JP2602937B2 - Dye for rope dyeing, 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 robustness of cotton as clothing fabric, and is widely used for work, women's trousers, children's clothes, and the like.

As jeans made of such denim, clothing called blue jeans has been widely used. Blue jeans are often used in this way because the unique color of the fabric dyed with indigo dye and the change in color over time are preferred, and clothing that emphasizes sensitivity by applying this change Is possible.

However, in recent years, along with diversification and individualization of fashion, demand for not only blue jeans but also so-called color jeans such as yellow, red, and black has been increasing. Therefore, denim, which is a fabric for jeans, is also required to be colored in various colors such as gray 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, color jeans dyed using these dyes have different properties of dyed goods from dyed goods with indigo dye, and the value as a product ranging from dyed fabric to clothing is different from conventional blue jeans 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 bleaching effect due to bleaching with chlorine.Therefore, when bleaching black denim consisting of black dyed cotton warp blended with indigo dye and ordinary yellow and red slen dye, only bleaching is achieved The product is decolorized and remains orange, significantly impairing its commercial value. That is, rope dyeing by blending indigo dye with other sulfur dyes, vat dyes, naphthol dyes, reactive dyes, and the like, these dyes are different from indigo dyes because bleaching with chlorine has a very small bleaching effect, so blue denim The fading effect as described in (1) cannot be expected and the product value is remarkably inferior.

In addition, the present applicant has previously disclosed a quinophthalone compound into which one or less halogen groups have been introduced (for example, 2-phthaloylmethylidin-3-hydroxyquinoline, 2-phthaloylmethylidin-3-hydroxy-4-bromoquinoline). Is shown in the rope dyeing behavior similar to that of the indigo dye, and the bleaching effect with chlorine was also recognized as a bleaching effect, and the application to rope dyeing was proposed.

After that, the present inventors continued further studies on this technology, and there was a problem that, with the above-mentioned proposed technology, the dyeability of a quinophthalone compound into which one or less halogen group was introduced was insufficient. He acknowledged the need for further improvement.

[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 provide a dyed material such as cotton yarn for color denim dyed in a color tone from green to black by blending with the above dye or indigo dye.

The object of the present invention has been achieved by using a specific quinophthalone derivative having two or more halogen atoms introduced therein as a dye.

Conventional quinophthalone compounds having one or less halogen atoms introduced therein (eg, 2-phthaloylmethylidin-3-hydroxyquinoline, 2-phthaloylmethylidin-3-hydroxy-4-bromoquinoline) are dyed in rope dyeing. This time, the present inventors have found that quinophthalone derivatives into which two or more halogen atoms have been introduced (hereinafter abbreviated as quinophthalone derivatives) have excellent dyeing properties in rope dyeing. Could be improved.

Moreover, similar to the indigo dye, the bleaching effect of bleach due to chlorine in the dyed product was also recognized, and the time-dependent change of the dyed product was found to be similar to the indigo dye. That is,
If the quinophthalone derivative is used alone, it can be colored in a single color to yellow. Further, by mixing and using this quinophthalone derivative and an indigo dye, it is possible to color from green to black. By using such a dye, a dyed product similar to the indigo dye can be obtained by the same dyeing method as the indigo dye, in which the dyeing state of the dye and the time-dependent change of the dyed product are similar.

Dyeing of cotton yarn using the dye composition containing the quinophthalone derivative alone or the quinophthalone derivative and an indigo dye can be performed by the following method.

For example, a large number of single yarns are arranged in a single rope to form a tow, wound in a spherical shape, and a large number of these spherical cotton yarns are simultaneously pulled out to a pair of dyeing baths equipped with a squeezing roll and an airing device. It is a continuous dyeing method that gradually dyes agricultural thickness by repeating the process of dyeing and oxidation for a short time,
A green to black color jeans can be obtained by immersing a rope-shaped cotton thread for denim in a dye bath containing a quinophthalone derivative and an indigo dye, and then squeezing and repeating air oxidation to dye.

[Means for solving the problem]

In general, denim cotton yarn for blue jeans is formed by forming a large number of single yarns into a single tow shape, winding spherically, pulling out a large number of these spherical cotton yarns at the same time, and reducing the number of yarns containing a liquid of indigo dye in a reduced form. Immersion and squeezing for a short time,
It is dyed continuously by repeating the oxidation process.

The present inventors have reported that a quinophthalone derivative into which one or less halogen atoms have been introduced usually has no dyeing property on cotton in a cellulosic fiber dyeing method. It has already been found that, by repeating the dyeing process, the color gradually becomes deep yellow.

According to subsequent studies, quinophthalone derivatives into which two or more halogen atoms have been introduced show the same dyeing behavior as indigo, and rope-like dyeing of denim cotton yarn by repeating immersion, squeezing, and air oxidation can be applied. In addition, the dyed material dyed using this has good light fastness,
In addition, the bleaching effect of bleaching due to chlorine and the change over time of the dyed material show the same properties as indigo, and the dyeing behavior is similar to that of indigo, so combination colors such as black by combination with indigo It has been found that the color jeans can be colored and that the color jeans can be met, and the present invention has been completed.

The quinophthalone derivative used in the present invention has the general formula (I) (Where X (n = 2 to 6) represents a Br or Cl atom), and specific examples include the following compounds.

1H-indene-1,3 (2H) -dione, 2- (ar, 4-dibromo-3-hydroxy-2 (1H) -quinolinylidene), monobromo-2- (4-bromo-3-hydroxy-2)
-Quinolinyl) -1H-indene-1,3 (2H) -dione, monobromo-2- (4-bromo-3-hydroxy-2
(1H) -quinolinylidene) -1H-indene-1,3 (2H)
-Dione, 1H-indene-1,3 (2H) -dione, 5-bromo-2-
(4-bromo-3-hydroxy-2 (1H) -quinolinylidene), 1H-indene-1,3 (2H) -dione, 2- (4,6-dibromo-3-hydroxy-2 (1H) -quinolinylidene) 1H-indene-1,3 (2H) -dione, 2- (ar, 4-dichloro-3-hydroxy-2 (1H) -quinolinylidene), monochloro-2- (4-chloro-3-hydroxy-2)
-Quinolinyl) -1H-indene-1,3 (2H) -dione, monochloro-2- (4-chloro-3-hydroxy-2)
(1H) -quinolinylidene) -1H-indene-1,3 (2H)
-Dione, 1H-indene-1,3 (2H) -dione, 5-chloro-2-
(4-chloro-3-hydroxy-2 (1H) -quinolinylidene), 1H-indene-1,3 (2H) -dione, 2- (4,6-dichloro-3-hydroxy-2 (1H) -quinolinylidene) Etc. are exemplified.

These derivatives exhibit a yellow hue and can meet the needs of yellow jeans by themselves.

With respect to the dye composition of the present invention, the yellow-based quinophthalone derivative and the indigo dye can be mixed to produce a green to black color.

In a composition containing one or more yellow quinophthalone derivatives and an indigo dye, various compositions capable of being colored from green to black can be prepared at various mixing ratios. For example, to get black jeans, 1H
-Indene-1,3 (2H) -dione, 2- (4,6-dibromo-
A dye composition containing (3-hydroxy-2 (1H) quinolinylidene) and indigo dye in a ratio of about 4: 6 can be used.

Although the compounding ratio of the indigo dye and the yellow quinophthalone derivative in the dye composition is not particularly limited, the indigo dye and the yellow quinophthalone derivative are used according to a desired hue,
Each contained in any proportion, based on 100 parts of this composition,
Various additives, for example, a neutral inorganic salt 1 such as anhydrous sodium sulfate
20 parts, anionic surfactant such as lignin dispersant
It is prepared containing up to 20 parts.

The dye composition obtained by such a method is usually provided as a powdery product, and the form of the composition may vary depending on the purpose of use, such as a powdery product, a granule product, and a paste product, depending on the purpose of use. Can be provided in the form of

The dyeing method of the present invention using the above-described derivative or composition comprises a step of forming a cotton yarn for denim into a rope and using the above-mentioned quinophthalone derivative of the general formula (I) alone or a yellow quinophthalone derivative and an indigo dye. , Squeezing, and air oxidation are repeated to carry out rope dyeing of cotton yarn for denim.

The dyeing bath containing these yellow quinophthalone derivatives is prepared by adding an alkali agent such as caustic soda or an alkali of a mixture of caustic soda and soda ash. The concentration of the quinophthalone derivative in the dyeing bath is determined according to the concentration of the desired dyed product. Generally, a concentrated stock solution is prepared as a separate bath in the range of 10 to 15 g /, and a dye bath having a concentration in a dyeing bath of 0.5 to 10 g / is prepared using this concentrated stock solution. The amount of the alkali used may be a small excess 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 can be used alone to obtain a yellow dyed product, or can be used in combination with an indigo dye to obtain a desired hue, for example, from 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 an individually prepared yellow quinophthalone derivative and an indigo dye, first use the indigo dye in a necessary amount according to a desired hue, and use an alkali such as caustic soda necessary for reducing the indigo dye. Add a reducing agent such as hydrosulfite and add room temperature or 70 ° C
And a reduction bath is prepared. Then, a yellow quinophthalone derivative is added to the indigo dye reduction bath to prepare a dye bath in which the two 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 the method of dyeing by preparing a dye bath containing only a yellow quinophthalone derivative as a dye and a reducing bath containing only an indigo dye, respectively, the dye bath containing a quinophthalone derivative has the alkali as described above. The reducing bath containing the indigo dye, prepared by the addition method, is a concentrated reducing bath, in which caustic soda and hydrosulfite are added to a concentrated reducing tank separate from the dyeing bath, and reduced at room temperature or 70 ° C. as described above. From the reduction bath to a dyeing bath of appropriate concentration.

A typical embodiment of the dyeing method of the present invention is as follows. In other words, like a general cotton thread for blue jeans, a large number of single yarns are arranged in a single rope and used in a tow shape, and a spherical cotton warp is used. Then, immersion 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.

When the dyeing bath containing the yellow quinophthalone derivative and the reducing bath containing the indigo dye are separately provided, the cotton warp for denim is immersed in a dyeing bath containing only the indigo reducing solution, squeezed with a mangle, and then squeezed. After repeating the oxidation step several times and dyeing it in dark blue, it is immersed in a dye solution containing an alkali solution of a yellow quinophthalone derivative or an alkali solution and hydrosulfite to dye over 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 mix and color cotton yarn for denim. This method is preferable from the viewpoint of workability.

[Action and effect]

If the method of the present invention is applied to continuous rope dyeing of cotton yarn for denim, it is possible to produce a yellow color or a green color by blending with an indigo dye and even a black color. The obtained dyed product has good light fastness and a decolorizing function by chlorine bleaching, and the change in color tone with time is almost the same as that of the indigo dye.

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.
Heat for 15 minutes to obtain a concentrated reducing solution of indigo. This liquid 60
Then, 1 part of hydrosulfite, 0.5 part of caustic soda and water are added to 1000 parts to prepare an indigo dyeing bath.

The cotton warp for denim washed with water is immersed in this at room temperature for 30 seconds, squeezed with a mangle, and then aired for 90 seconds. This immersion, squeezing, and airing steps are repeated six times. Next, this cotton warp is converted to formula II 2.0 parts of the dye, 1.5 parts of solid caustic soda and 1000
Immersed in a dye bath of the quinophthalone derivative at room temperature for 30 seconds, squeezed with a mangle, and aired for 90 seconds.

This process is continued twice. After washing with water and drying, a black denim cotton warp is obtained. This dyed product has excellent light fastness and is made of sodium hypochlorite containing 10% available chlorine.
When immersed in 3 g / liquid and treated at 40 ° C. for 20 minutes, a decolorizing effect was obtained.

Comparative Example 1 Instead of the compound of formula II of Example 1, a compound of formula III The same continuous dyeing was carried out using a yellow quinophthalone derivative into which one Br group had been introduced, followed by washing with water and drying.
Compared to the quinophthalone derivative having two Br groups of Formula II, the dyeing resistance was lower than that of the quinophthalone derivative in which two Br groups were introduced. Was obtained.

Example 2 8 parts of a yellow quinophthalone derivative represented by the formula II, 12 parts of Mitsui Indigo Pure-EX (manufactured by Mitsui Toatsu Dye Co., Ltd.), 20 parts of hydrosulfite, 20 parts of solid caustic soda and 1000 parts by adding water The concentrated solution is heated at 70 ° C. for 15 minutes to obtain a concentrated reducing solution.

To 250 parts of this solution, 1 part of hydrosulfite, 0.5 part of caustic soda and water are added to make 1000 parts, and a dyeing bath is prepared. The cotton-based yarn for denim washed with water is immersed in this at room temperature for 30 seconds, squeezed with a mangle, and then aired for 90 seconds. After repeating the steps of dipping, squeezing and airing three times, washing with water and drying, a black cotton warp for denim is obtained.

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

Example 5 Instead of the compound of formula II of Example 1, a compound of formula IV The same continuous dyeing was carried out using the yellow quinophthalone derivative of the above, washed with water and dried to obtain a cotton warp for black denim in the same manner as in Example 1, having excellent light resistance and hypochlorous acid containing 10% available chlorine. When treated with 3 g of an acid soda / solution at 40 ° C. for 20 minutes, a decolorizing effect was observed, and the hue was green.

Comparative Example 2 A representative yellow vat dye CIVat Yellow 2 (Miketh
Using 8 parts of ren Yellow GCN (manufactured by Mitsui Toatsu Dye Co., Ltd.) and 12 parts of Indigo Pure EX (manufactured by Mitsui Toatsu Dye Co., Ltd.), cotton warp yarn was dyed 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 of sodium hypochlorite containing 10% available chlorine
Treat with the solution at 40 ° C for 20 minutes.

 Table 1 shows the results.

Continuation of the front page (56) References JP-A-53-145845 (JP, A) JP-A-1-261462 (JP, A) JP-A-50-2729 (JP, A) JP-A-54-23634 (JP) JP-A-51-87535 (JP, A) JP-B-48-20476 (JP, B1) US Patent No. 3399028 (US, A)

Claims (4)

(57) [Claims] 1. The compound of the general formula (I) (In the formula, X (n = 2 to 6) represents a Br or Cl atom.)
A dye for rope dyeing containing the quinophthalone derivative represented. 2. A dye composition for rope dyeing comprising at least one yellow quinophthalone derivative represented by the general formula (I) according to claim 1 and an indigo dye. 3. The denim cotton yarn is in the form of a rope.
A rope dyeing method for cotton yarn for denim, comprising immersing in a dye bath containing the dye or the dye composition according to claim 2, squeezing, and repeatedly performing air oxidation. 4. A cotton thread for denim dyed by the dyeing method according to claim 3.