conjugate fiber in which the Et / VA-based copolymer is exposed on a part or the whole of the surface of the fiber and the hot water resistance thereof is lowered.

The cross-sectional shapes of the fibers and the conjugate fibers that are the object 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 polygon such as a triangle to an octagon, a T-shape, and a multilobed shape such as a 3 to 8 lobes can be used. Furthermore, those fibers and conjugate fibers can optionally contain optional additives such as optical brighteners, stabilizers, flame retardants, and colorants that are commonly used in fiber-forming polymers. .

In addition, the staining method of the present invention uses the modified Et / V
Long fibers such as monofilaments made of A-based copolymers, short fibers such as staples, filament yarns, spun yarns, mixed fibers and blended yarns of these fibers with natural fibers, semi-synthetic fibers, and other synthetic fibers. It can be applied to any of twisted yarns, and in that case, those fibers may be subjected to any treatment such as false twist crimping treatment and entanglement treatment. Furthermore, the dyeing method of the present invention is a knitted or woven fabric made from the above fibers or yarns,
It can be applied to any of non-woven fabric, final clothing, and textile products such as towels.

Et modified with a chelate compound (I)
/ VA-based copolymer fiber and composite fiber, cotton, silk, hemp,
When mixed-spun or interwoven with natural fibers such as wool, the presence of these natural fibers results in chelate compounds.
In some cases, the modification of the Et / VA copolymer by (I) may be hindered and the hot water resistance may not be improved. In that case, before mixing or weaving with natural fibers, Et /
Fibers or composite fibers made of VA-based copolymers
The hot water resistance can be improved by first modifying the chelate compound (I) in the form of a yarn such as cheese, heat-treating it, and then mixing or knitting it with natural fibers.

The Et / VA-based copolymer fiber or the composite fiber is modified with the chelate compound (I) in a circular knitted form, and then heat-treated at a high temperature to provide crimp, and then the circular knit is unwound. A crimped yarn is obtained by knitting or weaving the crimped yarn alone or after weaving or weaving the crimped yarn with a natural fiber, and then subjected to the dyeing treatment of the present invention, a soft feeling is further excellent and a good texture is obtained. It is possible to obtain a stretchable fabric dyed with an extremely good color tone.

[0061]

[Examples] The present invention will be specifically described below with reference to Examples, but the present invention is not limited thereto. In the following Examples and Comparative Examples, the compound (Ia) represented by the above formula (Ia) was used as the chelate compound (I). In the following Examples and Comparative Examples, the modification ratio of the alcoholic hydroxyl group in the Et / VA copolymer with the compound (Ia) and the degree of darkness of the dyed product were measured by the following methods. The degree of adhesion between the yarns in the dyed fabric is evaluated by cutting the dyed fabric in the horizontal direction, observing the cut surface with a microscope, and evaluating it according to the evaluation criteria shown in Table 1 below. Further, the evaluation of hot water resistance was carried out by checking the presence or absence of gloss and the texture before and after dyeing the fabrics obtained in each example according to the evaluation criteria shown in Table 1 below.

Change of alcoholic hydroxyl group by compound (Ia)
Measurement of sex 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 the degree of darkness of the dyed product: The reflectance of the dyed product was measured using a spectrophotometer (Hitachi 307 color analyzer; manufactured by Hitachi Ltd.), and the reflectance at the maximum wavelength on the spectral reflectance curve was measured. From (R), it is shown by the following mathematical formula 1.
K / S that expresses the degree of darkness using the Kubelka-Munk formula
The value was calculated. In Formula 1 below, the higher the K / S value, the higher the darkness of the dyed product.

[0064]

## EQU1 ## K / S = (1-R) ² / 2R

[0065]

[Table 1] Evaluation of fabric after dyeing Evaluation criteria for the degree of adhesion between yarns of a fabric : ◎ ・ No adhesion between yarns is observed at all ○ ・ ・ Adhesion between yarns is recognized but is 10% or less △ ・ ・ At a rate of about 10 to 80% Adhesion between yarns is recognized ..... Adhesion between yarns is recognized at about 80% or more. Fabric gloss evaluation criteria : ◎ ・ ・ Deep and very good gloss ○ ・ ・ Deep and good gloss △ ・ ・ Slightly poor gloss with a little lack of depth × ・ ・ White and no depth at all Evaluation criteria for the texture of the fabric : ◎ ・ Soft and swelling with extremely good texture ○ ・ ・ Soft and good texture △ ・ ・ Slightly sticky and slightly lacking in softness × ・ ・ The degree of sticking is large , Hard and bad feeling

Example 1 Methanol was used as a polymerization solvent, and azobis-4-methyloxy-2,4-dimethylvaleronitrile was used as a polymerization initiator.
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 satin woven fabric was manufactured using this multifilament as a warp and a weft. The above-mentioned greige satin fabric was treated with sodium hydroxide at 1 g / liter and Actinol R-100.
(Surfactant: Matsumoto Yushi Co., Ltd.) is treated with an aqueous solution containing 0.5 g / liter at 80 ° C. for 30 minutes for desizing, and then has the following treatment bath composition containing the compound (Ia). It was put in a treatment bath and impregnated at room temperature for 10 seconds.

Treatment bath composition Compound (Ia) (Sebran CR-N: Purity 25%) 4% Hexamethylenetetramine 0.2% (1/20 concentration to Zebran CR-N)

The satin fabric was then removed from the treatment bath and squeezed with a mangle to 60% impregnation. This was wound around a beam, the wound cloth was put in a polyethylene bag, rotated for 24 hours, taken out from the bag, pre-dried at 70 ° C., and heat-treated at 150 ° C. for 1 minute. At this point, the modification ratio of the alcoholic hydroxyl group in the Et / VA copolymer fiber constituting the cloth with the compound (Ia) was 0.5 mol% as measured by the above method.

The satin woven fabric modified with the compound (Ia) obtained above was dipped in a dyeing solution having the dyeing composition shown in Table 2 below and dyed at 115 ° C. for 40 minutes.

[0071]

[Table 2] Composition of dyeing liquid Dye: Sumikaron Blue SE-RPD (Sumitomo Chemical Co., Ltd.) 2% owf Additive: Compound (a) ¹⁾ (Kamo Demol SNB) As shown in Table 3 Compound (b) ²⁾ (Nika Kagaku Nikka ⁾ Sun salt 7000) As shown in Table 3 Compound (c) ³⁾ (Vanilex N manufactured by Sanyo Kokusaku Pulp Co., Ltd.) As shown in Table 3 pH adjustment As shown in Table 3 Boric acid concentration As shown in Table 3 Sodium sulfate concentration As shown in Table 3 1) Formalin condensate of sodium naphthalene sulfonate and sodium butyl naphthalene sulfonate (containing about 3 sodium naphthalene sulfonate groups) 2) Main component: sodium polyoxypropylene oxyethylene dodecyl ether sulfate (about 2 oxypropylene units)
, 14 oxyethylene units) 3) Sodium lignin sulfonate

The fabric is then removed from the dyebath and
Normal reduction washing was performed at 0 ° C. The hot water resistance was investigated by evaluating the degree of adhesion between the yarns constituting the dyed fabric obtained as a result of high-temperature dyeing at 115 ° C., the texture of the dyed fabric and the degree of gloss by the methods described above. The results are shown in Table 3 below.

[0073]

[Table 3]

From the results in Table 3 above, boric acid and compounds
Et / VA modified with compound (Ia) using a dyeing bath containing at least one of (a) to compound (c) and having a pH of 5 or less.
Nos. 7 to 1 for dyeing a woven fabric made of a system copolymer
It can be seen that in Nos. 0 and 13, there is no adhesion between the constituent yarns of the woven fabric, and it is possible to obtain a dyed woven fabric which is excellent in swelling feeling, drapability and suppleness and has a deep color tone.
On the other hand, boric acid is not contained or the compound (a) to
Dyeing bath without any of compound (c), or pH
In the case of Experiment Nos. 1 to 6 and 11 to 12 using the dyeing bath having a value of higher than 5, adhesion between the yarns constituting the woven fabric occurs, and the feel and feel of the dyed woven fabric are deteriorated. , It turns out to be white and dyed in a deep color tone.

Example 2 An Et / VA copolymer (intrinsic viscosity [η] = 1.10 dl / g) having a saponification degree of 99% and an ethylene content of 44 mol% and isophthalic acid of 8 mol% were used together. 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 was woven by weft-inserting two M and S twist 2500 T / M strong twist yarns alternately. The greige density was 164 warps / dimension and 97 wefts / dimension.

The natural satin crepe obtained above was tensed by a Shrink Suffer machine without tension.
A dry heat treatment at 50 ° C. was performed. Then, after performing refining desizing treatment at 80 ° C. for 30 minutes using a liquid containing 1 g / liter of sodium hydroxide and 0.5 g / liter of actinol R-100 (surfactant: manufactured by Matsumoto Yushi Co., Ltd.) The mixture was placed in a treatment bath having the following treatment bath composition containing the compound (Ia) and impregnated at room temperature for 10 seconds.

Treatment bath composition Compound (Ia) (Zebran CR-N; Purity 25%) 5% Glycerin 2% Hexamethylenetetramine 0.2%

The fabric was then removed from the treatment bath and squeezed with a mangle to 60% impregnation. Wind this on a beam,
The rolled fabric was put in a polyethylene bag, rotated for 24 hours, taken out from the bag, pre-dried at 70 ° C., and then heat-treated at 150 ° C. for 1 minute. At this time, the modification ratio of the alcoholic hydroxyl group in the Et / VA copolymer fiber constituting the cloth with the compound (Ia) was measured by the above method, and was 0.6 mol%. The woven fabric modified with the compound (Ia) obtained above was dipped in a dyeing solution having the dyeing composition shown in Table 4 below and dyed at 135 ° C. for 40 minutes.

[0080]

[Table 4] Composition of dyeing liquid Dye: Kayalon Polyester Black G-SF (Nippon Kayaku) 12% owf Additive: Compound (a) ¹⁾ (Sanyo Kokusaku Pulp Co., Ltd. Paflex N) 2% owf pH adjustment 3.5 Boric acid concentration 20 g / l Sulfuric acid Sodium concentration 20 g / liter Zirconium acetate concentration As shown in Table 5, bath ratio 50: 1

Then, the cloth was taken out from the dyeing bath and subjected to reduction washing at 70 ° C. for 30 minutes using a solution containing 1 g / l of hydrosulfite and 1 g / l of sodium carbonate. The hot water resistance was investigated by evaluating the degree of adhesion between the yarns constituting the dyed fabric obtained as a result of high-temperature dyeing at 135 ° C., the texture of the dyed fabric and the degree of gloss by the above-mentioned methods. The results are shown in Table 5 below.

<Embodiment 3> No tension state before desizing, 1
Satin crepe production, dyeing treatment, and final heat treatment were performed in the same manner as in Example 2 except that dry heat treatment at 50 ° C. was not performed. The hot water resistance was investigated by evaluating the degree of adhesion between the yarns constituting the obtained dyed fabric, the feel of the dyed fabric and the degree of gloss by the above-mentioned methods. The results are shown in Table 5 below.

Comparative Example 1 A satin crepe was produced in the same manner as in Example 2 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 135 ° C. I went. The hot water resistance was investigated by evaluating the degree of adhesion between the yarns constituting the obtained dyed fabric, the feel of the dyed fabric and the degree of gloss by the above-mentioned methods. The results are shown in Table 5 below.

[0084]

[Table 5]

From the results in Table 5 above, boric acid and compounds
Using a dyeing bath containing (a) and having a pH of 5 or less, the compound (I
When dyeing a woven fabric composed of the Et / VA-based copolymer modified in a), if the woven fabric is heat-treated before the dyeing treatment, and if a zirconium compound is added to the dyeing bath, the woven fabric is formed between the constituent yarns. It can be seen that it is possible to prevent the adhesion more satisfactorily, and to obtain a dyed product which is more excellent in terms of swelling feeling, drapeability and suppleness, and deep color tone. In addition, from the results of Table 5, compound (Ia)
In the case of a woven fabric made of an Et / VA-based copolymer which has not been modified with, when dyed with a dyeing bath containing boric acid and the compound (a) at a pH of 5 or less, the woven fabric is heat-treated before the dyeing treatment. In both cases, the zirconium compound was added to the dyeing bath,
It can be seen that adhesion occurs between the yarns constituting the woven fabric, the texture and feel of the dyed woven fabric are significantly reduced, and the dyed product is white and has no deep tone.

[0086]

EFFECT OF THE INVENTION Et / modified with chelate compound (I)
A fiber product such as a fiber, thread or cloth made of a VA-based copolymer, which contains boric acid or a salt of boric acid and a strong acid or a strong base, and at least one of compounds (a) to (c) and has a pH of 5 or less. In the case of the dyeing method of the present invention in which the dyeing bath is used, high-temperature dyeing is possible, and even when heating at the time of dyeing, no sticking or adhesion between fibers or yarns occurs, so that the texture is hardened and the appearance is improved. It is possible to obtain a dyed product which is free from deterioration and loss of gloss and has a good feeling such as swelling feeling, drapeability, firmness and elasticity. Moreover, the use of the compound (a), the compound (b) and / or the compound (c) further improves the darkening of the dyed product, so that it is not whitish,
It is possible to obtain a dyed product having a deep and extremely good color tone. The above-mentioned effects of the present invention can be further enhanced by subjecting the fabric to a heat treatment before the dyeing treatment and by further containing a zirconium compound in the dyeing bath.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location D06P 3/82 7306-4H 5/20 9160-4H (72) Inventor Kazuhiko Tanaka Sakazu, Kurashiki-shi, Okayama 1621 Kuraray Co., Ltd. (72) Inventor Masao Kawamoto 1621 Sakata, Kurashiki City, Okayama Prefecture Kuraray Co., Ltd.

Claims (5)

[Claims] 1. 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): (Wherein M represents a metal atom having a chelate-forming ability, R ¹ represents an alkyl group, and X represents a halogen atom), and is a modified ethylene-vinyl alcohol copolymer copolymer modified with at least one compound represented by Fibers made of coalescing,
(I) boric acid, or a salt of boric acid and a strong acid / strong base; and (ii) (a) naphthalene sulfonate or its formalin. An acidic region having a pH of 5 or less in a dyeing bath containing at least one compound selected from a condensate, (b) an alkyl (poly) oxyalkylene sulfate ester-based compound, and (c) a ligninsulfonate compound. A method for dyeing a fiber, a composite fiber, a yarn or a fiber product made of a modified ethylene-vinyl alcohol-based copolymer, which is characterized by dyeing with. 2. The dyeing method according to claim 1, wherein the dyeing bath further contains a zirconium compound. 3. A fiber, composite fiber, yarn or fiber product comprising an ethylene-vinyl alcohol copolymer modified with a compound of formula (I) is subjected to a high temperature below its melting point before dyeing treatment. The dyeing method according to claim 1 or 2, wherein heat treatment is performed. 4. Ethylene modified with a compound of formula (I)
Fibers made of vinyl alcohol copolymer, composite fibers,
The yarn or textile is a neutralizing agent in addition to the compound of formula (I);
And / or a fiber, a composite fiber, a yarn or a fiber product made of an ethylene-vinyl alcohol copolymer by using a treating agent further containing at least one hydroxyl group-containing compound selected from glycerin, ethylene glycol, polyethylene glycol and isopropyl alcohol. 4. The dyeing method according to any one of claims 1 to 3, which is obtained by denaturing. 5. A dyed product obtained by the method according to any one of claims 1 to 4.