JPH0718093B2 - Dyeing method for polyester-containing fiber and dyeing aid - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention prevents disperse dye from decomposing when exhaust dyeing polyester fiber in an alkaline region in an aqueous medium by using a disperse dye, and thus reproducibility is improved. The present invention relates to a dyeing method for performing good dyeing and a dyeing aid effective for the dyeing method.

[Conventional technology]

Dyeing of polyester fibers is generally carried out with a disperse dye in a weakly acidic (pH 5 to 7) dyeing bath at a temperature of 120 to 140 ° C. This is because the disperse dye is unstable in an alkaline dyeing bath, and it is difficult to dye the dyed fabric with the same color tone with good reproducibility when it is alkaline.

However, in recent years, new technical demands have emerged as to whether polyester fibers can be dyed in an alkaline range of pH 8 to 10. The first reason is that it is possible to rationalize the dyeing process by simultaneously performing the alkaline scouring treatment and the dyeing treatment of the polyester fiber in the same step.

That is, when dyeing polyester fiber, the oil agent used in the processes such as spinning, spinning, and woven cloth is usually used.
In order to eliminate the adverse effect on the dyeing process caused by the sizing agent, etc.
In general, alkaline scouring treatment is performed to remove the sizing agent and the like. This is because the oil agent can be removed by washing with a surfactant, but the sizing agent (polyacrylic acid ester type, polyvinyl alcohol type, etc.) can be removed only with an alkali. Therefore, from the viewpoint of energy saving and labor saving, various one-bath scouring and dyeing processes, in which the scouring process and the dyeing process are carried out in the same bath, are being studied as one of the rational dyeing methods in a dyeing factory.

However, the usual scouring process uses a large amount of alkali, and a large amount of alkali is indispensable for removing the sizing agent. However, when this amount of alkali and disperse dye are present in the same bath, the scouring process is performed. Under the subsequent dyeing condition, that is, at a temperature of 120 to 140 ° C., the disperse dye is decomposed by the action of alkali, and dyeing is not performed well.

Therefore, conventionally, as a method for avoiding this, a chemical that generates an acidic substance by heat is present in the dyeing bath, the scouring treatment is performed alkaline, and the temperature of the dyeing bath is increased during dyeing to increase the pH of the dyeing bath. A method and a drug have been proposed in which the disperse dye is dyed under a dyeing condition without decomposing the disperse dye (for example, JP-A-60-224884, the same).
60-17183 etc.). However, the above-mentioned pH slide method has not been put to practical use industrially because a slight difference in the conditions affects the dispersion speed of a drug that generates an acidic substance and the reproducibility of the dyeing and scouring effect is poor. .

On the other hand, the second reason is that a mixed fiber of polyester fiber and cellulose fiber or nitrogen-containing fiber (nylon fiber etc.) can be dyed simultaneously in an alkaline medium using both disperse dye and reactive dye. This is because.

That is, the dyeing of the cellulose fiber or the nitrogen-containing fiber is usually carried out by using a reactive dye in an alkaline range of pH 12 to 13,
It is carried out at a temperature of ~ 100 ° C. Therefore, the dyeing conditions for polyester fibers and cellulose fibers are clearly distinguished in terms of pH and temperature. Therefore, in the case of dyeing a mixed fiber of both fibers, it is necessary to divide the dyeing process into two and perform dyeing in different dyeing baths at different pH ranges and at different temperatures.

However, in recent years, a method of simultaneously dyeing the mixed fibers with one dye bath containing a disperse dye and a reactive dye has been attempted. In this method, the dyeing temperature is 120 to 140 ° C, and the pH is 8 to 1 which is between the dyeing pH of both fibers.
Adopt about 0. In this case, it is necessary to select, as the disperse dye, one relatively strong in alkalinity, and on the other hand, as the reactive dye, it is necessary to select one that is capable of proceeding with the reaction even in weak alkalinity and is stable even at high temperature. However, even with this method, decomposition of the disperse dye is hard to avoid, it is reproducible, and it is difficult to dye the polyester fiber.

[Problems to be Solved by the Invention]

In view of the above circumstances, the present inventors have used a disperse dye for polyester-containing fibers, in an aqueous medium, to prevent decomposition of the disperse dye during exhaust dyeing in an alkaline region, and to perform dyeing with good reproducibility. As a result of diligent examination of the method, it was found that good results can be obtained by the presence of an amino acid in the dyeing bath, and a patent application was filed first (JP-A-63).
-145038).

However, when a mixed fiber of polyester fiber and cellulose fiber or nitrogen-containing fiber is exhaust dyed in an alkaline region in the presence of amino acid using a disperse dye and a reactive dye, the polyester fiber is dyed well, but cellulose Insufficient dyeing of fibers. Therefore, as a result of further studies, when a specific amino acid derivative is present, the disperse dye and the reactive dye are stabilized, and the polyester fiber alone or the mixed fiber of the polyester fiber and the cellulose fiber or the nitrogen-containing fiber is obtained. It has been found that all can be dyed well.

[Means for Solving the Problems]

The gist of the present invention is to dye a polyester-containing fiber with a disperse dye, which comprises an amino acid derivative in which at least one hydrogen atom of an amino group is substituted with a specific organic group in a dyeing bath, and an alkali metal salt thereof. A dyeing method for a polyester-containing fiber, which comprises dyeing in an alkaline region in an aqueous medium in the presence of at least one amino acid selected from the group. Still another gist of the present invention is
The present invention relates to a dyeing auxiliary agent that enables the above dyeing method, that is, amino acids 2 to 50 selected from the group consisting of amino acid derivatives in which at least one hydrogen atom of an amino group is substituted with a specific organic group and alkali metal salts thereof. The present invention relates to a dyeing aid for polyester-containing fibers, which comprises an aqueous solution in which 0.5% by weight and an alkali metal compound of 0.5 to 10% by weight are dissolved.

Hereinafter, the present invention will be described in more detail.

The disperse dye used in the present invention is not particularly limited, but a monoazo system, an asso disperse dye such as a disazo system, and a substituent which is easily hydrolyzed in an alkaline atmosphere in the dye structure, for example, an acetylamino group, Examples include disperse dyes such as anthraquinone, phthalocyanine, and copper formazan having a cyano group and an —OCO—R group (where R is a C _1-3 alkyl group or a phenyl group) substituted on an aromatic ring. Dyes are preferably used. Examples of the structure of these dyes include disperse dyes represented by the following general formula.

(In the formula, X ^{1 to} X ³ are a hydrogen atom, a lower alkyl group, a nitro group, a cyano group or a halogen atom, Y ¹ is a hydrogen atom, a lower alkoxy group or a lower alkyl group, and Y ² is a hydrogen atom or an acylamino group. R ¹ and R ² are a hydrogen atom, a cyano group, a hydroxyl group, a halogen atom, an alkylcarbonyl group,
Lower alkylcarbonyloxy group, phenyl group, phenoxy group or lower alkyl group optionally substituted with benzoyloxy group) (In the formulas [II] and [III], X ^{4 to} X ⁵ represent a hydrogen atom, a halogen atom, or a nitro group, and Y ¹ , Y ² , R ¹ and R ² are the same as the above definition) (In the formula, X ⁶ represents a hydrogen atom, a nitro group, a lower alkyl group or a halogen atom, Y ³ represents a hydrogen atom, a lower alkyl group or a lower alkoxy group, and R ¹ and R ² are the same as defined above) (In the formula, X ⁷ has a hydrogen atom, a halogen atom, a nitro group or an alkoxylcarbonylamino group, and Y ¹ is the same as the above definition.) (In the formula, Z ¹ represents a hydrogen atom or a methyl group, and X ⁶ , Y ¹ , R ¹ and R ² are the same as the above definition.) Specific examples of the azo disperse dye in the present invention include: , And the disperse dyes having the following structural formulas.

On the other hand, when the polyester-containing fiber is a mixed fiber of polyester fiber and cellulose fiber or nitrogen-containing fiber, as the reactive dye used when dyeing this,
Examples thereof include water-soluble reactive dyes having a reactive group such as vinyl sulfone type, halogenotriazine type and triazine type substituted with nicotinic acids. The base structure of this reactive dye is usually a monoazo type, disazo type, anthraquinone type, phthalocyanine type, copper formazan type or the like. As such a reactive dye for dyeing mixed fibers, a dye which is already commercially available as a reactive dye stable at high temperature, for example, Nippon Kayaku Co., Ltd., trade name Kayacelon React Seri
es etc. can be used.

The dyeing method of the polyester-containing fiber in the present invention includes two cases of a dyeing method which also serves as an alkali scouring treatment of the polyester fiber and a method of dyeing a mixed fiber of the polyester fiber and the cellulose fiber in the same dyeing bath. .

However, in any case, the dyeing method of the present invention is an exhaust dyeing method from an aqueous medium, and it is premised that the pH of the dyeing bath is in the alkaline range. And, as the pH condition of the dyeing bath, the range of 8 to 11 is usually suitable. That is, it is common knowledge that a usual dyeing method using a disperse dye is carried out in a weakly acidic range, but in the present invention, only dyeing in an alkaline range is targeted.

As the pH adjuster, usually, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, sodium carbonate, or sodium hydrogen carbonate, an alkali metal compound such as a carbonate or hydrogen carbonate can be used, but preferably water. Sodium oxide is suitable.

In the present invention, when exhausting dyeing of polyester-containing fibers in such an alkaline range, it is essential that a specific amino acid derivative and / or its alkali metal salt be present in the dyeing bath.

The amino acid derivative targeted by the present invention is a compound in which at least one hydrogen atom of an amino group in an amino acid is substituted with a specific organic group. That is, it is a compound in which one or two, preferably two, of hydrogen atoms of an amino group are substituted with a specific organic group. In addition, 2 amino groups
For amino acids having three or more amino acids, it is sufficient if at least one hydrogen atom of one amino group is substituted. However, when used for dyeing a mixed fiber of polyester fiber and cellulose fiber, it is necessary that all hydrogen atoms of all amino groups are substituted. Examples of the amino acid portion of the amino acid derivative include neutral amino acids such as glycine, alanine, aminobutyric acid, aminocaproic acid, acidic amino acids such as aspartic acid and glutamic acid, and basic amino acids such as lysine and arginine, and preferably glycine. , Neutral amino acids such as alanine and glutamic acid, more preferably neutral amino acids such as glycine or alanine, and particularly preferably glycine. The amino acid substituent is not particularly limited as long as it does not impair the water solubility of the amino acid and does not have a bad influence in the dyeing bath, but is usually an alkyl group, an alkoxyalkyl group, a hydroxyalkyl group,
C, such as cyanoalkyl group, acyl group, allyl group, polyalkylene oxide group (n = 2 to 4), alkyl ether polyalkylene oxide group (n = 2 to 4), especially methyl group, ethyl group, propyl group, etc. ₁ -C ₄ alkyl group; methoxymethyl group, methoxyethyl group, C ₁ -C ₄ alkoxy C ₁ -C ₄ alkyl groups such as ethoxyethyl group; hydroxyethyl group, C ₁ -C ₄ hydroxyalkyl such as hydroxypropyl groups Group; C ₁ -C ₄ cyanoalkyl group such as cyanomethyl group, cyanoethyl group; acyl group such as acetyl group; allyl group such as alkenyl group; poly (lower alkylene oxide) group (n =
2-4); lower alkyl ether poly-lower alkylene oxide groups (n = 2-4) and the like, particularly C ₁ -C ₄ alkyl groups, C ₁ -C ₄ hydroxyalkyl groups, C ₁ -C ₄ alkoxy C. ₁ -C ₄ alkyl groups are preferred.

As the amino acid derivative, specifically, N, N-dimethylglycine, N-methylglycine, N, N-bishydroxyethylglycine and N-methylalanine are preferable, and particularly,
N, N-bishydroxyglycine is preferred.

The alkali metal salt of the amino acid derivative is usually a sodium salt. Since the amino acid derivative is added to the alkaline medium in the present invention, these are present as alkali metal salts in the system.

When dyeing mixed fibers of polyester fibers and cellulose fibers in the same bath, it is necessary to use an amino acid derivative in which all hydrogen atoms of amino groups are substituted with specific organic groups and / or salts thereof. This is because amino acids having an unsubstituted amino group adversely affect the reactive dye, resulting in poor dyeing of the cellulose fiber. The amino acid derivative effective for dyeing the mixed fiber is not particularly limited as long as it is an amino acid derivative in which all the hydrogen atoms of the amino group are substituted with a specific organic group among the above-mentioned amino acid derivatives, but a suitable amino acid derivative Is N, N
-Dimethylglycine and N, N-bishydroxyethylglycine, with N, N-bishydroxyethylglycine being especially preferred.

The amount of the amino acid derivative or salt thereof used is usually 0.02 to 0.8 g / dye from the viewpoint of the decomposition preventing effect of the disperse dye.
l, preferably in the range of 0.05 to 0.4 g / l.

As the target fiber of the dyeing method of the present invention, polyester fiber,
Also, the present invention can be applied to any woven fabric, knitted fabric, non-woven fabric, yarn or the like made of polyester fibers and other fibers. Examples of the other fibers include cellulose fibers such as cotton, hemp and rayon, and nitrogen-containing fibers such as nylon, wool and silk. As described above, the dyeing conditions are in the alkaline range, preferably pH 8 to 11, more preferably 8 to 1 as described above.
At 0, a temperature of 120 to 140 ° C. can be employed under pressure which is usually applied to dye polyester fibers. In order to carry out the dyeing of the present invention, a dyeing bath usually contains a dyeing aid comprising an aqueous solution in which 2 to 50% by weight of the above amino acids and 0.5 to 10% by weight of an alkali metal compound, preferably sodium hydroxide, are dissolved.
It is desirable to add a predetermined amount so that the pH and the content of amino acids in the dyeing bath are within the above ranges, and start the dyeing treatment.

In the dyeing method of the present invention, post-processing such as antistatic processing and softening processing for fibers which are generally carried out after dyeing according to the usual dyeing method can also be carried out according to a conventional method.

According to the present invention, even when the polyester fibers are dyed in the alkaline range, the disperse dye is not decomposed when the amino acid derivative is present in the dyeing bath, and the dyeing can be performed well.

Although the analysis of the action of such amino acids is insufficient, it is presumed that it is due to the effect of preventing the decomposition of the dye due to the buffering action, the chelating action and the like of the amino acids at present.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following description.

〔Example〕

Examples 1 to 10 and Reference Example 1 Disperse dye 20 represented by the following [A], [B] or [C]
40 parts of a naphthalene sulfonic acid formalin condensate, 40 parts of lignin sulfonic acid soda and water were added to form a slurry, which was then sufficiently pulverized using a sand mill. Then, it was dried with a spray dryer to produce each disperse dye composition.

Dyeing a mixture (black product) of disperse dye compositions obtained by mixing disperse dye compositions containing the disperse dyes represented by [A], [B] and [C] above in a ratio of 4: 2: 4 (weight ratio). Used as a dyeing aid at a leveling agent of 4% by weight,
aserver LR-PSL (trade name of Mitsubishi Kasei Co., Ltd.) 0.5 g / l, an amino acid derivative substituted with a hydrogen atom of an amino group shown in Table 1 as an additive is used in an amount shown in Table 1, and The pH of the dyeing bath was adjusted to 9.5 with the alkali shown in Table 1, and the unscoured polyester fabric, Tropical (trade name, manufactured by Toray Industries, Inc.) was dyed for 60 minutes at a bath ratio of 1:10 and a dyeing temperature of 130 ° C. It was Then, it was washed and dried according to a conventional method to obtain a dyed fabric.

Also, as the criteria for dyeing cloth evaluation, the same as above except that acetic acid and sodium acetate were used without adjusting the amino acid derivative, and the pH was adjusted to pH 5.0 (weakly acidic) generally adopted for dyeing polyester fibers. Then, the dyebath was adjusted to perform dyeing (Reference Example 1). The dyeing result of each dyeing cloth was evaluated based on the dyeing cloth obtained in Reference Example 1, and the results are shown in Table 1.

The evaluation method of the dyed cloth is as follows.

<Evaluation Method> Interfacial Density-Reflectance of the dyed cloth was measured with a Macbeth spectrophotometer (MS-2020), and the θ value was calculated according to DIN6164 (DIN color system), and in Reference Example 1. It was expressed as a relative value when the value was 100.

Color difference-Reflect the reflectance of dyed cloth by Macbeth spectrophotometer (MS
-2020), and the hue difference ΔE for the dyed fabric obtained in Reference Example 1 was determined from CIEL ^* a ^* b ^* . The larger the value of ΔE is, the more the color is different. As a measure of the color difference of the dyed product, ΔE of 1.0 or less causes no problem.

Fiber surface state-A scanning electron microscope was used to evaluate the adhesion state of the sizing agent remaining on the fiber surface and the polyester oligomer eluted during dyeing.

Comparative Example 1 Dyeing and evaluation of the dyeing result were carried out in the same manner as in Example 1 except that baking soda and soda ash were used as alkalis in order to maintain the pH of the dyeing bath at 9.5, and no amino acid derivative was added. It was The results are shown in Table 1.

Comparative Example 2 Dyeing and evaluation of the dyeing result were performed in the same manner as in Comparative Example 1 except that caustic soda was used as the alkali in place of sodium bicarbonate / soda ash. The results are shown in Table 1.

By this method, although the initial pH of the dyebath was adjusted to 9.5, the pH at the end was reduced to about 6.0. This is because caustic soda is a strong alkali, so a small amount of caustic soda is used to adjust the initial pH to 9.5, but this small amount of alkali was consumed by the polyester oligomer or the sizing agent.

As is clear from the results shown in Table 1, the refining is not performed in Reference Example 1 in which the unscoured polyester is dyed under the weakly acidic condition where the polyester is conventionally dyed.
The surface condition of the fiber is poor. Further, when dyeing unscoured polyester under alkaline conditions, in Comparative Example 1 in which no amino acid derivative is used, the surface condition of the fiber is good, but the surface density of the dyed cloth is poor and the color tone difference is large.
Further, in Comparative Example 2 in which the same caustic soda as in Example was used as an alkali and no amino acid derivative was used, the surface concentration and the color tone of the dyed cloth were almost the same as those in Reference Example 1, but the pH of the dyebath during dyeing was Since it descends, the scouring treatment is not carried out sufficiently and the surface condition of the fiber becomes poor. On the other hand, in the examples in which the unscoured polyester was dyed in the presence of the amino acid derivative under alkaline conditions, the surface density and color tone of the dyed cloth were the same as those in Reference Example 1, and the surface condition of the fiber was good. Yes, it can be seen that scouring and color mixing were performed at the same time.

Examples 11 to 55 Dye compositions were produced in the same manner as in Example 1 using the dyes shown in Table 2 in place of the dyes represented by [A], [B] or [C] in Example 1, Example 1 using these
Dyeing was carried out in the same manner as in. The results are shown in Table 2.

Examples 56 to 57, Comparative Example 3 and Reference Examples 2 to 3 (Dyeing Examples of Mixed Fiber) Disperse dye-containing compositions produced in the same manner as in Example 1 using the disperse dye represented by the following structural formula [D]. Of the dye (orange) and the reactive dye (orange) represented by the following structural formula [d] are used in an amount of 1% by weight based on the dyed material.
aserver DP-P liquid (Mitsubishi Kasei Co., Ltd., trade name) 3 g / l and the amino acid derivatives (Examples 56 and 57) or amino acids (Comparative Example 3) shown in Table 3 were included and adjusted to pH 9.5 with caustic soda. In 200 ml of a dyeing bath, 5 g of polyester woven fabric and 5 g of cotton woven fabric were dyed at a dyeing temperature of 130 ° C. for 60 minutes. Then, it was washed and dried according to a conventional method to obtain a dyed fabric.

In addition, dyeing of cotton was performed by adjusting a dyeing bath in the same manner except that an amino acid derivative was not used as a criterion for dyeing cloth evaluation and soda ash was used as an alkali, and the pH was adjusted to 9.5 (Reference Example 2). . In addition, as a criterion for dyeing cloth evaluation, acetic acid and sodium acetate are generally used for dyeing polyester fibers without using amino acid derivatives.
Dyeing of polyester was performed by adjusting the dyeing bath in the same manner except that the pH was adjusted to 5.0 (weakly acidic) (Reference Example 3).

Dyeing results of each dyed fabric based on the dyed fabrics obtained in Reference Examples 2 and 3 were evaluated in the same manner as in Example 1, and the results are shown in Table 3.

As is clear from the results of Examples 56 and 57 in Table 3, both polyester and cotton are dyed well when dyeing is carried out in the presence of the amino acid derivative using both the disperse dye and the reactive dye. And is therefore effective for dyeing mixed fibers, as is apparent from Comparative Example 3, when dyeing is performed in the same manner in the presence of the amino acid glycine, the surface density of cotton is remarkably reduced, that is, The dyeing rate is significantly reduced. Therefore, it is practically impossible to dye the mixed fiber alkaline in the presence of the amino acid.

〔The invention's effect〕

According to the present invention, by allowing a specific amino acid derivative and / or its alkali metal salt to be present in the dyeing bath,
Even when the dyeing of the polyester fiber, which has been conventionally performed in the weakly acidic region, is performed in the alkaline region, it is possible to perform the dyeing with good reproducibility while preventing the disperse dye from being decomposed. Therefore, the one-bath scouring / color mixing method of polyester fabric, which has been difficult to industrially adopt with the conventional technology, becomes possible. or,
It is also suitable for a one-bath dyeing method in which a mixed fiber of polyester fiber and cellulose fiber is dyed in the same bath by using a disperse dye and a reactive dye, which is extremely important in the dyeing industry.

In the case of dyeing with alkaline, polyester oligomers that precipitate in the dye bath from the inside of the fiber under the dyeing conditions dissolve in the dye bath. There is also an advantage that it can prevent rings, dusting, etc.).

Claims (7)

[Claims] 1. When dyeing polyester-containing fibers with a disperse dye, at least one hydrogen atom of an amino group in the dyebath is an alkyl group, an alkoxyalkyl group, a hydroxyalkyl group, a cyanoalkyl group, an acyl group. From an amino acid derivative substituted with an organic group selected from the group consisting of an allyl group, a polyalkylene oxide group (n = 2 to 4), and an alkyl ether polyalkylene oxide group (n = 2 to 4) and its alkali metal salt A method for dyeing a polyester-containing fiber, comprising dyeing at least one kind of amino acid selected from the group consisting of: dyeing in an alkaline region in an aqueous medium. 2. When dyeing a mixed fiber of polyester fiber and cellulose fiber or nitrogen-containing fiber with a disperse dye and a reactive dye, all of the hydrogen atoms of the amino group in the dye bath are alkyl groups or alkoxyalkyl groups. An organic group selected from the group consisting of a hydroxyalkyl group, a cyanoalkyl group, an acyl group, an allyl group, a polyalkylene oxide group (n = 2 to 4), and an alkyl ether polyalkylene oxide group (n = 2 to 4). A method for dyeing a polyester-containing fiber, which comprises dyeing in an alkaline region in an aqueous medium in the presence of at least one amino acid selected from the group consisting of a substituted amino acid derivative and an alkali metal salt thereof. 3. An organic group which replaces a hydrogen atom of an amino group is C ₁
To C ₄ alkyl group or C _{1 to} C ₄ hydroxyalkyl group. 4. The staining method according to claim 1, wherein the amino acid is glycine, alanine or glutamic acid. 5. At least one hydrogen atom of an amino group is an alkyl group, an alkoxyalkyl group, a hydroxyalkyl group, a cyanoalkyl group, an acyl group, an allyl group, a polyalkylene oxide group (n = 2 to 4), an alkyl ether poly. Amino acid derivatives substituted with an organic group selected from the group consisting of alkylene oxide groups (n = 2 to 4) and 2 to 50% by weight of amino acids selected from the group consisting of alkali metal salts thereof, and an alkali metal compound of 0.5 to A dyeing aid for polyester-containing fibers, which comprises an aqueous solution in which 10% by weight is dissolved. 6. An organic group which replaces a hydrogen atom of an amino group is C ₁
Dyeing agent according to claim 5 -C ₄ alkyl radical or C ₁ -C ₄ hydroxyalkyl groups. 7. The dyeing auxiliary agent according to claim 5, wherein the amino acid is glycine, alanine or glutamic acid.