JP2575791B2 - 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 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 fabric dyed with indico 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, demand for not only blue jeans but also so-called color jeans such as red, yellow, green, and black has increased with the diversification and individualization of fashion. Therefore, denim, which is a fabric for jeans, is also required to be colored in various colors such as red to brown and 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 dyes, in order to process with rope dyeing equipment for blue jeans using indigo dyes that have been widely used in the past, the dyeing behavior of these dyes and indigo dyes is too different Therefore, conventional equipment is difficult to apply to such a dyeing process. In addition, 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 dyes, only bleaching is achieved Is decolorized and yellow remains, significantly impairing the commercial value. That is, rope dyeing by blending indico dyes with other sulfur dyes, vat dyes, naphthol dyes, reactive dyes, and the like, these dyes differ from indigo dyes in that bleaching with chlorine has a very small bleaching effect, so blue The fading effect as 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 the same decoloring effect as bleaching as 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 using the above-mentioned dye or dye composition and dyeing in a color tone such as red, orange to brown, or gray to black. 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 single color to a unique color.By mixing and using the yellow and red quinophthalone derivatives, the color becomes orange to brown, and the quinophthalone derivative and indigo are used. It is possible to color gray to black by using a mixture with a dye. 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 dye composition comprising the quinophthalone derivative alone or the red and yellow quinophthalone derivatives, or the dye composition containing 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 in which dyeing is gradually and densely performed by repeating the steps of dyeing and oxidizing for a short time.Rope-shaped denim cotton yarn is immersed in a dye bath containing a quinophthalone derivative, squeezed, air By repeating the oxidation and dyeing, color jeans of red, orange to brown, and further gray to black can be obtained.

[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 the spherical cotton yarns are simultaneously pulled out, and are led to several pairs of dye baths containing a reduced form of indigo dye solution, and are continuously dyed by repeating the steps of immersion, squeezing, and oxidation for a short time. .

The present inventors have found that the quinophthalone derivative generally has no dyeing property on cotton in the cellulosic fiber dyeing method, but surprisingly, by repeating the dyeing process for denim cotton yarn as described above, the general formula ( The quinophthalone derivative represented by I) or (II) is gradually dyed red to orange, and the quinophthalone derivative represented by the general formula (III) or (IV) is dyed gradually thick yellow. The quinophthalone derivative showed the same dyeing behavior as the indigo dye, and it was found that rope dyeing of denim cotton yarn by repeating immersion, squeezing, and air oxidation was 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 produce a compound color such as black by combination with the indigo dye, and it is possible to meet the demand for color jeans. It has 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, Y represents H, -COOR or -NHR (where R represents an alkyl group)). The dye composition of the present invention comprises one or more of these derivatives of the general formula (I) or (II) and an indigo dye, a compound of the general formula (I) or (II).
At least one derivative of the formula (III) or (IV) (Wherein, X is H, Br or Cl atoms, Y is H, -COOR or -COOC ₂ H ₄ OR group (wherein, R represents shows the an alkyl group)) yellow quinophthalone derivative represented by the Or a composition comprising these three dyes.

Further, the dyeing method of the present invention is characterized in that a cotton warp for denim is formed into a rope, immersed in a dye bath containing the dye or the dye composition as described above, squeezed, and repeatedly dyed by air oxidation. This is a rope dyeing method for cotton yarn for denim.

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

The yellow quinophthalone derivative used in the present invention is represented by the above general formula (III) or (IV), and specific examples include the following compounds.

That is, 2-phthaloylmethylidin-3-hydroxyquinoline, 2-phthaloylmethylidin-3-hydroxy-4-bromoquinoline, 2- (ethoxyethoxycarbonylphthaloylmethylidyne) -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.

Further, the red quinophthalone derivative used in the present invention,
Represented by the above general formula (I) or (II),
Specifically, as the compound of formula (I), As the compound of formula (II), Is exemplified.

These derivatives show a reddish hue in a wide range, and can meet the demand of color jeans such as red jeans by using alone.

As the dye composition of the present invention, those containing the above-mentioned red quinophthalone derivative and the yellow quinophthalone derivative, those containing the red quinophthalone derivative and the indigo dye, and those containing the red quinophthalone derivative and the indigo dye It contains a quinophthalone derivative and an indigo dye, and the red and yellow quinophthalone derivatives may be used alone or in combination of two or more.

In a composition containing the one or more red quinophthalone derivatives and one or more yellow quinophthalone derivatives and / or indigo dyes, the composition becomes red, orange to brown, or gray to black according to various blending ratios. Various colorable compositions can be prepared. For example, in order to obtain black jeans, 2-phthaloylmethylidine-3
-Hydroxy-4-bromoquinolinequinoline and formula (II)
It is preferable to apply a dye composition comprising the compound of formula (1) and indigo in a ratio of about 3: 6: 1.

In the dye composition, the compounding ratio of the indigo dye and the red-based and yellow-based quinophthalone derivatives is not particularly limited, and the indigo dye and the red-based quinophthalone derivative and the yellow-based quinophthalone derivative may be mixed at an arbitrary ratio depending on a desired hue. And 100 parts of this composition, with respect to 100 parts of this composition, various additives, for example, a neutral inorganic salt such as anhydrous sodium sulfate 1 to 20
Part, anionic surfactant such as lignin dispersant
It is prepared by containing 20 parts or less. The dye composition obtained by such a method is usually provided as a powdery product,
The composition can be provided in various forms as desired, such as a powdery product, a granule product, and a paste product, depending on the purpose of use.

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 shape, and using the red quinophthalone derivative represented by the general formula (I) or (II) or a dye containing the red quinophthalone derivative. The cotton yarn for denim is subjected to rope dyeing by immersing in a dye bath containing the composition, squeezing, and repeating air oxidation.

Dye baths containing these red and yellow quinophthalone derivatives, as an alkaline agent, for example, caustic soda,
It is prepared by adding 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 10 to 50 concentrated stock solution
A separate bath is prepared in the range of g / g. Using this concentrated stock solution, a dye bath having a concentration in the dye bath of 0.5 to 10 g / is prepared.

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, in addition to using the red quinophthalone derivative alone to obtain a dyed product having a red to orange hue,
By using it in combination with a yellow quinophthalone derivative and / or indigo, the hue of the dyed product can be made a desired hue, for example, from orange to brown or from gray to black.

For this purpose, a method of dyeing the two kinds of quinophthalone derivatives and indigo dye by coexisting in the same dyeing bath, and containing the dye bath of the red quinophthalone derivative, the dye bath of the yellow quinophthalone derivative and the indigo dye. A method in which reduction baths are separately prepared, and dyeing is performed by using them is exemplified.

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 individually prepared red and yellow quinophthalone derivatives and indigo dyes, first use the required amount of indigo dye according to the desired hue, alkali required to reduce the indigo dye, For example, a reducing agent such as caustic soda and hydrosulfite is added, and the mixture is reduced at room temperature or 70 ° C. to prepare a reducing bath. Then, a red-based and yellow-based quinophthalone derivative is added to the indigo dye-reducing bath to prepare a three-component reducing bath. To prepare a dye bath. 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.

In the method of separately preparing and dyeing a dye bath containing only a red and yellow quinophthalone derivative as a dye, and a reduction bath containing only an indigo dye, the dye bath containing a quinophthalone derivative is as described above. Prepared by a method of adding an alkali, and a reducing bath containing an indigo dye is prepared by adding caustic soda and hydrosulfite to a concentrated reducing tank separate from the dyeing bath, and at room temperature or 70 ° C. as described above.
And a concentrated reducing bath is prepared, and the reducing bath is led to a dyeing bath having an appropriate concentration.

Also, when dyeing by using a red quinophthalone derivative and a yellow quinophthalone derivative in combination, each may be prepared in a separate bath or may be made to coexist in the same dyeing bath.

A typical embodiment of the dyeing method of the present invention is as follows. That is, similar to the cotton warp yarn for general blue jeans, a large number of single yarns are arranged in a single rope and used in a tow shape, and the spherical cotton warp yarn is used. It is pulled out, immersed for a short time in several pairs of dye baths containing the dye bath or the reducing solution prepared as described above, then squeezed, and further repeatedly air-oxidized to dye continuously.

For example, when using a dye bath containing a red and yellow quinophthalone derivative and a reduction bath containing an indigo dye, respectively, the cotton yarn for denim is immersed in a dye bath containing only the indigo reducing solution and squeezed with a mangle. After repeating the process of air oxidation several times and dyeing it in dark blue, immerse it in an alkaline solution of red and yellow quinophthalone derivatives or a dye bath containing hydrosulfite in addition to it and dye it with red and yellow I do. 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.

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]

If the method of the present invention is applied to continuous rope dyeing of denim cotton yarn, a wide range of colors such as red, orange to brown, and gray to black can be obtained. 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 as 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 same.

〔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
1 part of hydrosulfite, 0.5 part of caustic soda 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. This immersion, drawing, and airing steps were repeated six times. Next, this cotton warp is expressed by the following formula (A). 1 part of a red quinophthalone compound represented by the following formula (B) Was immersed in a dye bath prepared by adding 1.5 parts of a yellow quinophthalone compound represented by the following formula, 1.5 parts of solid caustic soda, and 1000 parts of water at room temperature for 30 seconds, squeezed with a mangle, and then aired for 90 seconds.

This step was repeated twice. After washing with water and drying, a black cotton warp for denim was 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.

Example 2 Red quinophthalone compound 2 represented by the formula (A)
And 6 parts of the yellow quinophthalone compound represented by the formula (B), 12 parts of Mitsui Indigo Pure EX (Indigo manufactured by Mitsui Toatsu Dye Co., Ltd.), 20 parts of hydrosulfite, 20 parts of solid caustic soda and 1000 parts by adding water. 70 ° C
For 15 minutes to obtain a concentrated reducing solution.

100 parts of this solution was added to 1 part of hydrosulfite, 0.5 part of caustic soda and water to make 1000 parts, and a dyeing bath was prepared. 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 immersion, squeezing, and airing were repeated three times, followed by washing with water and drying to obtain a black denim cotton warp.

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

Example 3 In Example 2 Indigo Pure EX and Formula (B)
When treated under the same conditions as in Example 2 except that the yellow quinophthalone compound was removed, a red cotton warp yarn for denim was obtained. This dyed product has excellent light fastness and is immersed in 3 g / solution of sodium hypochlorite containing 10% available chlorine at 40 ° C for 2 hours.
When treated for 0 minutes, the color decolored to pale red.

Example 4 Formula (C) was used for Indigo Pure EX60 part. 5 parts of anhydrous sodium sulfate was added to 10 parts of the red quinophthalone compound and 30 parts of 2-phthaloylmethylidin-3-hydroxy-4-bromoquinoline to prepare a dye composition.

A solution obtained by adding 20 parts of this dye composition, 20 parts of solid caustic soda, 20 parts of hydrosulfite and 1000 parts by adding water,
Heat at 70 ° C for 15 minutes to prepare a concentrated reducing solution. 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 cotton warp for denim washed with hot water was immersed in the dyeing bath at room temperature for 30 seconds, squeezed with a mangle, and then aired for 90 seconds. The steps of dipping, squeezing, and airing were repeated six times, followed by washing with water and drying to obtain a black denim cotton warp.

This dyed product has excellent light fastness, and is immersed in 3 g / solution of sodium hypochlorite containing 10% available chlorine and treated at 40 ° C for 20 minutes to be decolorized, the overall density becomes pale and the hue is gray Met.

Example 5 The same dyeing was carried out using the orange quinophthalone compound represented by the formula (C) in place of the compound of the formula (A) in Example 1, washed with water and dried to obtain black denim as in Example 1. Cotton warp yarn is obtained, and its light resistance is excellent,
When immersed in 3 g / solution of sodium hypochlorite containing 10% available chlorine and treated at 40 ° C. for 20 minutes, a decolorizing effect was observed, and the hue was gray.

Example 6 In Example 3, when the compound of the formula (C) was used in place of the compound of the formula (A) and treated under the same conditions, an orange denim cotton warp was obtained. It has excellent light fastness similar to that of No. 3, and when it was immersed in 3 g / solution of sodium hypochlorite containing 10% available chlorine and treated at 40 ° C. for 20 minutes, it was discolored to pale orange.

Comparative Example 1 Representative yellow vat dye CIVat Red 31 (Mikethre
n Example using Red F3B s / f: Mitsui Toatsu Dye Co., Ltd.) and Indigo Pure EX (Mitsui Toatsu Dye Co., Ltd.)
The cotton warp was dyed in the same manner as described above. 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
Immerse in the solution and process at 40 ° C for 20 minutes.

 Table 1 shows the results.

Claims (6)

(57) [Claims] 1. A compound of the formula (I) or (II) (Wherein X represents an H, Br or Cl atom, and Y represents H, -COOR or -NHR (where R represents an alkyl group)). Dye for dyeing cotton yarn for denim. 2. A dye for denim cotton yarns, comprising at least one red quinophthalone derivative represented by the general formula (I) or (II) according to claim 1 and an indigo dye. dye. 3. A red quinophthalone derivative represented by the general formula (I) or (II) according to claim 1 and a compound represented by the general formula (III) or (IV): (Wherein, X is H, Br or Cl atoms, Y is H, -COOR or -COOC ₂ H ₄ OR group (wherein, R represents shows the an alkyl group)) yellow quinophthalone derivative represented by the A dye for dyeing cotton yarn for denim, characterized by comprising at least one of the following. 4. A red quinophthalone derivative represented by the general formula (I) or (II) according to claim 3, and a yellow quinophthalone derivative represented by the general formula (III) or (IV). A dye for dyeing cotton yarn for denim, comprising the above and an indigo dye. 5. The denim cotton thread is in the form of a rope.
A cotton yarn for denim, which is immersed in a dye bath containing the dye according to claim 2, the dye according to claim 2, the dye according to claim 3, or the dye according to claim 4, squeezed, and repeatedly dyed by air oxidation. Rope dyeing method. 6. A cotton thread for denim dyed by the dyeing method according to claim 5.