JP2515361B2 - Dye for dyeing cotton yarn for denim, dyeing method using the same, and dyed material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to the dyeing of cotton yarns for denim, and more particularly to dyes and dye compositions for dyeing cotton yarns such as cotton warp yarns for denim, dyes or dyes thereof. The present invention relates to a method for dyeing cotton yarn using the composition, and a dyed product colored using the dye or the dye composition.

Denim is preferred for the feel and durability of cotton as a cloth for clothing, and is widely used for work, ladies' pants, children's clothing and the like.

As jeans made of such denim, clothing called blue jeans has been widely used for a long time. Blue jeans are often used in this way because they prefer the unique shade of fabric dyed with indigo dye and the change in shade over time, and clothing that emphasizes sensitivity by applying this change. It is possible to develop.

However, in recent years, along with the diversification and individualization of fashion, not only blue jeans but also so-called color jeans such as yellow, green, and black have increased in demand. Therefore, denim, which is a material for jeans, is also required to be colored in various color tones such as yellow to green to black.

[Conventional technology]

For dyeing cotton yarn for color denim required by the trend of color jeans, sulfur dyes, vat dyes, reactive dyes or naphthol dyes are used. However, the color jeans dyed using these dyes differ in the properties of the dyed product from the dyed product due to the indigo dye, and the value as a product ranging from dyed fabrics to clothing is different from conventional blue jeans. It will be.

As described above, blue jeans are preferred as clothing because of their unique colors and properties, and such performance is similarly desired for colored jeans. However, such performance cannot be obtained with a dyed product such as a sulfur dye, a vat dye, a reactive dye or a naphthol dye.

For example, when using the above-mentioned dyes, in order to process with rope dyeing equipment for blue jeans using indigo dyes that have been widely used conventionally, the dyeing behavior of these dyes and indigo dyes is too different. However, conventional equipment is difficult to apply to such a dyeing process. Moreover, these dyes can hardly be expected to have a decolorizing effect by bleaching with chlorine, and therefore, when bleaching is applied to black denim made of black-dyed cotton warp mixed with indigo dye and ordinary yellow slene dye, only blue is decolorized. The yellow color remains and the commercial value is significantly impaired. That is, rope dyeings made by blending indigo dyes with other sulfur dyes, vat dyes, naphthol dyes, reactive dyes, etc., have a very small decolorizing effect due to chlorine bleaching unlike these indigo dyes. The fading effect like in denim cannot be expected, and the product value is remarkably inferior.

As described above, conventionally, a dyeing behavior similar to that of indigo dye, and a dye having similar performance has not yet been introduced, therefore, a method of dyeing cotton yarn using a novel dye having such performance, There is no dyed cotton denim or color jeans using such denim.

[Problems to be Solved by the Invention]

An object of the present invention is to provide a dye and a dye composition which exhibit the same dyeing behavior as an indigo dye and exhibit a decolorizing effect as in the case of bleaching which is similar to that of an indigo dye.

A second object of the present invention is to provide a rope dyeing method for denim cotton yarn using the above-mentioned dye or dye composition.

Further, a third object of the present invention is to dye the above dye or dye composition, such as cotton yarn for color denim, which is dyed in a color tone such as yellow or green to black by blending with an indigo dye. Is to provide.

The object of the present invention has been achieved by using a specific quinophthalone derivative as a dye. That is, if the quinophthalone derivative is used alone, it can be colored in a unique color with a single color, and by mixing with the indigo dye, it can be colored from green to black. By using such a dye, a dyed product similar to the indigo dye can be obtained by a dyeing method similar to the indigo dye dyeing method, in which the dyeing state of the dye and the change with time of the dyed product are similar. Dyeing of cotton yarn using the quinophthalone derivative alone or the dye composition containing the quinophthalone derivative and the indigo dye can be performed by the following method. For example, a large number of single yarns are arranged in a rope shape into a tow shape, wound in a spherical shape, and many spherical cotton yarns are drawn out at the same time, into several pairs of dye baths with squeeze rolls and air ring devices. It is a continuous dyeing method in which the dyeing is gradually and gradually dyed by repeating the steps of dyeing and oxidation for a short time.A rope-shaped denim cotton yarn is dipped in a dye bath containing a quinophthalone derivative, squeezed, and aired. Yellow to black color jeans can be obtained by a method of dyeing by repeating oxidation.

[Means for solving the problem]

In general, denim cotton yarn for blue jeans is formed by arranging a large number of single yarns into a single rope shape, forming a tow shape, winding spherically,
A large number of these spherical cotton threads are pulled out at the same time and introduced into several pairs of dyeing baths containing a reduced form of indigo dye solution, which is continuously dyed by repeating the steps of dipping and squeezing for a short time and oxidation. .

The inventors of the present invention have found that quinophthalone derivatives usually have no dyeing property on cotton by the method of dyeing cellulose fibers, but surprisingly, by repeating the above-mentioned dyeing process of cotton yarn for denim, the density gradually increases. It was found that they are dyed yellow, that is, these quinophthalone derivatives exhibit the same dyeing behavior as indigo dyes, and rope dyeing of cotton yarn for denim by repeating dipping, squeezing and air oxidation is applicable. . In addition, the dyed article was found to have good light fastness and, like the indigo dyed article, exhibit the same bleaching effect as bleaching due to chlorine and the same time-dependent change in the dyed article as the indigo dyed article. Since the dyeing behavior is similar to that of the indigo dye, it is possible to color the compounded color including black by combining with the indigo dye, and it is possible to meet the demand of color jeans, and to complete the present invention. I arrived.

The quinophthalone derivative used in the present invention has the general formula (I) or (II) (Wherein, X represents an H, Br or Cl atom, and Y represents an H, —COOR or —COOC ₂ H ₄ OR group (wherein R represents an alkyl group)) The dye composition of the present invention is a dye composition containing one or more of these derivatives and an indigo dye.

Further, the dyeing method of the present invention uses the above quinophthalone derivative, or a dye composition containing a quinophthalone derivative and an indigo dye, a denim cotton yarn in the form of a rope, and a dye containing the above dye or the dye composition. This is a rope dyeing method for denim cotton yarn, which is characterized by immersing in a bath, squeezing, and repeating air oxidation for dyeing.

Further, the dyed product of the present invention is a dyed product colored by such a method.

The quinophthalone derivative of the present invention is represented by the above general formula (I) or (II), and specific examples thereof include the following compounds.

That is, 2-phthaloylmethylidine-3-hydroxyquinoline, 2-phthaloylmethylidine-3-hydroxy-4-bromoquinoline, 2- (ethoxyethoxycarbonylphthaloylmethylidine) -3-hydroxyquinoline, 2- ( Methoxycarbonylphthaloylmethylidine)
Examples thereof include -3-hydroxyquinoline, 2-phthaloylmethylidin-3-hydroxy-4-chloroquinoline and 2-naphthaloylmethylidin-3-hydroxyquinoline.

These derivatives exhibit a wide range of yellow hues and can meet the needs of yellow jeans when used alone.

The dye composition of the present invention comprises the above quinophthalone derivative and an indigo dye, and the quinophthalone derivative may be used alone or in combination of two or more in accordance with a desired color tone. .

In the composition containing the one or more quinophthalone derivatives and the indigo dye, the content ratio is not specified, and various compositions capable of being colored from yellow to green or black can be adjusted by various mixing ratios. For example, in order to obtain black jeans, a dye composition containing 2-phthaloylmethylidine-3-hydroxy-4-bromoquinolinequinoline and indigo in a ratio of about 4: 6 can be applied.

The dyeing composition is not particularly limited in the compounding ratio of the indigo dye and the quinophthalone derivative, but it contains the indigo dye and the quinophthalone derivative in a ratio of 1: 9 to 9: 1 according to the desired hue, and the composition 100 For each part, various additives,
For example, it is prepared by containing 1 to 20 parts of a neutral inorganic salt such as anhydrous sodium sulfate and 20 parts or less of an anionic surfactant such as a lignin-based dispersant. The dye composition obtained by such a method is usually provided as a powdery product, but the form of the composition may be a powdery product, a granular product, a paste product, or the like, depending on the intended purpose, and various types of products. It can be provided as a form.

The dyeing method of the present invention using the above-mentioned derivative or composition is a dye bath containing a denim cotton yarn in a rope shape and containing the quinophthalone derivative of the general formula (I) or (II), or the quinophthalone derivative and an indigo dye. Rope dyeing of cotton yarn for denim is carried out by repeatedly immersing in, squeezing, and air oxidation.

A dyebath containing these quinophthalone derivatives is prepared by adding caustic soda or an alkali of a mixture of caustic soda and soda ash as an alkaline agent. The concentration of the quinophthalone derivative in the dyeing bath is determined according to the concentration of the desired dyed product. Generally, the concentrated stock solution is prepared as a separate bath in the range of 10 to 50 g /, and the concentration in the dyeing bath is 0 using this concentrated stock solution.
Prepare 5-10 g / dye bath respectively.

Further, the amount of alkali used may be a small excess amount from the amount capable of dissolving the quinophthalone derivative. However, the quinophthalone derivative does not necessarily need to be completely dissolved in the dyeing bath.

In the method of the present invention, the quinophthalone derivative is used alone to obtain a dyeing product having a yellow hue, and in combination with an indigo dye, the dyeing product can have a desired hue, for example, green to black. .

For this purpose, the quinophthalone derivative and the indigo dye are dyed by coexisting in the same dyeing bath, and the dyeing bath containing the quinophthalone derivative and the reducing bath containing the indigo dye are separately prepared to prepare both baths. And the like.

In a dye bath in which a quinophthalone derivative and an indigo dye coexist in the same dye bath, the quinophthalone derivative and the indigo dye prepared separately may be used, or the dye composition of the present invention may be used.

When using the individually prepared quinophthalone derivative and indigo dye, first use the indigo dye in the required amount according to the desired hue, and use the alkali necessary for reducing the indigo dye, such as caustic soda and hydrosal. A reducing agent such as phyt is added and reduced at room temperature to 70 ° C. to prepare a reducing bath, and then a quinophthalone derivative is added to the reducing bath of the indigo dye to prepare a dyeing bath in which both are present. Also in the case of using the dye composition of the present invention, a dyeing bath is prepared by adding an amount of a reducing agent and an alkali necessary for reduction.

Further, in a method of separately preparing and dyeing a dyeing bath containing only a quinophthalone derivative as a dye, and a reducing bath containing only an indigo dye, the dyeing bath containing a quinophthalone derivative is prepared by adding an alkali as described above. Prepared, the reducing bath containing the indigo dye is added a caustic soda and hydrosulfite to a concentrated reducing tank that is separate from the dyeing bath, and similarly to the above, a concentrated reducing bath is prepared by reducing at room temperature or 70 ° C., This reducing bath leads to a dyeing bath of appropriate concentration.

A typical embodiment of the dyeing method of the present invention is as follows. That is, similar to general blue jeans cotton warp, spherical cotton warp is used in which a large number of single yarns are aligned in a rope shape and formed into a tow shape and wound in a spherical shape. Pull out and soak for a short time in several pairs of dye baths containing the dye bath or reducing solution prepared as described above,
Subsequently, it is squeezed and dyed continuously by repeating the air oxidation process.

In the case of using separate baths containing a quinophthalone derivative and a reducing bath containing an indigo dye, a step of immersing cotton yarn for denim in a dyeing bath containing only an indigo reducing solution, squeezing with a mangle, and then air-oxidizing The above procedure is repeated several times to dye a dark blue color, and the dye is then immersed in a dye solution containing an alkali solution of a quinophthalone derivative or hydrosulfite in addition to the dye, and dyed with yellow. The above method is repeated several times depending on the desired hue of the cotton thread for denim, and the overdyeing is performed.

By such a method, it is possible to color-mix a cotton yarn for denim. This method is preferable from the viewpoint of workability.

In the method of the present invention, the quinophthalone derivative can be dyed gradually and densely by repeating the immersion of the denim cotton yarn in the alkali solution without particularly applying a reducing operation, but the same as in the case of the indigo dye By giving a reducing operation, the dyeing effect can be further increased.

[Action and effect]

When the method of the present invention is applied to continuous rope dyeing of denim cotton yarn, it is possible to color yellow or even black by blending with an indigo dye. The obtained dyed product has good light fastness and a decolorizing function by chlorine bleaching, and there is almost no change in color tone over time.

The dyed cotton yarn can be used as, for example, a warp yarn to produce a color denim using an undyed yarn or a dyed yarn and a twill weave, and can meet the demand of the market as a colored jeans using the dyed cotton yarn.

〔Example〕

Hereinafter, the present invention will be described with reference to examples. In addition, "part"
Indicates parts by weight.

Example 1 A liquid prepared by adding 50 parts of Mitsui Indigo Pure EX (Indigo manufactured by Mitsui Toatsu Dye Co., Ltd.), 40 parts of solid caustic soda, 45 parts of hydrosulfite and 1000 parts by adding water at 70 ° C.
After heating for 15 minutes, a concentrated reduced solution of indigo was obtained. This liquid 60
To 1 part, hydrosulfite (1 part), caustic soda (0.5 parts) and water were added to 1000 parts to prepare an indigo dyeing bath. The cotton warp for denim washed with hot water was immersed in this at room temperature for 30 seconds, squeezed with a mangle, and then aired for 90 seconds. The steps of dipping, squeezing and air ring were repeated 6 times. Next, this cotton warp is expressed by the following formula (III) 1000 parts by adding 2.5 parts of dye, 1.5 parts of solid caustic soda and water
Dip in a quinophthalone dye bath for 30 seconds at room temperature,
Only squeezed with mangle aired for 90 seconds. This process was continued twice. After washing with water and drying, a black cotton warp for denim was obtained. This dyed product has excellent light resistance,
A decolorizing effect was obtained by immersing in 3 g / solution of sodium hypochlorite containing 10% available chlorine and treating at 40 ℃ for 20 minutes.

Example 2 The following formula (IV) 8 parts of quinophthalone derivative, 12 parts of Mitsui Indigo Pure EX (Indigo manufactured by Mitsui Toatsu Dyestuff Co., Ltd.), 20 parts of hydrosulfite, 20 parts of solid caustic soda and 1000 parts of water are added to 70 ° C. And heated for 15 minutes to obtain a concentrated reducing solution.

A dye bath was prepared by adding 1 part of hydrosulfite, 0.5 part of caustic soda and water to 100 parts of this solution to make 1000 parts. The cotton warp for denim washed with hot water was immersed in this at room temperature for 30 seconds, squeezed with a mangle, and then aired for 90 seconds. Only by repeating the dipping, squeezing and air ring steps three times, washing with water and drying gave a black cotton warp for denim.

This dyed product had excellent light fastness, and a decolorizing effect was obtained when treated with 3 g / solution of sodium hypochlorite containing 10% of available chlorine at 40 ° C for 20 minutes.

Example 3 A yellow denim cotton warp was obtained by treating under the same conditions as in Example 2 except that Indigo Pure EX was removed. This dyed product has excellent light resistance and
40 ° C with 3g / solution of sodium hypochlorite containing 10% available chlorine
It was decolorized in pale yellowish white after being treated for 20 minutes.

Example 4 A dye composition was prepared by adding 60 parts of Indigo Pure EX to 40 parts of 2-phthaloylmethylidine-3-hydroxy-4-bromoquinoline and 5 parts of anhydrous Glauber's salt.

A solution containing 20 parts of this dye composition, 20 parts of solid caustic soda, 20 parts of hydrosulfite and water to make 1000 parts,
A concentrated reducing solution was prepared by heating at 70 ° C for 15 minutes. To 250 parts of this preparation, 1 part of hydrosulfite and 0.5 part of solid caustic soda were added, and the mixture was adjusted to 1000 parts with water to prepare a dye bath. The denim cotton warp that had been washed with hot water was immersed in this dye bath at room temperature for 30 seconds and aired for 90 seconds only by squeezing with a mangle. The dipping, squeezing and air ring steps were repeated 6 times, followed by washing with water and drying to obtain a black cotton warp for denim.

This dyed product has excellent light fastness and is treated with 3 g / solution of sodium hypochlorite containing 10% of available chlorine at 40 ° C for 20 minutes to be decolorized and the overall density to be light and the hue to be dark green. .

Example 5 The same continuous dyeing was carried out by using 2-phthaloylmethylidine-3-hydroxy-4-bromoquinoline instead of the compound of the formula (III) of Example 1, washed with water and dried to obtain the same as Example 1. A black cotton warp for denim is obtained, which has excellent light resistance, and is made of sodium hypochlorite containing 10% available chlorine.
Decolorization effect can be seen by treating with 3g / solution at 40 ℃ for 20 minutes.
The hue was dark green.

Example 6 When 2-phthaloylmethylidine-3-hydroxy-4-bromoquinoline was used in place of the compound of formula (IV) in Example 3 and treated under the same conditions, a yellow denim cotton warp was obtained. As with Example 3, this dyed product has excellent light fastness, and contains 3 g / sodium hypochlorite containing 10% available chlorine.
When treated with the solution at 40 ° C for 20 minutes, it was decolorized to a pale yellow color.

Comparative Example 1 CIVat Yellow 2 (Mik
ethren Yellow GCN: manufactured by Mitsui Toatsu Dye Co., Ltd.) and Indigo Pure EX (manufactured by Mitsui Toatsu Dye Co., Ltd.) were used to dye a cotton warp in the same manner as in Example 2. For comparison with the cotton warp obtained in Example 2, the dyed state was observed and a decolorization test was performed by the following method.

Dyeing state: The dyed yarn was cut with a cutter knife and the fiber cross section was observed.

Decolorization test: 3 g / sodium hypochlorite containing 10% available chlorine
The solution was treated at 40 ° C for 20 minutes.

 Table 1 shows the results.

Claims (3)

(57) [Claims] 1. General formula (I) or (II) (In the formula, X represents an H, Br or Cl atom, and Y represents an H, —COOR or —COOC ₂ H ₄ OR group (wherein R represents an alkyl group)), or A dye for dyeing cotton yarn for denim, comprising one or more quinophthalone derivatives and an indigo dye. 2. A denim cotton thread in the form of a rope, represented by the general formula (I) or (II) (In the formula, X represents an H, Br or Cl atom, and Y represents an H, —COOR or —COOC ₂ H ₄ OR group (wherein R represents an alkyl group)), or A rope dyeing method for cotton yarn for denim, which comprises immersing in a dyeing bath containing one or more of this quinophthalone derivative and indigo dye, squeezing and repeating air oxidation to dye. 3. General formula (I) or (II) (In the formula, X represents an H, Br or Cl atom, and Y represents an H, —COOR or —COOC ₂ H ₄ OR group (wherein R represents an alkyl group)), or Cotton thread for denim dyed with one or more of this quinophthalone derivative and indigo dye.