JP2899151B2 - Cationic dye-dyeable ethylene-vinyl alcohol copolymer fiber and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber product such as ethylene-vinyl alcohol-based copolymer fiber, yarn, cloth and the like which has a good feeling and is dyeable with a cationic dye, and a method for producing the same. More specifically, the present invention relates to the above-described fibers, yarns, and fiber products which are dyeable with a cationic dye and exhibit vivid coloration and light-collecting properties not found in conventional synthetic fibers.

[0002]

2. Description of the Related Art Synthetic fibers such as polyester and polyamide are monotonous in their denier and cross-sectional shape.
Woven fabric, knitted fabric, when made into a fiber structure such as nonwoven fabric, compared with fiber structure made of natural fibers such as cotton and hemp,
The gloss and the like were monotonous and cold, and tended to be low quality products. In addition, synthetic fibers produced by melt spinning have a specific specular gloss, and when dyed, have drawbacks such as difficulty in obtaining vividness and color depth compared to natural fibers such as wool and silk.

[0003] In recent years, in order to remedy such drawbacks in synthetic fibers, deformation of the fiber cross section, crimping, formation of composite fibers, and various other methods have been attempted. As an example, a method of forming a composite fiber of an easily soluble polymer and polyester and then performing post-processing to impart a feeling of tingling and unique gloss to the fabric by dry touch (Japanese Patent Application Laid-Open No. 56-165015) JP-A-57-5921, JP-A-58-98425 and JP-A-61-239010), a method of improving the feel by providing unevenness in the length direction of the fiber (Japanese Patent Publication No. 51-7207). issue,
JP-A-58-70711, JP-A-62-133118
No. 53-35633, and Japanese Patent Publication No. 56-162.
No. 31, JP-A-63-6161) and the like.

As another example, a method of producing false twisted / fused yarn to impart hemp-like sharpness (Japanese Patent Publication No. 45-1)
No. 8072), a method of preparing a mixed fiber fusion-processed yarn (JP-A-63-6123), a method of making polyester fibers dyeable with a cationic dye (Japanese Patent Publication No. 34-10479),
A method of forming ultra-fine irregularities on the fiber surface to suppress specular gloss and produce a deep color (Japanese Patent Publication No. 59-24233) can be mentioned.

However, any of the above-mentioned methods
It was not satisfactory enough to give synthetic fibers a feeling similar to that of natural fibers, and also to give good color developability and vivid colors as in triacetate fibers and acrylic fibers. In addition, synthetic fibers such as polyester are inferior in hydrophilicity and water absorption, and thus are inferior to natural fibers such as cotton and hemp in terms of comfort.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a natural dye which is excellent in color development after dyeing, has a vivid coloration and can exhibit light-collecting properties, and is soft and excellent in bulkiness. Synthetic fibers with good texture and good hygroscopicity and water absorption similar to fibers can be easily obtained without causing troubles or undesirable coloring of fibers in the polymer design, fiberization process, and post-processing process. is there.

[0007]

Means for Solving the Problems The present inventors have continued research to achieve the above object. As a result, they have found that the above-mentioned object can be achieved by forming a fiber from an ethylene-vinyl alcohol copolymer and introducing a specific sulfonic acid group or a sulfonate (sulfonate) group into the fiber, thereby completing the present invention.

That is, in the present invention, the basic skeleton is composed of an ethylene-vinyl alcohol-based copolymer, and the alcoholic hydroxyl group in the copolymer has the formula:> CH- (CH ₂ ) _n —SO ₃ M (I) wherein n is an integer of 1 to 10, and M is hydrogen or a formula
(I) sulfoxyl group -SO ₃ of ^- and salt-modified are modified by at least one of the groups represented by showing a cation] capable of forming an ethylene - is a fiber comprising a vinyl alcohol copolymer.

Further, the present invention relates to a composite fiber comprising a modified ethylene-vinyl alcohol copolymer modified with at least one of the groups represented by the above formula (I) and another thermoplastic polymer. is there. The present invention also encompasses yarns, fiber products, and methods for producing the same, which comprise the above fibers and / or composite fibers.

The fibers, conjugate fibers, yarns and fiber products modified by the group represented by the above formula (I) include fibers made of ethylene-vinyl alcohol copolymer, ethylene-vinyl alcohol copolymer and other fibers. composite fibers comprising a thermoplastic polymer or yarns and fibers obtained therefrom, of the _{formula: OHC- (CH 2) n -SO} 3 M (Ia) ( wherein, n and M are as defined above ), And the formula:

[0011]

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Wherein n and M are the same as above.
After acetalization using at least one of the compounds represented by the formula (1), when the group M is hydrogen, it can be produced by treating it with an alkali compound as necessary to convert the sulfonic acid group into a salt form. The present invention also includes such a manufacturing method.

Ethylene which is a basic skeleton of the fiber of the present invention
The vinyl alcohol-based copolymer (hereinafter referred to as “Et / VA-based copolymer”) has a repeating unit ratio of ethylene of about 30 to 70 mol%, and the remainder is vinyl alcohol alone or vinyl alcohol and other alcohols. What consists of a repeating unit of a vinyl monomer is preferable.

When the proportion of ethylene units in the copolymer is 3
If the amount is less than 0 mol%, that is, if the proportion of the vinyl alcohol unit is more than 70 mol%, the spinnability at the time of fiberization becomes poor and single yarn breakage and breakage during spinning or drawing increase, and moreover, It lacks flexibility. Also, E
In a composite fiber comprising a t / VA copolymer and another thermoplastic polymer, when a high melting point polymer such as polyethylene terephthalate is used as the other thermoplastic polymer, a high spinning temperature of usually 250 ° C. or higher is used. The temperature is used. In this case, if the proportion of the ethylene unit is less than 30 mol%, the heat resistance of the Et / VA copolymer becomes insufficient, and good conjugate fibers cannot be obtained.

On the other hand, when the proportion of the ethylene unit exceeds 70 mol%, the proportion of the vinyl alcohol unit, ie, the hydroxyl group is inevitably reduced, so that the hydrophilicity of the fiber is lowered and a natural fiber-like feeling is obtained. Disappears. In addition, the above equation
The modification ratio by the group represented by (I) [hereinafter referred to as “group (I)”] decreases, and it becomes impossible to impart the cationic dye dyeability, which is characterized by the desired sharpness, to the fiber. Become. From the viewpoint that good cationic dyeability and hydrophilicity can be imparted, the ratio of vinyl alcohol units in the Et / VA copolymer is about 30 to 70 mol%, particularly about 40 to 70 mol%.
Desirably, it is mol%.

Here, the Et / VA-based copolymer constituting the basic skeleton may be a non-crosslinked chain-like one or a crosslinked one by an appropriate method as described later. . This Et / VA copolymer can be obtained by saponifying the vinyl acetate portion of the ethylene / vinyl acetate copolymer, in which case the degree of saponification is about 9
It is good to be 5% or more. When the degree of saponification decreases, not only the crystallinity of the copolymer decreases, but also the physical properties such as strength decrease, but the copolymer also easily softens, causing troubles in the fiberizing step, and the obtained fiber. The feeling is inferior, which is not preferable.

As the Et / VA copolymer, it is generally preferred to use one having a number average molecular weight of about 8,000 to 20,000. Et / VA copolymer are, for example, Ltd. under the trade name EVAL ^R from Kuraray and Nippon Synthetic Chemical Industry Co., Ltd. is commercially available under the trade name Soarnol ^R from readily available. However, a commercially available copolymer of ethylene and vinyl acetate is purchased and saponified, or an Et / vinyl acetate copolymer is produced from ethylene and vinyl acetate by radical polymerization or the like and saponified. May be.

In any case, when an alkali metal ion such as sodium ion or potassium ion or an alkaline earth metal ion such as calcium or magnesium is present in the Et / VA copolymer, the main chain is cleaved in the copolymer. , Side chain elimination, excessive cross-linking, etc. occur, lowering the thermal stability of the copolymer, thread breakage during spinning due to gelation of the copolymer, clogging of the spinning filter, and the accompanying pressure reduction of the spin pack. It causes a sharp rise, shortens the life of the nozzle, etc., so that the content of these ions is minimized, usually about 100 ppm or less, preferably 50 ppm or less, more preferably 10 p
pm or less.

In the fiber, yarn and fiber product of the present invention, the alcoholic hydroxyl group in the Et / VA copolymer must be modified with at least one of the above groups (I). The Et / VA copolymer has one type of group (I).
Or two or more groups
It may be modified by (I).

The modification ratio of the Et / VA copolymer with the group (I) is about 0.1 to 30 mol%, particularly 1 to 10 mol%, based on the number of moles of vinyl alcohol units in the copolymer.
It is preferred that The number of moles of the vinyl alcohol unit as used herein refers to a saponified vinyl alcohol unit, an unsaponified vinyl acetate unit, or such a group when the hydroxyl group of vinyl alcohol is converted to an ether group or the like by acetalization or the like. Means the total number of moles. If the modification ratio of the vinyl alcohol unit by the group (I) is less than 0.1 mol%, the dyeing seat of the cationic dye is insufficient, so that a sufficient density of color development cannot be obtained, which is not preferable. On the other hand, when the modification ratio exceeds 30 mol%, the swelling of the Et / VA-based copolymer fiber in water becomes too large and the dimensional stability is deteriorated. The feeling becomes worse.

In the modification of the alcoholic hydroxyl group with the group (I), fibers or conjugate fibers are produced by melt spinning from an Et / VA copolymer, and if necessary, a fiber product such as a yarn or fabric is further produced from the fibers. Or by using a commercially available Et / VA-based copolymer fiber, yarn, fiber product, or the like, converting them into the compound represented by the above formula (Ia) or (Ib) (Ia) and compound (Ib)], and when M is hydrogen, then, if necessary, further treat with an alkali compound to convert the sulfonic acid group into a salt (sulfonate group). Performed by

The above-mentioned acetalization treatment of the fibers or fiber products of the Et / VA copolymer is preferably carried out using a strong acid such as sulfuric acid or hydrochloric acid as an acetalization catalyst. It is desirable to use The concentration of the strong acid is preferably about 0.1 to 2 normal, particularly preferably 0.2 to 1 normal. If the concentration of the strong acid is lower than 0.1N, the acetalization with the compound (Ia) and / or the compound (Ib) is not sufficiently performed, and even when dyed with a cationic dye, the dyed product has a satisfactory color tone with excellent sharpness. Can not be obtained. On the other hand, if the concentration of the strong acid is higher than 2N, the fibers become brittle, which is not desirable. The temperature of the acetalization reaction is about 40 to 110 ° C.
If the temperature is lower than 40 ° C., the acetalization reaction rate is extremely low, and the acetalization cannot be performed efficiently. It is not desirable because it may cause the formation of a polymer.

The concentration of compound (Ia) and / or compound (Ib) in the acetalization treatment solution is such that the total amount of both compounds is about 0.005 to 0.5 mol per liter of treatment solution,
Preferably, it is 0.02 to 0.2 mol. When the concentration of the aldehyde compound (Ia) and / or the compound (Ib) is lower than 0.005 mol / liter, the proportion of the group (I) introduced into the ethylene-vinyl alcohol copolymer is reduced, and good cations are obtained. Dye dyeability cannot be obtained.

The above acetalization treatment and, if necessary, subsequent treatment with an alkali compound give the group (I)
Each of the two bonds (i.e.,> C on one side) are bonded to the alcoholic hydroxyl group of the Et / VA-based copolymer via -O- (acetal bond), and
A modified polymer in which the group (I) is pendantly bonded to the main chain of the Et / VA copolymer is formed.

As described above, the group (I) and the compound (Ia)
And in the compound (Ib), n is an integer of 1 to 10, and M is hydrogen or a cation capable of forming a salt with a sulfonic acid group. Among them, n is preferably an integer of 5 to 8, and in particular, compound (Ia) and compound wherein n is 7
(Ib) is preferable because it has good reactivity with the alcoholic hydroxyl group in the Et / VA copolymer. M is preferably a cation, and as the cation, various metal ions;
Ammonium ions, quaternary ammonium ions, and the like can be given. When M is a divalent or higher cation,
Its valence equal to the number of sulfoxyl group (sulfoxyl anion) -SO ₃ ^- and ionically bonded to form a salt. M is preferably an alkali metal ion such as sodium or potassium, an alkaline earth metal ion such as calcium or magnesium, or an ammonium ion. Among them, sodium ion and potassium ion can exhibit the dyeing ability of a cationic dye to the maximum. preferable.

The fibers, yarns, and fiber products of the Et / VA copolymer are acetalized with the compound (Ia) and / or the compound (Ib) in which M is hydrogen, and then treated with an alkali compound and introduced. When the sulfonic acid group is in the form of a salt (sulfonate group), the salt forming treatment can be performed at any stage before the final product is obtained, and it is particularly preferable to perform the treatment before dyeing. The formation of a salt can be achieved by compound (I) wherein M is hydrogen.
a) and / or a fiber product such as a fiber, a yarn or a fabric into which the group (I) has been introduced by acetalization treatment with the compound (Ib) is converted to an alkali metal or alkaline earth metal hydroxide, carbonate, ammonium hydroxide. Or by immersing in an aqueous solution of a salt-forming agent such as an amine, or by applying the aqueous solution of the salt-forming agent to fibers, threads, textiles, or the like by a method such as padding, spraying, or showering. As the salt forming agent (alkali compound) at that time, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, calcium hydroxide, magnesium hydroxide and the like are particularly preferable.

The compound (Ia) and compound (Ib) used in the present invention, in which a linear aliphatic group having 1 to 10 carbon atoms is bonded to a sulfonic acid group or a sulfonate group, is an Et / VA copolymer. It has excellent reactivity with alcoholic hydroxyl groups in it, so it is possible to lower the reaction temperature during acetalization and reduce the acid catalyst concentration, and as a result, it is possible to suppress coloring during acetalization. it can.

On the other hand, aromatic aldehyde compounds having an aromatic sulfonate group or a sulfonic acid group such as sodium ortho-benzaldehyde sulfonate other than the compounds (Ia) and (Ib) are Et /
The reactivity with the alcoholic hydroxyl group in the VA copolymer is extremely low, and it is necessary to raise the reaction temperature for acetalization and increase the acid catalyst concentration. For this reason, it causes coloring during acetalization and makes it impossible to dye, or lowers the commercial value of textile products. When an aliphatic group bonded to a sulfonic acid group or a sulfonate group is a branched aliphatic or an aliphatic aldehyde compound is used, the same as when an aromatic aldehyde compound is used. Leads to poor results.

The modified Et / VA copolymer acetalized with the compound (Ia) and / or the compound (Ib) is
Usually, it has a melting point of about 150 to 180 ° C., and in hot water, a phenomenon of melting point drop occurs, and it becomes easy to soften even at 150 ° C. or less. Therefore, depending on the processing method and conditions, a softening phenomenon may be caused to cause sticking between the single fibers and the feeling may become hard. Therefore, the Et / VA copolymer may be cross-linked as described below. .

That is, E before the acetalization treatment is performed.
The t / VA-based copolymer or the modified Et / VA-based copolymer after acetalization with the compound (Ia) and / or the compound (Ib) is improved in its softening point, heat resistance, hot water resistance and the like. Therefore, crosslinking can be performed separately from the above-mentioned modification treatment. As a crosslinking method at that time, any method known as a crosslinking method of a vinyl alcohol unit-containing copolymer can be adopted, for example, a divinyl compound, a monoaldehyde represented by formaldehyde, an aldehyde compound such as a dialdehyde, Examples of the crosslinking include crosslinking with an organic crosslinking agent such as polyisocyanate such as diisocyanate, crosslinking with an inorganic crosslinking agent such as a boron compound, and crosslinking with radiation or light such as γ-ray or electron beam.

For example, when the cross-linking acetalization treatment is performed with dialdehyde, it is preferable to use a strong acid such as sulfuric acid, hydrochloric acid, formic acid or the like. In this case, the concentration of the strong acid used is about 0.05.
~ 5 normal, the concentration of dialdehyde solution is about 0.2 ~ 500
g / liter, and the reaction temperature is preferably about 15 to 135 ° C. Glutaraldehyde as the dialdehyde,
1,9-Nonandial, 2-methyl-1,8-octanedial and the like have a high reaction rate and are practically preferable. The degree of crosslinking acetalization with dialdehyde is preferably about 2 to 5 mol% with respect to the alcoholic hydroxyl group unit from the viewpoints of resistance to high-temperature dyeing at 110 ° C. or higher and iron resistance, etc. When higher, compound (Ia)
And / or the degree of acetalization by compound (Ib) is undesirably reduced. If unreacted aldehyde remains after the cross-linked acetalization treatment, the dyed product may be discolored. Therefore, it is preferable to oxidize with an oxidizing agent to form a carboxylic acid or a salt thereof.

The above-mentioned cross-linking treatment may be carried out before, simultaneously with, or after the denaturation treatment of the fiber, the conjugate fiber, the yarn or the fiber product with the compound (Ia) and / or the compound (Ib). It may be performed at a stage, and particularly preferably performed after the modification treatment, from the viewpoint of processability, workability, and the like. Therefore, in the present invention, at least one of the groups (I)
Fibers, conjugate fibers, yarns and fiber products comprising a seed-modified Et / VA copolymer include both those not subjected to the above-mentioned cross-linking treatment and those subjected to the cross-linking treatment.

Further, as described above, the present invention provides a compound of the formula (I)
In addition to the fiber consisting of the modified Et / VA copolymer alone, a composite fiber consisting of the modified Et / VA copolymer and another thermoplastic polymer is included. When a composite fiber is used, the composite ratio of the modified Et / VA copolymer: other thermoplastic polymer is about 10:90 to 90: 1 by weight.
It is desirable to set it to 0. If the ratio is out of this range, the composite ratio becomes unbalanced, and the spinnability tends to be poor. As the other thermoplastic polymer used for the conjugate fiber, from the viewpoint of heat resistance and dimensional stability, it is preferable to use a crystalline thermoplastic polymer having a melting point of 150 ° C. or more, and a typical example thereof is a fiber-forming polymer. Polyester, polyamide, polyolefin, polyvinyl chloride and the like.

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

In the case of a composite fiber composed of a modified Et / VA copolymer and polyester, shrinkage may occur in the modified Et / VA copolymer during the dyeing treatment under high temperature and high pressure. In such cases, shrinkage can be prevented by dyeing in the presence of one or more of a salt of a strong acid or strong base and boric acid in the dyeing solution.

The composite form of the composite fiber can be any form such as a core-in-sheath type, a sea-island type, a bonded type, or a mixed type thereof. In the case of the core-sheath type, any of a two-layer core-sheath type and a multilayer core-sheath type having three or more layers may be used. In the case of 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 a fiber cross section perpendicular to the fiber length direction, the bonding surface may be in any state of a straight line, an arc, or any other random curved shape, The plurality of bonding portions may be parallel to each other, may be radial, or may have any other shape.

In the composite fiber of the present invention, the modified Et /
Other thermoplastic polymers to be combined with the VA copolymer are:
It may be a kind or two or more kinds. In any case, in order to impart good cationic dyeability to the conjugate fiber of the present invention, a part or the entire surface of the fiber is used.
It is preferable that the Et / VA copolymer modified with (I) is exposed and present, and in particular, 10% or more of the fiber surface is made of the Et / VA copolymer modified with the group (I). Good to be. On the other hand, when the entire fiber surface is covered with the other fibers described above, it becomes difficult to impart cationic dye dyeability.

The cross-sectional shape of the fiber and the conjugate fiber of the present invention may be any shape, and may be circular or irregular. In the case of an irregular cross section, for example, a flat shape, an elliptical shape, a rectangular shape such as a triangle to an octagon, a T-shape,
Any shape such as a multi-leaf shape such as a 3 to 8 leaf shape can be used. Further, the fiber and the conjugate fiber of the present invention may contain optional additives such as a fluorescent whitening agent, a stabilizer, a flame retardant, and a coloring agent which are usually used in the fiber-forming polymer, if necessary. it can. Further, the fiber and yarn of the present invention,
Long fibers such as monofilaments, short fibers such as staples,
Any of a filament yarn, a spun yarn, a mixed fiber of the fiber of the present invention with a natural fiber, a semi-synthetic fiber, and other synthetic fibers, a mixed spun yarn, and a ply-twisted yarn may be used. Further, the fiber of the present invention may have been subjected to any treatment such as false twist crimping and entanglement. Furthermore, the fiber product of the present invention may be any of knitted and woven fabrics, nonwoven fabrics, and final garments made of such fibers and yarns, and is particularly suitable as outer garments.

When the above-mentioned fiber, yarn and fiber product of the present invention containing the Et / VA copolymer modified with the group (I) is dyed with a cationic dye, a color which cannot be obtained with conventional synthetic fibers is obtained. , A fiber, a yarn, and a fiber product having extremely good color developability, exhibiting the depth, vividness, light-collecting property, and the like.

[0040]

The reason for having extremely good coloring properties cannot be stated at this time, but is presumed to be due to the following reasons.
The intrinsic molecular extinction coefficient (ε) of the dye (“Fiber and Industry” 196
No. 9, 2, No. 6) has an azo type disperse dye of about 2.8 × 10
^{In 4} , the anthraquinone-based disperse dye is about 1.3 × 10 ⁴ , whereas the cationic dye is as large as about 4.7 × 10 ⁴ . Therefore, the cationic dye has a higher light absorption and less reflection than the disperse dye, so that a deep color is easily developed. This is supported by the fact that the polyester fiber obtained by copolymerizing sodium 5-sulfoisophthalate with a cationic dye has a greater color depth than the conventional polyester fiber dyed with a dispersion fiber.

However, polyester fibers obtained by copolymerizing sodium 5-sulfoisophthalate have an increased color depth, but still have insufficient color vividness. The reason that the fiber of the present invention has a sharper color and more improved coloring property than the conventional cationic dye dyeable polyester fiber copolymerized with 5-sulfoisophthalic acid sodium salt is because the fiber It is believed to be related to the refractive index of the resulting polymer.

That is, the refractive index of polyester fiber is 1.73 and that of silk is 1.59, while the refractive index of silk is 1.59.
The refractive index of the fiber composed of the Et / VA copolymer modified by (I) slightly varies depending on the ethylene content, but is about 1.5, which is lower than that of polyester fiber or silk. . By the way, as is well known as a post-processing agent for textile products, when a material having a low refractive index is applied to a fiber surface with a low refractive index, when the fiber surface is wetted with water, which is generally referred to. Such a wet feather color is exhibited, and the vividness of the dyed product is further improved. For this reason,
In the fiber of the present invention having a low refractive index comprising the Et / VA copolymer modified with (I), the color depth based on the above-described large molecular extinction coefficient by the cationic dye and the color sharpness due to the low refractive index are improved. It is considered that both of these are expressed, and extremely good color developability appears.

Further, the fiber of the present invention having a low refractive index comprising the Et / VA copolymer modified with the group (I) is formed into a colorless and transparent fiber, and the transparent fiber is converted into a cationic dye exhibiting a fluorescent color. In the case of dyeing in the later, as a result of absorbing direct light and dispersed light from the surroundings, and the absorbed light is emitted as fluorescent light, it will exhibit a fluorescent color having a strong light shine, Surprisingly, it has also been found that when viewed from the cross-sectional direction, a very bright color tone having a light-collecting property is obtained. Such a thing was not known at all, and was first discovered by the present inventors.

[0044]

The present invention will be specifically described below with reference to examples and the like. In the following Examples and Comparative Examples, Compound (Ia)
(Ie Et / OH / (CH ₂ ) ₇ —SO ₃ Na
The modification ratio (mol%), dyeing rate (%), K / S value, lightness (%) and chroma (%) of the alcoholic hydroxyl group in the VA copolymer were measured as follows. The feeling was evaluated by directly touching the obtained dyed product with hands.

According to the compound (Ia) of the alcoholic hydroxyl group
Measurement of modification ratio The value obtained by subtracting the polymerization ratio (mol%) of ethylene units from the Et / VA copolymer is regarded as a vinyl alcohol unit,
Among the vinyl alcohol units, the above compound
The ratio modified by (Ia) [that is, the modification ratio (mol%) with respect to 100 mol% of vinyl alcohol] was calculated from the weight increase of the Et / VA copolymer after the modification treatment.

Measurement of Dyeing Rate The dyeing rate was determined from the change in absorbance due to the dyeing of the dye solution according to the following equation. Dyeing ratio = 100 × (BA) / B B: Absorbance at maximum absorption wavelength before dyeing of dye solution A: Absorbance at maximum absorption wavelength after dyeing of dye solution

Measurement of K / S value [0047] The obtained dyed product was obtained from the Kubelka-Munk equation obtained from the spectral reflectance measured using a Hitachi 307 type color analyzer (manufactured by Hitachi, Ltd .; automatic recording type spectrophotometer). The K / S value [that is, K / S = (1−R) ² / 2R; R is the reflectance at the position of the maximum absorption wavelength from the visible light reflectance curve of the dyed cloth] was determined.

Measurement of lightness The lightness was determined in accordance with JIS Z 8701 "Method of displaying colors using a 2-degree visual field XYZ system".

Measurement of Saturation : Saturation was determined according to JIS Z 8701, “Method of displaying colors using a 2-degree visual field XYZ system”.

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 subjected to radical polymerization at a temperature of ° C. and under pressure to produce an ethylene / vinyl acetate random copolymer having an ethylene content of 44 mol% (number average polymerization degree: about 350). Next, this Et / vinyl acetate random copolymer is saponified in a methanol solution containing caustic soda to obtain a wet Et / VA copolymer in which 99 mol% or more of the vinyl acetate units in the copolymer are saponified. A coalescence was produced. This Et / V
After the A-type copolymer is repeatedly washed with a large excess of pure water to which a small amount of acetic acid is added, the washing is further repeated with a large excess of pure water to obtain alkali metal ions and alkaline earth in the copolymer. After reducing the content of each metal ion to about 10 ppm or less, water was separated from the copolymer by a dehydrator, and then sufficiently dried by vacuum drying at a temperature of 100 ° C. or less to obtain an Et / VA copolymer (85%). % Intrinsic viscosity [η] = 1.05 when measured at 30 ° C. in a water-containing phenol solvent.
dl / g).

The Et / VA copolymer obtained above was melt-spun at a die temperature of 260 ° C. and wound up at a spinning speed of 1000 m / min. After that, it is stretched by a conventional method to obtain 75 denier /
A 24-filament Et / VA copolymer multifilament was obtained. The fiberization step described above was good and no trouble occurred. Using the multifilament obtained above as a warp and a weft, a 1/1 plain woven fabric was produced.
The above greige plain fabric is treated at 80 ° C. for 30 minutes with an aqueous solution containing 1 g / l of sodium hydroxide and 0.5 g / l of actinol R-100 (surfactant: manufactured by Matsumoto Yushi Co., Ltd.). After desizing, the compound (I
a) It was placed in a treatment bath containing the following treatment bath composition containing [OHC- (CH ₂ ) ₇ -SO ₃ Na] and having a bath ratio of 50: 1 at a temperature of 90 ° C. and shown in Table 1 below. The acetal modification treatment was performed for each time.

Treatment bath composition OHC- (CH ₂ ) ₇ -SO ₃ Na 5 g / l Sulfuric acid 0.4 standard The weight of the dry plain fabric obtained in each case was measured, and Et / V
The modification ratio (mol%) of the alcoholic hydroxyl group of the copolymer A with the compound (Ia) was measured by the above method.

Each of the plain fabrics obtained above was immersed in a dyeing solution of the following dyeing composition and dyed at 90 ° C. for 40 minutes. Dyeing solution composition Catilon Brill Red 4GH (manufactured by Hodogaya Chemical Co., Ltd.) 2% owf sodium sulfate 3 g / l acetic acid (48%) 1% owf sodium acetate 0.5% owf Bath ratio 50: 1 Dry the dyed product obtained above. Then, the dyeing rate (%), K /
The S value, lightness (%), saturation (%), and hand were examined by the methods described above. The results are shown in Table 1 below.

[0054]

[Table 1] Treatment with Compound (Ia) Concentration of Compound (Ia) (%) 5 5 5 5 5 Sulfuric acid concentration (Normal) 0.4 0.4 0.4 0.4 0.4 Treatment time (hr) 0 0.5 2 10 20 Binding amount of Compound (Ia) 0 0.4 5 20 35 (mol%) Characteristic dyeing rate (%) 5 50 80 90-K / S value 0.5 12 35 38-Lightness (%) 25 15 13 13-Saturation (%) 5 60 80 90- Hand ○ ○ × × ¹ ) 1) Agglomeration occurred during acetalization with compound (Ia), and the compound was cured.

From the results shown in Table 1 above, when the ratio of acetalization by the compound (Ia) is about 0.4 to 20 mol%, a dyeing material having good cationic dyeing properties and excellent feeling can be obtained. It is understood that it is possible.

Comparative Examples 1 and 2 The procedure of Example 1 was repeated except that sodium ortho-benzaldehyde sulfonate (hereinafter referred to as "BSN") was used in place of compound (Ia) and subjected to acetalization under the conditions shown in Table 1. Acetalization and dyeing treatment were performed in the same manner as in Example 1, and the dyeing rate (%) and K / S
The value, lightness (%), chroma (%) and hand were examined by the methods described above.

Comparative Example 3 A multi-filament of 75 denier / 24 filaments of polyethylene terephthalate obtained by copolymerizing 2.5 mol% of 5-sulfosodium isophthalic acid was used as a warp and a weft to produce a 1/1 plain woven fabric. did. This plain fabric is subjected to 40 ° C at 120 ° C using a dyeing bath having the same dyeing composition as used in Example 1.
After dyeing for one minute, the dyeing rate (%), K / S value, lightness (%), chroma (%), and hand were examined by the methods described above. The results of Comparative Examples 1 to 3 are shown in Table 2 below together with the results when the binding ratio of the compound (Ia) in Example 1 was 5 mol%.

[0058]

[Table 2] Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Aldehyde compound treated aldehyde compound (Ia) BSN BSN-Aldehyde concentration (%) 5 4.5 4.5-Sulfuric acid concentration (regulated) 0.4 0.4 4.0-Treatment time (hr) 2 2 2- Aldehyde bond amount 0 0-1 ⁾ -(mol%) Characteristic dyeing rate (%) 806-90 K / S value 35 0.6-20 Lightness (%) 13 25-8 Saturation (%) 806- 63 texture ○ ○ − × ²⁾ 1) The next dyeing process was stopped because of significant coloration during acetalization. 2) Plastic-like texture without softness.

From the results shown in Table 2 above, in the case of Example 1 of the present invention using the compound (Ia) in which a sodium sulfonate group is bonded to an aldehyde group through a linear aliphatic group, Even when the concentration is low, acetalization is carried out smoothly and a fabric excellent in dyeing properties of a cationic dye is obtained. On the other hand, BSN which is a compound in which a sodium sulfonate group is bonded to an aldehyde group via a benzene nucleus. In Comparative Example 1 and Comparative Example 2 using a low concentration of sulfuric acid, the acetalization reaction does not proceed when the sulfuric acid concentration is low, so that the dyeability of the cationic dye is not improved. In addition, when the sulfuric acid concentration is increased to promote the acetalization, marked coloring occurs. It turns out that the purpose cannot be achieved because of the occurrence. In addition, from the results of Comparative Example 3, when 5-sulfonylisophthalic acid, which is considered to have a good affinity for the cationic dye, was copolymerized in polyethylene terephthalate, the fiber had no soft feeling and the feeling was poor. It turns out to be something.

Example 2 Each of the Et / VA copolymers having a copolymerization ratio of ethylene (Et) shown in Table 3 below and having a degree of saponification of vinyl acetate units of 99% was used. This was melt-spun at a die temperature of 260 ° C. and wound up at a spinning speed of 1000 m / min to obtain each Et / VA copolymer multifilament yarn of 75 denier / 24 filaments. Each of the multifilament yarns obtained above was used as a warp and a weft to produce a taffeta fabric. The taffeta fabric was acetalized and dyed in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The results are shown in Table 3 below.

[0061]

[Table 3] Et copolymerization rate Et / VA copolymer weight Dyeing rate by compound (Ia) K / S Saturation Hand (mol%) Spinnability of body ¹⁾ Modification ratio (mol%) (%) Value (%) 25 Spinning impossible − − − − − 35 good 7 90 37 85 ○ 60 good 1.6 65 30 65 ○ 80 good 0.2 15 4 50 × ² ) 1) Et / VA copolymer before modification treatment with compound (Ia) Spinnability. 2) There is no soft feeling and the texture is plastic-like.

From the results in Table 3 above, it is found that if the copolymerization ratio of ethylene in the Et / VA copolymer is too low, the fiberization processability decreases and spinning becomes impossible. Compound (Ia)
It can be seen that the ratio of denaturation by the dye decreases and the dyeability by the cationic dye becomes inferior.

Example 3 Each Et / VA copolymer having an ethylene copolymerization ratio shown in Table 4 below was mixed with polyethylene terephthalate (PET) (in a mixed solvent of equal amounts of phenol and tetrachloroethane at 30 ° C.). [Η] of 0.62 dl / g at the time of measurement was subjected to composite spinning and stretching at a weight ratio shown in Table 4, and the cross-sectional shape was a perfect circle and Et
A composite filament yarn of 75 denier / 25 filaments composed of a two-layer concentric core-sheath type composite fiber in which the / VA copolymer constitutes a sheath and polyethylene terephthalate constitutes a core was produced.

Plain fabrics were prepared using the drawn composite yarns obtained above as warps and wefts. After desizing was performed in the same manner as in Example 1, each plain fabric was treated with the compound (Ia) [OHC having the same treatment bath composition as used in Example 1.
-(CH ₂ ) ₇ -SO ₃ Na] in the solution containing 50:
1 for 10 hours at 90 ° C., and then dyed with a cationic dye in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The results are shown in Table 4 below.

[0065]

[Table 4] Et copolymerization Dyeing ratio at composite ratio (Ia) K / S Saturation Hand ratio Et / VA: PET spinnability Modification ratio (%) Value (%) (mol%) (weight) (mol%) 23 50:50 Spinning impossible-----32 50:50 Good 15 90 35 85 ○ 44 5:95 Spinning not possible-----44 30:70 Good 6 65 30 65 ○ 44 50:50 Good 10 85 33 80 ○ 44 70:30 Good 14 90 35 85 ○ 44 95: 5 Unspinnable − − − − − 60 50: 50 Good 7 75 30 60 ○ 75 50: 50 Good 0.1 10 35 × ¹ ) 1) There is no soft feeling and the texture is plastic-like.

From the results shown in Table 4 above, it can be seen that the woven fabric of the present invention comprising the conjugate fiber modified with the compound (Ia) has extremely good cationic dye dyeing properties. Furthermore, from the results in Table 4, in order to improve the fiberization processability, Et / V
It is understood that it is necessary to adjust the copolymerization ratio of ethylene in the A copolymer and the ratio of the Et / VA copolymer and the polyester in the conjugate fiber.

[0067]

The fibers, yarns and textiles of the present invention have extremely good dyeing properties of cationic dyes, and when dyed with cationic dyes, give a vivid and deep color that is not seen in conventional synthetic fibers. This gives a dyed product having, and is particularly suitable as an outer garment. In addition, the fibers, yarns and fiber products of the present invention can exhibit light-collecting properties, and have a good feel, moisture absorption and water absorption similar to natural fibers which are soft and have an excellent bulkiness.

Further, in the case of the method of the present invention, the copolymerization ratio of ethylene in the Et / VA copolymer, the modification ratio by group (I) and / or group (II),
By adjusting the compounding ratio of the Et / VA copolymer and other thermoplastic polymer, etc., there is no decrease in fiber strength, etc., and furthermore, troubles in polymer design and fiberization process, undesired coloring, etc. , A fiber, a yarn and a fiber product having excellent cationic dyeability can be easily obtained.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification symbol FI // D06M 101: 24 (72) Inventor Masao Kawamoto 1621 Sazu, Kurashiki-shi, Okayama Prefecture Kuraray Co., Ltd. (72) Inventor Tomoyasu Tsuda 2045, Sakurazu, Kurashiki City, Okayama Prefecture Kuraray Co., Ltd. (58) Field surveyed (Int.Cl. ⁶ , DB name) D01F 6/64 D01F 8/10-8/14 D06M 13 / 137,13 / 256

Claims (4)

(57) [Claims] 1. The basic skeleton is composed of an ethylene-vinyl alcohol-based copolymer, and an alcoholic hydroxyl group in the copolymer has a formula:> CH- (CH ₂ ) via an oxygen atom of the alcoholic hydroxyl group. _n -SO ₃ M (I) [wherein, n an integer from 1 to 10 and M is hydrogen or the formula,
And a cation capable of forming a salt with the sulfoxyl group of (I).] A fiber comprising a modified ethylene-vinyl alcohol copolymer modified with at least one group represented by the following formula: 2. The basic skeleton is composed of an ethylene-vinyl alcohol-based copolymer, and the alcoholic hydroxyl group in the copolymer has the formula:> CH- (CH ₂ ) via an oxygen atom of the alcoholic hydroxyl group. _n -SO ₃ M (I) [wherein, n an integer from 1 to 10 and M is hydrogen or the formula,
And a cation capable of forming a salt with the sulfoxyl group of (I)]. A composite comprising a modified ethylene-vinyl alcohol-based copolymer modified with at least one of the groups represented by the following formulas and another thermoplastic polymer: fiber. 3. A yarn or fiber product comprising at least one of the fibers according to claim 1 and component 2. 4. A fiber comprising an ethylene-vinyl alcohol-based copolymer, a composite fiber comprising an ethylene-vinyl alcohol-based copolymer and another thermoplastic polymer, or a yarn comprising at least one of these fibers as a component. or textiles, _{wherein: OHC- (CH 2) n -SO} 3 M (Ia) [ wherein, n an integer from 1 to 10 and M is hydrogen or the formula,
And a cation capable of forming a salt with the sulfoxyl group of (I)], and the formula: (Wherein n and M are the same as described above), and then acetalized using at least one of the compounds represented by the formula (1), and when the group M is hydrogen, optionally treated with an alkali compound to obtain a sulfonic acid fibers according to any one of claims 1 to 3, characterized in that the group in the form of a salt, the production method of composite fibers, yarns or textiles.