JP6918123B2 - Reactive dye composition and dyeing method using it - Google Patents

Description

The present invention relates to a reactive dye composition suitable for dyeing cellulose fibers or cellulose fiber-containing fibers, and a dyeing method using the same.

In dyeing of cellulose fibers, a method is known in which a yellow reactive dye, a red reactive dye, and a blue or dark blue reactive dye are used as dyes for three primary colors, and they are mixed in various ratios for dyeing. ..

The dyes for the three primary colors have excellent build-up and leveling properties of each dye, the dyeing speeds of the three primary colors are almost equal and the temperature dependence is uniform, and the color development and fastness are excellent. is needed. In addition, against the background of energy saving in recent years, dyeing with a low bath ratio dyeing machine is mainly used in the field, and it is difficult to make the dyeing bath ratio on the laboratory scale and the dyeing bath ratio on the factory scale the same. Is. Furthermore, there is a strong demand for dyes that do not meet the amine substance regulations related to the safety of textile products worldwide.

However, each dye used as a conventional dye for three primary colors has different dyeing behavior due to different affinity and reactivity with cellulose fibers, and further, a problem of color difference due to a change in dyeing bath ratio occurs, and reproducibility occurs. There is a defect. Therefore, from the viewpoint of improving productivity and environmental friendliness, dyes for three primary colors having excellent reproducibility are strongly desired.

In order to solve such a problem, for example, various studies have been made in the following Patent Documents 1 to 9, but satisfactory results have not yet been obtained.

Japanese Patent No. 3168624 Japanese Unexamined Patent Publication No. 2000-44830 Special Fair 1-24826 Gazette U.S. Pat. No. 6,090,164 Special Fair 1-12787 Gazette European Patent No. 0022575 Japanese Unexamined Patent Publication No. 2004-269863 Japanese Unexamined Patent Publication No. 56-118976 Japanese Unexamined Patent Publication No. 56-15881

An object of the present invention is to develop a reactive dye composition for dyeing cellulose fibers or cellulose fiber-containing fibers with good reproducibility, good leveling property, and high fastness, and a dyeing method using the same.

As a result of intensive studies for the above purpose, the present inventors have found a specific reactive dye composition and a dyeing method using the same, and have completed the present invention.

［式中、Ｙ_１はＳＯ_２ＣＨ＝ＣＨ_２又はＳＯ_２ＣＨ_２ＣＨ_２Ｚを表し、Ｚはアルカリで脱離する基を表す。］

［式中、Ｙ_２、Ｙ_３はそれぞれ独立にＳＯ_２ＣＨ＝ＣＨ_２又はＳＯ_２ＣＨ_２ＣＨ_２Ｚを表し、Ｚはアルカリで脱離する基を表す。］

［式中、Ｙ_９はＳＯ_２ＣＨ＝ＣＨ_２又はＳＯ_２ＣＨ_２ＣＨ_２Ｚを表し、Ｚはアルカリで脱離する基を表す。］

［式中、Ｒ_１は水素原子、ハロゲン原子、又は（Ｃ１〜Ｃ４）アルコキシ基を表し、Ｙ_５はＳＯ_２ＣＨ＝ＣＨ_２又はＳＯ_２ＣＨ_２ＣＨ_２Ｚを表し、Ｚはアルカリで脱離する基を表す。］

［式中、Ｙ_６はＳＯ_２ＣＨ＝ＣＨ_２又はＳＯ_２ＣＨ_２ＣＨ_２Ｚを表し、Ｚはアルカリで脱離する基を表す。］

［式中、Ｒ_２は水素原子又は（Ｃ１〜Ｃ４）アルキル基を表し、Ｙ_７はＳＯ_２ＣＨ＝ＣＨ_２又はＳＯ_２ＣＨ_２ＣＨ_２Ｚを表し、Ｚはアルカリで脱離する基を表す。］

［式中、Ｙ_８はＳＯ_２ＣＨ＝ＣＨ_２又はＳＯ_２ＣＨ_２ＣＨ_２Ｚを表し、Ｚはアルカリで脱離する基を表す。］That is, the present invention relates to the following 1) to 10).
1) A reactive dye composition containing any of the following (I) to (IV) as a dye component.
(I) The reaction dye (R) for red containing the reactive dye whose free acid form is represented by the following formula (1) and the reactive dye whose free acid form is represented by the following formula (2), and the free acid form. Combination with a yellow reactive dye (Y) containing a reactive dye represented by the following formula (8).
(II) The red reactive dye (R), the reactive dye whose free acid form is represented by the following formula (4), and the reactive dye and free acid form whose free acid form is represented by the following formula (5). Is a combination with a blue reactive dye (B) containing at least one reactive dye selected from the reactive dyes represented by the following formula (6).
(III) A dark blue reactive dye containing the red reactive dye (R), a reactive dye whose free acid form is represented by the following formula (5), and a reactive dye whose free acid form is represented by the following formula (7). Combination with (N).
(IV) A combination of the red reactive dye (R), the yellow reactive dye (Y), and the blue reactive dye (B) or the dark blue reactive dye (N).

[In the formula, Y ₁ represents SO ₂ CH = CH ₂ or SO ₂ CH ₂ CH ₂ Z, and Z represents a group desorbed with alkali. ]

[In the formula, Y ₂ and Y ₃ independently represent SO ₂ CH = CH ₂ or SO ₂ CH ₂ CH ₂ Z, and Z represents a group desorbed by alkali. ]

[In the formula, Y ₉ represents SO ₂ CH = CH ₂ or SO ₂ CH ₂ CH ₂ Z, and Z represents a group desorbed with alkali. ]

[In the formula, R ₁ represents a hydrogen atom, a halogen atom, or (C1 to C4) alkoxy group, Y ₅ represents SO ₂ CH = CH ₂ or SO ₂ CH ₂ CH ₂ Z, and Z is eliminated with an alkali. Represents the group to be used. ]

[In the formula, Y ₆ represents SO ₂ CH = CH ₂ or SO ₂ CH ₂ CH ₂ Z, and Z represents a group desorbed with alkali. ]

[In the formula, R ₂ represents a hydrogen atom or (C1 to C4) alkyl group, Y ₇ represents SO ₂ CH = CH ₂ or SO ₂ CH ₂ CH ₂ Z, and Z represents a group desorbed by alkali. .. ]

[In the formula, Y ₈ represents SO ₂ CH = CH ₂ or SO ₂ CH ₂ CH ₂ Z, and Z represents a group desorbed with alkali. ]

［式中、Ｙ_４はＳＯ_２ＣＨ＝ＣＨ_２又はＳＯ_２ＣＨ_２ＣＨ_２Ｚを表し、Ｚはアルカリで脱離する基を表す。］2) The content of the reactive dye represented by the formula (1) in the red reactive dye (R) is 30% by mass to 70% by mass, and the content of the reactive dye represented by the formula (2) is The reactive dye composition according to 1) above, which is 30% by mass to 70% by mass.
3) The reactive dye composition according to 1) above, wherein the red reactive dye (R) further contains a reactive dye whose free acid form is represented by the following formula (3).

[In the formula, Y ₄ represents SO ₂ CH = CH ₂ or SO ₂ CH ₂ CH ₂ Z, and Z represents a group desorbed with alkali. ]

4) The content of the reactive dye represented by the formula (1) in the red reactive dye (R) is 20% by mass to 40% by mass, and the content of the reactive dye represented by the formula (2) is The reactive dye composition according to 3) above, wherein the content is 30% by mass to 50% by mass and the content of the reactive dye represented by the formula (3) is 10% by mass to 30% by mass.
5) The content of the reactive dye represented by the formula (4) in the blue reactive dye (B) is 10% by mass to 90% by mass, and the reactive dye represented by the formula (5) and the above formula ( The reactive dye composition according to any one of 1) to 4) above, wherein the total content of at least one reactive dye selected from the reactive dyes shown in 6) is 10% by mass to 90% by mass. ..
6) The content of the reactive dye represented by the formula (4) in the blue reactive dye (B) is 10% by mass to 30% by mass, and the reactive dye represented by the formula (5) and the above formula ( The reactive dye composition according to any one of 1) to 4) above, wherein the total content of at least one reactive dye selected from the reactive dyes shown in 6) is 70% by mass to 90% by mass. ..
7) The content of the reactive dye represented by the formula (4) in the blue reactive dye (B) is 10% by mass to 30% by mass, and the content of the reactive dye represented by the formula (5) is The reactive dye composition according to any one of 1) to 4) above, wherein the content of the reactive dye is 50% by mass to 60% by mass and the content of the reactive dye represented by the formula (6) is 20% by mass to 30% by mass. thing.
8) The content of the reactive dye represented by the formula (5) in the dark blue reactive dye (N) is 5% by mass to 95% by mass, and the content of the reactive dye represented by the formula (7) is The reactive dye composition according to any one of 1) to 4) above, which is 5% by mass to 95% by mass.
9) The content of the reactive dye represented by the formula (5) in the dark blue reactive dye (N) is 80% by mass to 95% by mass, and the content of the reactive dye represented by the formula (7) is The reactive dye composition according to any one of 1) to 4) above, which is 5% by mass to 20% by mass.
10) A dyeing method comprising dyeing a cellulose fiber or a cellulose fiber-containing fiber with the reactive dye composition according to any one of 1) to 9) above.

According to the reactive dye composition of the present invention and the dyeing method using the same, there is no change in hue due to a change in the dyeing bath ratio, the temperature dependence is good, and the dyeing property is uniform, so that the cellulose fibers can be reproduced with good reproducibility. It is possible to provide products that can be dyed with high fastness and high color development, and that do not meet the recent amine substance regulations related to the safety of textile products.

The reactive dye composition of the present invention contains any of the following (I) to (IV) as a dye component.
(I) The reaction dye (R) for red containing the reactive dye whose free acid form is represented by the above formula (1) and the reactive dye whose free acid form is represented by the above formula (2), and the free acid form. Combination with a yellow reactive dye (Y) containing a reactive dye represented by the above formula (8).
(II) The red reactive dye (R), the reactive dye whose free acid form is represented by the above formula (4), and the reactive dye and free acid form whose free acid form is represented by the above formula (5). Is a combination with a blue reactive dye (B) containing at least one reactive dye selected from the reactive dyes represented by the above formula (6).
(III) A dark blue reactive dye containing the red reactive dye (R), a reactive dye whose free acid form is represented by the above formula (5), and a reactive dye whose free acid form is represented by the above formula (7). Combination with (N).
(IV) A combination of the red reactive dye (R), the yellow reactive dye (Y), and the blue reactive dye (B) or the dark blue reactive dye (N).

The reactive dye represented by the above formula (1) contained in the red reactive dye (R) is described in Patent Document 6 and the like, and the reactive dye represented by the above formula (2) is described in Patent Documents 2 and 4 and the like. It can be produced by a method known per se, or it can be commercially available. Examples of the reactive dye represented by the above formula (1) include C.I. I. Reactive Red 195, C.I. I. Reactive Red 241 and the like can be mentioned.

The ratio of each reactive dye in the red reactive dye (R) is not particularly limited, but the content of the reactive dye represented by the above formula (1) in the red reactive dye (R) is 30% by mass to 70% by mass. The content of the reactive dye represented by the above formula (2) is preferably 30% by mass to 70% by mass.

The red reactive dye (R) preferably further contains a reactive dye whose free acid form is represented by the above formula (3). The reactive dye represented by the above formula (3) is described in Patent Document 8 and the like, and can be produced by a method known per se or commercially available.

When the red reactive dye (R) contains the reactive dye represented by the above formula (3), the content of the reactive dye represented by the above formula (1) in the red reactive dye (R) is 20% by mass to 40% by mass. The content of the reactive dye represented by the above formula (2) is 30% by mass to 50% by mass, and the content of the reactive dye represented by the above formula (3) is 10% by mass to 30% by mass. Is preferable.

The red reactive dye (R) may contain other reactive dyes in addition to the reactive dyes represented by the above formulas (1) to (3). However, the content of the other reactive dye is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 0% by mass in the red reactive dye (R). .. That is, it is preferable that the red reactive dye (R) does not contain a reactive dye other than the reactive dyes represented by the above formulas (1) to (3).

The reactive dye represented by the above formula (8) contained in the yellow reactive dye (Y) is described in Patent Document 9 and the like, and can be produced by a method known per se or commercially available. .. Examples of the reactive dye represented by the above formula (8) include C.I. I. Reactive Yellow 145 and the like can be mentioned.

The yellow reactive dye (Y) may contain other reactive dyes in addition to the reactive dye represented by the above formula (8). However, the content of the other reactive dye is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 0% by mass in the yellow reactive dye (Y). .. That is, it is preferable that the yellow reactive dye (Y) does not contain a reactive dye other than the reactive dye represented by the above formula (8).

The reactive dye represented by the above formula (4) contained in the blue reactive dye (B) is described in Patent Document 3 and the like, and the reactive dye represented by the above formula (5) is described in Patent Document 5 and the like in the above formula (6). The reactive dyes shown are described in Japanese Patent Publication No. 3-10669, etc., and can be produced by a method known per se, or can be commercially available. Examples of the reactive dye represented by the above formula (4) include C.I. I. Examples thereof include Reactive Blue 220 and the like, and examples of the reactive dye represented by the above formula (6) include C.I. I. Reactive Blue 221 and the like can be mentioned.

The ratio of each reactive dye in the blue reactive dye (B) is not particularly limited, but the content of the reactive dye represented by the above formula (4) in the blue reactive dye (B) is 10% by mass to 90% by mass. The total content of the reactive dye represented by the above formula (5) and at least one reactive dye selected from the reactive dye represented by the above formula (6) is 10% by mass to 90% by mass. Is preferable. More preferably, the content of the reactive dye represented by the above formula (4) in the blue reactive dye (B) is 10% by mass to 30% by mass, and the reactive dye represented by the above formula (5) and the above formula. The total content of at least one reactive dye selected from the reactive dyes represented by (6) is 70% by mass to 90% by mass. More preferably, the content of the reactive dye represented by the above formula (4) is 10% by mass to 30% by mass, and the content of the reactive dye represented by the above formula (5) is 50% by mass to 60% by mass. Yes, the content of the reactive dye represented by the above formula (6) is 20% by mass to 30% by mass.

The blue reactive dye (B) may contain other reactive dyes in addition to the reactive dyes represented by the above formulas (4) to (6). However, the content of the other reactive dye is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 0% by mass in the blue reactive dye (B). .. That is, it is preferable that the blue reactive dye (B) does not contain a reactive dye other than the reactive dyes represented by the above formulas (4) to (6).

The reactive dye represented by the above formula (5) contained in the dark blue reactive dye (N) is described in Patent Document 5 and the like, and the reactive dye represented by the above formula (7) is described in C.I. I. It is a compound known as Reactive Black 5, which can be produced by a method known per se or commercially available.

The ratio of each reactive dye in the dark blue reactive dye (N) is not particularly limited, but the content of the reactive dye represented by the above formula (5) in the dark blue reactive dye (N) is 5% by mass to 95% by mass. The content of the reactive dye represented by the above formula (7) is preferably 5% by mass to 95% by mass. More preferably, the content of the reactive dye represented by the above formula (5) is 80% by mass to 95% by mass in the dark blue reactive dye (N), and the content of the reactive dye represented by the above formula (7). Is 5% by mass to 20% by mass.

The dark blue reactive dye (N) may contain other reactive dyes in addition to the reactive dyes represented by the above formulas (5) and (7). However, the content of the other reactive dye is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 0% by mass in the dark blue reactive dye (N). .. That is, it is preferable that the dark blue reactive dye (N) does not contain a reactive dye other than the reactive dyes represented by the above formulas (5) and (7).

In the reactive dyes represented by the above formulas (1) to (8), Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₇ , Y ₈ , and Y ₉ are SO ₂ CH = CH _2. Or SO ₂ CH ₂ CH ₂ Z, where Z is a group desorbed with alkali. When Z is eliminated with an alkali, SO ₂ CH = CH ₂ . As the Z can be used are various groups known as leaving group, for example, a sulfonic acid group such as OSO 3 _H is preferred.

In the reactive dye represented by the above formula (4), R ₁ represents a hydrogen atom, a halogen atom, or an alkoxy group (C1 to C4). Examples of the halogen atom include a chlorine atom and a bromine atom. Examples of the (C1 to C4) alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an isobutoxy group and the like. A hydrogen atom is preferable as _{R 1.}

In the reactive dye represented by the above formula (6), R ₂ represents a hydrogen atom or an alkyl group (C1 to C4). Examples of the (C1 to C4) alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isobutyl group and the like. The R _2, ethyl group is preferred.

The replacement positions of Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₇ , Y ₈ , Y ₉ , and R ₁ are not particularly limited as long as they can be replaced.

The reactive dyes represented by the above formulas (1) to (8) are shown in the form of free acids, but they may be salts, and their counter cations are not particularly limited. Of these, alkali metal salts or alkaline earth metal salts are preferable, and sodium salts, potassium salts, and lithium salts are more preferable.

In the reactive dye composition of the present invention, the blending method of each reactive dye is not particularly limited. For example, a method in which each reactive dye is produced separately and then blended; a method in which a reaction solution containing each reactive dye produced during production is mixed and then dried to form a composition; each in a dyeing bath. A method of dissolving the reactive dye and making the composition the same as each composition in the dyeing bath; etc. can be adopted. At that time, the mixing ratio of each reactive dye is appropriately adjusted according to the desired color tone. Further, if necessary, the reactive dye composition of the present invention contains a known additive such as a concentration adjusting agent, a dispersant, a leveling agent, a precipitation inhibitor, a sequestrant, a reduction inhibitor and the like. You may let me.

When each of the above reactive dyes and, if necessary, the above additives are added to the dyeing bath, padding bath, and printing paste to prepare and dye the dyeing bath, etc., the order in which the dyes, additives, etc. are dissolved is It may be in any order.

The present invention also includes a method for dyeing a cellulose fiber or a cellulose fiber-containing fiber using the reactive dye composition of the present invention. In dyeing, the amount of the reactive dye composition used is usually about 0.0005% by mass to 15% by mass with respect to the fiber.

The reactive dye composition of the present invention is useful for dyeing cellulose fibers and fibers containing the same. Examples of the target fiber include cellulose fibers such as cotton, hemp, rayon, polynosic, cupra, and lyocell, or mixed fibers of these. Further, blended spinning or mixed woven products of these fibers or mixed fibers with other fibers such as polyester fibers, acetate fibers, polyacrylic nitrile fibers, wool, silk, polyamide fibers such as nylon and the like can be mentioned.

Dyeing using the reactive dye composition can be performed according to, for example, the following method, but the dyeing is not limited to this method. For example, in dyeing cellulose fibers such as cotton, the reactive dye composition of the present invention according to a desired hue and concentration is added to the dyeing bath, and an inorganic neutral salt (sodium hydroxide, sodium chloride, etc.) and an acid binder (acid binder (salt, etc.)) are added. Sodium carbonate, sodium bicarbonate, caustic soda, sodium tertiary phosphate, etc.) can be used alone or in combination, respectively. There is no particular limitation on the amount of the inorganic neutral salt or acid binder used. The inorganic neutral salt and the acid binder may be added to the dyeing bath all at once, or may be added separately. After the dyeing is completed, after washing with water and hot water dyeing, washing is performed in a soaping bath containing a commercially available soaping agent by a conventional method, and the dyeing is completed.

Hereinafter, the present invention will be described in more detail with reference to Examples.
For each of the dyes of the above formulas (1) to (8), the following corresponding compounds (A) to (H) were used as reactive dyes.
Unless otherwise specified, "parts" in the text represents parts by mass. In addition, C.I. I. Reactive means a color index generic name.

[Example 1]
Formulation Example 1 of the present invention Gray
Formulation composition
Reactive dye for red
Compound (A) 0.15 part
Compound (B) 0.19 parts
Reactive dye for blue
Compound (D) 0.15 parts
Compound (E) 0.38 parts
Compound (F) 0.20 part
Reactive dye for yellow
Compound (H) 0.50 parts

[Example 2]
Formulation Example 2 of the present invention Gray
Formulation composition
Reactive dye for red
Compound (A) 0.12 part
Compound (B) 0.18 parts
Compound (C) 0.06 part
Reactive dye for blue
Compound (D) 0.15 parts
Compound (E) 0.38 parts
Compound (F) 0.20 part
Reactive dye for yellow
Compound (H) 0.50 parts

[Example 3]
Formulation Example 3 of the present invention Gray
Formulation composition
Reactive dye for red
Compound (A) 0.14 parts
Compound (B) 0.21 part
Reactive dye for blue
Compound (D) 0.18 parts
Compound (E) 0.50 parts
Reactive dye for yellow
Compound (H) 0.47 parts

[Example 4]
Formulation Example 4 of the present invention Gray
Formulation composition
Reactive dye for red
Compound (A) 0.11 part
Compound (B) 0.26 parts
Compound (C) 0.08 part
Reactive dye for blue
Compound (D) 0.26 parts
Compound (F) 0.71 part
Reactive dye for yellow
Compound (H) 0.50 parts

[Example 5]
Formulation Example 5 of the present invention Gray
Formulation composition
Reactive dye for red
Compound (A) 0.11 part
Compound (B) 0.20 part
Reactive dye for dark blue
Compound (E) 0.93 parts
Compound (G) 0.11 part
Reactive dye for yellow
Compound (H) 0.45 parts

[Example 6]
Formulation Example 6 of the present invention Gray
Formulation composition
Reactive dye for red
Compound (A) 0.09 part
Compound (B) 0.21 part
Compound (C) 0.06 part
Reactive dye for dark blue
Compound (E) 0.93 parts
Compound (G) 0.11 part
Reactive dye for yellow
Compound (H) 0.47 parts

[Comparative Example 1]
Comparative formulation example 1 Gray
Formulation composition
Reactive dye for red C. I. Reactive Red 195 0.35 copies
Reactive dye for blue C. I. Reactive Blue 220 0.90 copies
Reactive dye for yellow C. I. Reactive Yellow 145 0.50 copies

[Comparative Example 2]
Comparative formulation example 2 Gray
Formulation composition
Reactive dye for red C. I. Reactive Red 195 0.30 copies
Reactive dye for blue C. I. Reactive Blue 5 0.65 copies
Reactive dye for yellow C. I. Reactive Yellow 145 0.40 copies

[Comparative Example 3]
Comparative formulation example 3 Gray
Formulation composition
Reactive dye for red
Compound (B) 0.25 parts
Reactive dye for blue C. I. Reactive Blue 220 0.90 copies
Reactive dye for yellow C. I. Reactive Yellow 145 0.45 copies

[Comparative Example 4]
Comparative formulation example 4 Gray
Formulation composition
Reactive dye for red
Compound (C) 0.40 parts
Reactive dye for blue C. I. Reactive Blue 221 0.90 copies
Reactive dye for yellow C. I. Reactive Yellow 145 0.40 copies

[Comparative Example 5]
Comparative formulation example 5 Gray
Formulation composition
Reactive dye for red
Compound (B) 0.28 parts
Reactive dye for blue
Compound (E) 0.80 parts
Reactive dye for yellow C. I. Reactive Yellow 145 0.40 copies

[Bath ratio dependence test]
(1) Dyeing at a bath ratio of 1:10 Water was added to 10 parts of the dye and anhydrous sodium sulfate of each formulation example to prepare a dyeing bath having a total volume of 500 parts. 50 parts of cotton knitted fabric was put into this dyeing bath and treated at 60 ° C. for 15 minutes, then 10 parts of sodium carbonate was put in and dyed at the same temperature for 60 minutes. Then, after washing with water and hot water, soaping is performed at 100 ° C. for 15 minutes in 1000 parts of an aqueous solution containing a commercially available soaping agent (Scoreroll C-1200, Kitahiro Chemical Co., Ltd., 1 g / L), and then washed with water. And dried to obtain a dyed product.

(2) Dyeing at a bath ratio of 1:30 Water was added to 30 parts of the dye and anhydrous sodium sulfate of each formulation example to prepare a dyeing bath having a total volume of 1500 parts. 50 parts of cotton knitted fabric was put into this dyeing bath and treated at 60 ° C. for 15 minutes, then 30 parts of sodium carbonate was put in and dyed at the same temperature for 60 minutes. Then, after washing with water and hot water, soaping was performed at 100 ° C. for 15 minutes in 1000 parts of an aqueous solution containing the above soaping agent, and then washing with water and drying was performed to obtain a dyed product.

(3) Dyeing at a bath ratio of 1:60 Water was added to 60 parts of the dye and anhydrous sodium sulfate of each formulation example to prepare a dyeing bath having a total volume of 3000 parts. 50 parts of cotton knitted fabric was put into this dyeing bath and treated at 60 ° C. for 15 minutes, then 60 parts of sodium carbonate was put in and dyed at the same temperature for 60 minutes. Then, after washing with water and hot water, soaping was performed at 100 ° C. for 15 minutes in 1000 parts of an aqueous solution containing the above soaping agent, and then washing with water and drying was performed to obtain a dyed product.

(Judgment method)
Based on the dyed product obtained at a bath ratio of 1:10, the hue difference ΔEa * b * of the dyed product obtained under each condition was measured by the colorimeter Color Eye CE7100 (manufactured by Macbeth), under a D65 light source, and C. .. I. It was calculated using the E color difference formula. The results are shown in Table 1. The closer the value of the hue difference ΔEa * b * is to 0, the better.

[Dyeing property (rate) test]
Water was added to 10 parts of the dye and anhydrous sodium sulfate of each formulation example to prepare a dyeing bath having a total amount of 480 parts. 50 parts of cotton knitted fabric is put into this dyeing bath and treated at 60 ° C. for 15 minutes, then 0.5 part of sodium carbonate is put in and treated at the same temperature for 10 minutes, and then 3 parts of sodium carbonate is put in and the same temperature. Then, 6.5 parts of sodium carbonate was added and treated at the same temperature for 10 minutes, and then stained for another 40 minutes. Then, after washing with water and hot water, soaping is performed at 100 ° C. for 15 minutes in 1000 parts of an aqueous solution containing a commercially available soaping agent (Scoreroll C-1200, Kitahiro Chemical Co., Ltd., 1 g / L), and then washed with water. And dried to obtain a dyed product.

Taking the dyed product dyed for 70 minutes as the standard dyeing rate of 100%, the dyeing rate of the dyed product obtained at each processing time was measured under a colorimeter Color Eye CE7100 (manufactured by Macbeth) and a D65 light source. , The dyeing rate (%) was calculated from the reflectance of each component (yellow, red, blue, dark blue). The results are shown in Tables 2 and 3. It should be noted that the closer the dyeing rate of each component is to each treatment time, the better.

As can be seen from Tables 1 to 3, the results of the bath ratio dependence test and the dyeing property test of the dyed products obtained in Examples 1 to 6 showed that the bath ratio fluctuated greatly regardless of the combination of the reactive dyes. Even in this case, the hue change was extremely small, the dyeing rate at each treatment time was similar, and the dyeing reproducibility was extremely excellent.

Claims (10)

A reactive dye composition containing any of the following (I) to (IV) as a dye component.
(I) and red reactive dye comprising a reactive dye the free acid form of the form of reactive dyes and the free acid is represented by the following formula (1) is represented by the following formula (2) (R), the free acid form Combination with a yellow reactive dye (Y) containing a reactive dye represented by the following formula (8).
(II) The red reactive dye (R), the reactive dye whose free acid form is represented by the following formula (4), and the reactive dye and free acid form whose free acid form is represented by the following formula (5). Is a combination with a blue reactive dye (B) containing at least one reactive dye selected from the reactive dyes represented by the following formula (6).
(III) A dark blue reactive dye containing the red reactive dye (R), a reactive dye whose free acid form is represented by the following formula (5), and a reactive dye whose free acid form is represented by the following formula (7). Combination with (N).
(IV) A combination of the red reactive dye (R), the yellow reactive dye (Y), and the blue reactive dye (B) or the dark blue reactive dye (N).

[In the formula, Y ₁ represents SO ₂ CH = CH ₂ or SO ₂ CH ₂ CH ₂ Z, and Z represents a group desorbed with alkali. ]

[In the formula, Y ₂ and Y ₃ independently represent SO ₂ CH = CH ₂ or SO ₂ CH ₂ CH ₂ Z, and Z represents a group desorbed by alkali. ]

[In the formula, Y ₉ represents SO ₂ CH = CH ₂ or SO ₂ CH ₂ CH ₂ Z, and Z represents a group desorbed with alkali. ]

[In the formula, R ₁ represents a hydrogen atom, a halogen atom, or (C1 to C4) alkoxy group, Y ₅ represents SO ₂ CH = CH ₂ or SO ₂ CH ₂ CH ₂ Z, and Z is eliminated with an alkali. Represents the group to be used. ]

[In the formula, Y ₆ represents SO ₂ CH = CH ₂ or SO ₂ CH ₂ CH ₂ Z, and Z represents a group desorbed with alkali. ]

[In the formula, R ₂ represents a hydrogen atom or (C1 to C4) alkyl group, Y ₇ represents SO ₂ CH = CH ₂ or SO ₂ CH ₂ CH ₂ Z, and Z represents a group desorbed by alkali. .. ]

[In the formula, Y ₈ represents SO ₂ CH = CH ₂ or SO ₂ CH ₂ CH ₂ Z, and Z represents a group desorbed with alkali. ] The content of the reactive dye represented by the formula (1) in the red reactive dye (R) is 30% by mass to 70% by mass, and the content of the reactive dye represented by the formula (2) is 30% by mass. The reactive dye composition according to claim 1, which is% to 70% by mass. The reactive dye composition according to claim 1, wherein the red reactive dye (R) further comprises a reactive dye whose free acid form is represented by the following formula (3).

[In the formula, Y ₄ represents SO ₂ CH = CH ₂ or SO ₂ CH ₂ CH ₂ Z, and Z represents a group desorbed with alkali. ] The content of the reactive dye represented by the formula (1) in the red reactive dye (R) is 20% by mass to 40% by mass, and the content of the reactive dye represented by the formula (2) is 30% by mass. The reactive dye composition according to claim 3, wherein the content is from% to 50% by mass and the content of the reactive dye represented by the formula (3) is 10% to 30% by mass. The content of the reactive dye represented by the formula (4) in the blue reactive dye (B) is 10% by mass to 90% by mass, and the reactive dye represented by the formula (5) and the above formula (6). The reactive dye composition according to any one of claims 1 to 4, wherein the total content of at least one reactive dye selected from the reactive dyes represented by is 10% by mass to 90% by mass. The content of the reactive dye represented by the formula (4) in the blue reactive dye (B) is 10% by mass to 30% by mass, and the reactive dye represented by the formula (5) and the above formula (6). The reactive dye composition according to any one of claims 1 to 4, wherein the total content of at least one reactive dye selected from the reactive dyes represented by is 70% by mass to 90% by mass. The content of the reactive dye represented by the formula (4) in the blue reactive dye (B) is 10% by mass to 30% by mass, and the content of the reactive dye represented by the formula (5) is 50% by mass. The reactive dye composition according to any one of claims 1 to 4, wherein the content of the reactive dye represented by the formula (6) is 20% by mass to 30% by mass, which is% to 60% by mass. The content of the reactive dye represented by the formula (5) in the dark blue reactive dye (N) is 5% by mass to 95% by mass, and the content of the reactive dye represented by the formula (7) is 5% by mass. The reactive dye composition according to any one of claims 1 to 4, which is% to 95% by mass. The content of the reactive dye represented by the formula (5) in the dark blue reactive dye (N) is 80% by mass to 95% by mass, and the content of the reactive dye represented by the formula (7) is 5% by mass. The reactive dye composition according to any one of claims 1 to 4, which is% to 20% by mass. A dyeing method comprising dyeing a cellulose fiber or a cellulose fiber-containing fiber with the reactive dye composition according to any one of claims 1 to 9.