JPWO2005085368A1 - Reactive dye composition and dyeing method using the same - Google Patents

Abstract

Any of the red reactive dye whose free acid form is represented by formula (A) and the red reactive dye whose free acid form is represented by formula (B-1), formula (B-2) and formula (B-3) A red reactive dye composition containing one or more kinds, or a reactive dye composition containing the red reactive dye composition and a specific blue reactive dye and / or a specific yellow reactive dye, to produce cellulose fibers or cellulose. With respect to the fiber-containing fiber material, it is possible to perform a dyeing process with balanced affinity and reactivity, excellent reproducibility and level dyeing, and fastness, particularly sweat light fastness. [Chemical formula 1] [Chemical formula 2] [Chemical formula 3] [Chemical formula 4]

Description

  The present invention relates to a reactive dye composition suitable for dyeing cellulose fibers and cellulose fiber-containing fiber materials, and a dyeing method using the same. More specifically, the reactive dye composition is capable of dyeing cellulose fibers and cellulose fiber-containing fiber materials to obtain a dyed product excellent in levelness and dyeing reproducibility and excellent in fastness such as sweat light fastness. The present invention also relates to a method for dyeing cellulose fibers and cellulose fiber-containing fiber materials using the same.

Reactive dyes are frequently used for dyeing cellulose fibers such as cotton and rayon. In dyeing cellulose fiber materials using reactive dyes, it is known that yellow, red and blue reactive dyes are used as dyes for the three primary colors, and they are blended in various proportions and dyeed.
However, when the affinity, reactivity, dyeing speed, etc. of the respective dyes used as the three primary color dyes are different from each other, there is a problem of leveling property in which spotting occurs in the middle of dyeing, and color differences occur between dyeing lots. May cause problems such as dyeing reproducibility. With regard to leveling and dyeing reproducibility, in recent years, with the diversification of types and forms of fiber materials, automation of dyeing plants, and simplification of operations for shortening the dyeing time, more leveling and dyeing reproducibility have been achieved. Good reactive dyes are highly desired. In addition, in recent years, reactive dyes with excellent fastness to sweat light resistance have become strong due to the problem that dyed clothing that absorbs sweat is likely to cause discoloration and discoloration when exposed to sunlight, mainly in sportswear clothing. It is desired. Various studies have been made to solve such problems (for example, see Patent Document 1), but satisfactory results have not yet been obtained.

Japanese Patent No. 3168624

  The present invention is a reactive dye for solving the above-mentioned problems and for dyeing cellulose fibers or cellulose fiber-containing fiber materials with excellent reproducibility and cleanability with good levelness and high fastness. The aim is to develop compositions and dyeing methods.

  In order to solve the problems of the prior art, the present inventors have intensively studied, and as a result, a red reactive dye composition containing a specific red reactive dye as an essential component, or a specific blue reactive dye and By using a reactive dye composition containing a specific yellow reactive dye, the affinity and dyeing speed of each dye constituting the dye composition are matched, and the cellulose fiber is leveled and reproducible. The present inventors have found that dyeing can be performed well and sweat light fastness is excellent, and the present invention has been completed.

（式（Ｂ−１）、（Ｂ−２）及び（Ｂ−３）において、置換基−ＳＯ₂ＣＨ₂ＣＨ₂ＯＳＯ₃Ｈは、これが分解して形成する−ＳＯ₂ＣＨ＝ＣＨ₂であってもよい。）That is, the present invention shows a red reactive dye in which the form of the free acid is represented by the formula (A), and the form of the free acid is represented by the formula (B-1), the formula (B-2) and the formula (B-3). The present invention relates to a red reactive dye composition containing any one or more of the red reactive dyes.

(Formula (B-1), the (B-2) and (B-3), the substituent _{-SO 2 CH 2 CH 2 OSO 3} H , This is met -SO ₂ CH = CH ₂ which is formed by decomposition May be.)

（式（Ｃ−１）及び（Ｃ−２）において、置換基−ＳＯ₂ＣＨ₂ＣＨ₂ＯＳＯ₃Ｈは、これが分解して形成する−ＳＯ₂ＣＨ＝ＣＨ₂であってもよい。）Furthermore, the present invention relates to the above-mentioned red reactive dye composition, a blue reactive dye in which the form of the free acid is represented by the formula (C-1) and / or a blue reaction in which the form of the free acid is represented by the formula (C-2). The present invention relates to a reactive dye composition containing a dye.

(In the formula (C-1) and (C-2), the substituents _{-SO 2 CH 2 CH 2 OSO 3} H , this may be a -SO ₂ CH = CH ₂ which is formed by decomposition.)

（式（Ｄ）において、置換基−ＳＯ₂ＣＨ₂ＣＨ₂ＯＳＯ₃Ｈは、これが分解して形成する−ＳＯ₂ＣＨ＝ＣＨ₂であってもよい。）The present invention further relates to a reactive dye composition containing the above-mentioned red reactive dye composition and a yellow reactive dye whose free acid form is represented by the formula (D).

(In the formula (D), the substituent _{-SO 2 CH 2 CH 2 OSO 3} H , this may be a -SO ₂ CH = CH ₂ which is formed by decomposition.)

  Furthermore, the present invention relates to the above-mentioned red reactive dye composition, a blue reactive dye in which the form of the free acid is represented by the formula (C-1) and / or a blue reaction in which the form of the free acid is represented by the formula (C-2). The present invention relates to a reactive dye composition containing a yellow reactive dye whose dye and / or free acid form is represented by the formula (D).

Furthermore, the present invention relates to a method for dyeing cellulose fiber or cellulose fiber-containing fiber material, characterized by using the above-mentioned red reactive dye composition or any one of the above reactive dye compositions.
Furthermore, this invention relates to the dyeing | staining method of the cellulose fiber or a cellulose fiber containing fiber material characterized by processing a cellulose fiber or a cellulose fiber containing fiber material in the dyeing bath containing said red reactive dye composition.
Furthermore, the present invention relates to the above-mentioned red reactive dye composition, a blue reactive dye in which the form of the free acid is represented by the formula (C-1) and / or a blue reaction in which the form of the free acid is represented by the formula (C-2). Cellulose fiber or cellulose fiber-containing fiber, characterized by treating cellulose fiber or cellulose fiber-containing fiber material in a dye bath containing a yellow reactive dye of the form of dye and / or free acid represented by formula (D) The present invention relates to a dyeing method for materials.

  By using the red reactive dye composition or reactive dye composition of the present invention, the cellulose fiber or cellulose-containing fiber material can be dyed and processed with good reproducibility and levelness with balanced affinity and reactivity. In addition, it can be dyed with excellent fastness, particularly fastness to sweat and light.

  The red reactive dye whose free acid form is represented by formula (A) is disclosed in JP-T-2003-532569 and the like, and the red reactive dye whose free acid form is represented by formula (B-1) and formula (B-2). In Japanese Patent Publication No. 7-91483 and Japanese Patent Application Laid-Open No. 2000-192374, and the red reactive dye whose free acid form is represented by the formula (B-3) is disclosed in Japanese Patent No. 3116461. The blue reactive dye represented by the formula (C-1) is disclosed in Japanese Patent Publication No. 3-10669, and the blue reactive dye whose free acid is represented by the formula (C-2) is disclosed in Japanese Patent Publication No. 1-284826. In addition, the yellow reactive dyes whose free acid form is represented by the formula (D) are known dyes described in JP-A No. 56-15481, etc., and are produced according to the methods described in those publications. Or can be easily obtained from the market.

（式（１）において、置換基−ＳＯ₂ＣＨ₂ＣＨ₂ＯＳＯ₃Ｈはこれが分解して形成する−ＳＯ₂ＣＨ＝ＣＨ₂であってもよい。）で示される赤色染料であるが、これに限定されるものではない。As the red reactive dye in which the form of the free acid is represented by the formula (B-1), the form of the free acid is preferably the formula (1).

(In the formula (1), the substituent _{-SO 2 CH 2 CH 2 OSO 3} H may be -SO ₂ CH = CH ₂ this is formed by decomposition.) Is a red dye represented by this It is not limited to.

（式（２）において、置換基−ＳＯ₂ＣＨ₂ＣＨ₂ＯＳＯ₃Ｈはこれが分解して形成する−ＳＯ₂ＣＨ＝ＣＨ₂であってもよい。）で示される赤色染料であるが、これに限定されるものではない。As the red reactive dye whose free acid form is represented by the formula (B-2), the free acid form is preferably represented by the formula (2).

(In the formula (2), the substituents _{-SO 2 CH 2 CH 2 OSO 3} H may be -SO ₂ CH = CH ₂ this is formed by decomposition.) Is a red dye represented by this It is not limited to.

（式（３）において、置換基−ＳＯ₂ＣＨ₂ＣＨ₂ＯＳＯ₃Ｈはこれが分解して形成する−ＳＯ₂ＣＨ＝ＣＨ₂であってもよい。）で示される赤色染料であるが、これに限定されるものではない。As the red reactive dye whose free acid form is represented by the formula (B-3), the free acid form is preferably represented by the formula (3).

(In the formula (3), the substituent _{-SO 2 CH 2 CH 2 OSO 3} H may be -SO ₂ CH = CH ₂ this is formed by decomposition.) Is a red dye represented by this It is not limited to.

In the present invention, the red reactive dye composition includes a red reactive dye whose free acid form is represented by the formula (A) and a free acid form represented by the formula (B-1), formula (B-2) and formula (B-3). 1 type or 2 types or more of the red reactive dye shown by this is contained as an essential component. Their composition ratios are as follows: the red reactive dye whose free acid form is represented by the formula (A), and the free acid form represented by the formulas (B-1), (B-2) and (B-3). Any one or two or more of the red reactive dyes are usually 95% to 5% and 5% to 95%, preferably 95% to 55% and 5% to 45%, respectively. Wt%, more preferably 85 wt% to 65 wt% and 15 wt% to 35 wt%. The composition ratio when the form of the free acid contains any two of the red reactive dyes represented by formula (B-1), formula (B-2) and formula (B-3) is preferably, for example, 85 to 65% by weight of a red reactive dye whose free acid form is represented by the formula (A), 10 to 25% by weight of a red reactive dye whose free acid form is represented by the formula (B-1) and The red reactive dye whose free acid form is represented by the formula (B-2) is 5% by weight to 10% by weight.
Further, other than the red reactive dye whose free acid form is represented by formula (A) and the red reactive dye whose free acid form is represented by formula (B-1), formula (B-2) and formula (B-3) These reactive dyes can also be used in combination. The reactive dye used in combination is preferably a reactive dye having a reactive group of the same type as the formula (A), (B-1), (B-2) and (B-3) in the form of the free acid. In order to obtain a color tone by mixing several kinds of dyes, reactive dyes of various hues having other reactive groups can be used in combination.

（式（４）において、置換基−ＳＯ₂ＣＨ₂ＣＨ₂ＯＳＯ₃Ｈはこれが分解して形成する−ＳＯ₂ＣＨ＝ＣＨ₂であってもよい。）で示される青色染料であるが、これに限定されるものではない。In the present invention, among the reactive dyes of other hues that can be used in combination, the dye preferably used as the blue reactive dye is a blue reactive dye and / or a free acid whose free acid form is represented by the formula (C-1) Is a blue reactive dye represented by the formula (C-2). As a blue reactive dye in which the form of the free acid is represented by the formula (C-1), the form of the free acid is preferably the formula (4).

(In the formula (4), the substituent _{-SO 2 CH 2 CH 2 OSO 3} H may be -SO ₂ CH = CH ₂ this is formed by decomposition.) Is a blue dye represented by this It is not limited to.

（式（５）において、置換基−ＳＯ₂ＣＨ₂ＣＨ₂ＯＳＯ₃Ｈはこれが分解して形成する−ＳＯ₂ＣＨ＝ＣＨ₂であってもよい。）で示される青色反応染料であるが、これに限定されるものではない。As a blue reactive dye in which the form of the free acid is represented by the formula (C-2), the form of the free acid is preferably the formula (5).

(In the formula (5), the substituent _{-SO 2 CH 2 CH 2 OSO 3} H may be -SO ₂ CH = CH ₂ this is formed by decomposition.) Is a blue reactive dyes represented by, It is not limited to this.

  A preferable blue reactive dye is a combination of a blue reactive dye having a free acid form represented by the formula (C-1) and a blue reactive dye represented by the formula (C-2). The composition ratio is usually 95 wt% to 5 wt% and 5 wt% for the blue reactive dye represented by the formula (C-1) and the blue reactive dye represented by the formula (C-2), respectively. % To 95% by weight, preferably 95% to 65% by weight and 5% to 35% by weight, more preferably 95% to 75% by weight and 5% to 25% by weight. Furthermore, reactive dyes other than the blue reactive dyes whose free acid forms are represented by formulas (C-1) and (C-2) can also be used in combination.

（式（６）において、置換基−ＳＯ₂ＣＨ₂ＣＨ₂ＯＳＯ₃Ｈはこれが分解して形成する−ＳＯ₂ＣＨ＝ＣＨ₂であってもよい。）で示される黄色反応染料であるが、これに限定されるものではない。Among the other reactive dyes that can be used in combination, the yellow dye includes a yellow reactive dye whose free acid form is represented by the formula (D). As the yellow reactive dye whose free acid form is represented by the formula (D), the preferred free acid form is represented by the formula (6).

(In the formula (6), the substituent _{-SO 2 CH 2 CH 2 OSO 3} H may be -SO ₂ CH = CH ₂ this is formed by decomposition.) Is a yellow reactive dye represented by, It is not limited to this.

  The form of the free acid is formula (A), formula (B-1), formula (B-2), formula (B-3), formula (C-1), formula (C-2), formula (D), All of the reactive dyes represented by the formulas (1) to (6) may exist in the form of a free acid, or may exist in the form of a salt thereof. As the salt, an alkali metal salt or an alkaline earth metal salt is preferable, and a sodium salt, a potassium salt, or a lithium salt is particularly preferable.

  In the red reactive dye composition or reactive dye composition of the present invention, the method for blending each reactive dye is not particularly limited. For example, each reactive dye is produced separately, then blended, the reaction solution containing each reactive dye produced during production is mixed, then dried to form a composition, and further each dyed bath. The dye can be dissolved and the same composition as each composition in the dyeing bath can be employed. The mixing ratio of the red reactive dye composition and the blue reactive dye and / or the yellow reactive dye at that time is blended according to the desired color tone and is not particularly limited. Further, if necessary, the composition of the present invention may contain a known additive such as a concentration adjusting agent, a dispersing agent, a leveling agent, a suspending agent, a sequestering agent, an antireducing agent and the like. .

  In the above, the dyeing bath, padding liquid, and printing paste are prepared by directly adding the dyes constituting the red reactive dye composition of the present invention or the reactive dye composition and the above-mentioned additives and dyeing the dyeing bath. The order of dissolving the respective dyes and additives may be any order. The amount of each drug to be used is also appropriately determined according to a publicly known method.

In the dyeing method using the red reactive dye composition or reactive dye composition of the present invention, the amount used is usually 0.005 to 15% by weight based on the fiber weight.
The red reactive dye composition or reactive dye composition of the present invention is useful for dyeing cellulose fibers and fiber materials containing them. Examples of the target cellulose fiber and cellulose fiber-containing fiber material include cellulose fibers such as cotton, hemp, rayon, polynosic, cupra, and lyocell, or mixed fibers of these materials. Furthermore, these fibers or mixed fibers and other fibers such as polyester fiber, acetate fiber, polyacrylonitrile fiber, polyamide fiber such as wool, silk, nylon and the like, or a woven product can be mentioned.

In the present invention, the staining method can be performed according to a method known per se, for example, as described below.
As a dyeing method, for example, in dyeing cellulose fibers such as cotton, the red reactive dye composition or reactive dye composition of the present invention corresponding to a desired hue and concentration is added to a dye bath, and a known inorganic neutral salt, for example, Dyeing is performed using anhydrous sodium sulfate, sodium chloride and acid binders such as sodium carbonate, sodium bicarbonate, caustic soda and sodium triphosphate alone or in combination. The amount of the inorganic neutral salt or acid binder used at this time is not particularly limited, but it is preferably at least 1 g / L. In addition, the inorganic neutral salt or the acid binder may be added to the dye bath at a time, or may be divided and added. In addition, dyeing aids such as bath softener and leveling agent may be used in combination by known methods, but the dyeing aid is not particularly limited to these. The dyeing temperature is 40 to 90 ° C, preferably 50 to 70 ° C. The to-be-dyed product: dye bath with a bath ratio is usually 1: 5 to 1:50.

  In the continuous dyeing method, an acid binder, for example, sodium carbonate, sodium bicarbonate, caustic soda, etc. alone or in combination of two or more of them is added to the dye padding solution, padded by a known method, and then dried. One bath padding method for dyeing by dry heat or steaming by a known method, and after padding the dye and drying, a known inorganic neutral salt such as anhydrous sodium sulfate, salt, etc. and an acid binder, for example, A two-bath padding method in which caustic soda, sodium silicate, etc. are padded and dyed by dry heat or steam heat by a known method is exemplified, but the continuous dyeing method is not limited thereto.

In the printing method, use sodium alginate, emulsion paste, etc. as the original paste, and print the printing paste containing dye and acid binder such as sodium bicarbonate by a known method and then dry or steam by a known method. To do.
After completion of the dyeing step, washing with water and hot water is followed by washing in a soaping bath containing a commercially available soaping agent of 0.1 to 5 g / L by a conventional method, and the dyeing is finished.
The red reactive dye composition or reactive dye composition and the dyeing method of the present invention have very good leveling and reproducibility and good build-up property in dyeing cellulose fibers and fiber materials containing the same. The dyed product is excellent in various dyeing properties and has excellent fastnesses, particularly sweat light fastnesses.

Hereinafter, the present invention will be described in more detail with reference to examples. In the examples, “parts” represents parts by weight unless otherwise specified.
Example 1
Composition of reactive dyes Table 1 shows the combinations of reactive dyes and the amounts used. In Table 1, CI Reactive means a color index general name.

Table 1: Composition
Formulation Example 1 of the present invention :
Red reactive dye
Dye of formula (A) 0.11 part
0.03 part of dye of formula (1)
0.01 parts of dye of formula (2)
Blue reactive dye
Dye of formula (4) 0.09 part
Dye of formula (5) 0.02 part
Yellow reactive dye
0.14 parts of dye of formula (6)
Formulation example 2 for comparison :
Red reactive dye
CIReactive Red 195 0.08 parts
Blue reactive dye
CIReactive Blue 221 0.11 parts
Yellow reactive dye
CIReactive Yellow 145 0.14 parts
Formulation example 3 for comparison :
Red reactive dye
CIReactive Red 271 0.20 parts
Blue reactive dye
CIReactive Blue 235 0.11 part
Yellow reactive dye
CIReactive Yellow 206 0.12 parts

Bath ratio dependency test (1) Dyeing at a bath ratio of 1:10 A dye bath having a total amount of 490 parts was prepared by adding water to 15 parts of the dyes of each composition shown in Table 1 and anhydrous sodium sulfate. 50 parts of cotton knitted fabric was added to this dye bath, and the temperature was raised to 60 ° C. in 20 minutes. After treatment at 60 ° C. for 20 minutes, 10 parts of sodium carbonate was added and dyed at the same temperature for 60 minutes. Next, after washing with water and hot water, soaping is performed for 15 minutes at 100 ° C. in 1000 parts of an aqueous solution containing a commercially available soaping agent (Scorerol C-1200 Kitahiro Chemical Co., Ltd. 1 g / L). It dried and obtained the brown dyeing | staining.
(2) Dyeing at a bath ratio of 1:30 Dye baths with a total amount of 1470 parts were prepared by adding water to 45 parts of the dyes of each formulation composition shown in Table 1 and anhydrous sodium sulfate. 50 parts of cotton knitted fabric was added to this dye bath, and the temperature was raised to 60 ° C. in 20 minutes. After treatment at 60 ° C. for 20 minutes, 30 parts of sodium carbonate was added and dyed at the same temperature for 60 minutes. Subsequently, after washing with water and hot water, soaping was performed in 100 parts of an aqueous solution containing the soaping agent at 100 ° C. for 15 minutes, followed by washing with water and drying to obtain brown dyeings.
(3) Determination method The hue difference of the dyed product obtained at the bath ratio of 1:30 was visually determined based on the dyed product obtained at the bath ratio of 1:10. The determination index is as follows.
○: Hue difference small ×: Hue difference large ××: Hue difference significantly large

Absorption and fixing behavior test Dye of each composition shown in Table 1 and 30 parts of anhydrous sodium sulfate were added with water to prepare a total of 980 parts of dyebath for each dye. 50 parts of cotton knitted fabric was added to each dye bath, and each dye bath was treated by the following methods (1) to (4) to test the absorption and fixing behavior.
(1) After treatment at 30 ° C. for 10 minutes, the dyed fabric was taken out from the dye bath, and divided into two equal parts, and the following post-treatment (A) or (B) was performed.
(A) The dyed cloth was squeezed, dehydrated and then naturally dried (absorbent cloth).
(B) The dyed cloth was washed with water and hot water, then soaped in 1000 parts of an aqueous solution containing the soaping agent at 100 ° C. for 15 minutes, washed with water and dried (fixed cloth).
(2) Next, 20 parts of sodium carbonate (a total of 1000 parts of a dye bath) was added, and after dyeing at 30 ° C. for 15 minutes, the dyed cloth was taken out and divided into two equal parts, respectively (A) or (B) After-treatment was performed.
(3) Further, when the temperature was raised to 60 ° C. in 15 minutes, the dyed fabric was taken out and divided into two equal parts, and the post-treatment (A) or (B) was performed.
(4) Further, after dyeing at 60 ° C. for 40 minutes, the last dyed cloth was taken out and divided into two equal parts, and the post-treatment (A) or (B) was performed.
Judgment method (a)
In each of the above (1) to (4), the hue difference of the treated cloth (B) was visually determined based on the treated cloth (A). The determination index is as follows.
○: All of (1) to (4) have a small hue difference ×: There is a part of any of the hue differences of (1) to (4) Judgment method (b)
In the treated fabric of (B), the degree of hue change between (1), (2), (3), and (4) was visually determined. The determination index is as follows.
○: Hue of the same system of (1) to (4) (adequate balance of fixing speed of the three primary colors)
×: Large hue change in (1) to (4) (adequate fixing speed balance of the three primary colors)

Light fastness test for sweat (1) Sample preparation conditions Dyeing is performed according to the dyeing conditions at the bath ratio of 1:10 in the bath ratio dependency test (1) using the dyes having the respective composition shown in Table 1. A dyed cloth as a brown sample was obtained.
(2) Test condition for light fastness to sweat ATTS: Textile Technology Research Group The test was conducted according to the weak method.
After immersing the dyed cloth in the acidic and alkaline artificial sweat shown in Table 2 at a bath ratio of 1:50 at room temperature for 30 minutes, take out the dyed cloth and press it lightly 2-3 times between filter papers to remove excess sweat. Drain the liquid. The dyed cloth was immediately attached to a light resistance tester (JIS L 0824) in a wet state, and irradiated for 7 hours in accordance with JIS L 0842: Dye fastness test method against carbon arc fluorescence.

Table 2: Preparation of artificial sweat
Acidic alkaline
Sodium chloride 5.0g 5.0g
Disodium phosphate ・ 12H ₂ O 5.0g 5.0g
Lactic acid 5.0g 5.0g
DL-aspartic acid 0.5g 0.5g
D-Sodium pantothenate 5.0 g 5.0 g
Glucose 5.0g 5.0g
L-histidine hydrochloride / H ₂ O 0.5 g 0.5 g
Acetic acid pH3.5 −
Sodium hydroxide-pH 8.0
Total liquid volume (in water) 1 liter 1 liter

(3) Determination method The degree of color fading of the irradiated part relative to the unirradiated part was determined by JIS L 0804: Gray scale for color fading. The determination index is as follows.
4: considerably superior 3-4: excellent 3: moderate 2: inferior 1-2: considerably inferior

Judgment results Table 3 shows the comparison results of the bath ratio dependency, the absorption, the fixing behavior, and the light fastness to sweat for Formulation Example 1 of the present invention and Comparative Formulation Examples 2 to 3.

Table 3: Test results
Bath ratio dependent absorption, adsorption behavior Sweat fastness to light
Determination method (a) Determination method (b) Acidic alkaline Formulation example 1 ○ ○ ○ 4 3-4
Formulation Example 2 × × ○ 2 1-2
Formulation Example 3 XXX XX 3-4 3

  When dyeing is performed with the combination of the reactive dyes of Formulation Example 1 of the present invention, the dyeing properties of the red reactive dye, the blue reactive dye, and the yellow reactive dye are the same, even when the dyeing conditions such as the bath ratio vary. The hue change is small, the absorption rate and the fixing rate are almost the same, the dyeing reproducibility and leveling property are excellent, and the light fastness to sweat is extremely excellent. When dyeing was performed with the combination of the reactive dyes of Formulation Example 1 of the present invention, both the dyeability such as dyeing reproducibility and levelness and fastness to sweat light were satisfied.

Examples 2-12
In place of the combination and usage amount of the reactive dye of Formulation Example 1 of Example 1, water was added to 40 parts of anhydrous sodium sulfate using the combination and usage amount (parts) of the dye shown in Table 4, and the total amount was 980 parts. Each dyebath was prepared. 50 parts of cotton knitted fabric was added to this dye bath, and the temperature was raised to 60 ° C. in 20 minutes. After treatment at 60 ° C. for 20 minutes, 20 parts of sodium carbonate was added and dyed at the same temperature for 60 minutes.
Subsequently, after washing with water and hot water, soaping was performed in 1000 parts of an aqueous solution containing the soaping agent at 100 ° C. for 15 minutes, followed by washing with water and drying to obtain dyed products.

Table 4: Formulation composition
Example 2 :
Red reactive dye
0.60 parts of dye of formula (A)
0.20 parts of dye of formula (1)
Example 3 :
Red reactive dye
0.60 parts of dye of formula (A)
0.20 parts of dye of formula (2)
Example 4 :
Red reactive dye
0.60 parts of dye of formula (A)
0.20 parts of dye of formula (3)
Example 5 :
Red reactive dye
0.60 parts of dye of formula (A)
0.14 parts of the dye of formula (1)
Dye of formula (2) 0.06 part
Example 6 :
Red reactive dye
0.36 parts of dye of formula (A)
0.08 parts of dye of formula (1)
0.04 parts of dye of formula (2)
Blue reactive dye
0.27 parts of dye of formula (4)
Dye of formula (5) 0.05 part
Example 7 :
Red reactive dye
0.24 parts of dye of formula (A)
0.06 part of dye of formula (1)
Dye of formula (2) 0.02 part
Yellow reactive dye
0.48 parts of dye of formula (6)
Example 8 :
Red reactive dye
0.23 parts of dye of formula (A)
0.08 parts of dye of formula (1)
Blue reactive dye
0.17 parts of dye of formula (4)
0.03 parts of dye of formula (5)
Yellow reactive dye
Dye of formula (6) 0.30 part
Example 9 :
Red reactive dye
0.23 parts of dye of formula (A)
0.08 parts of dye of formula (2)
Blue reactive dye
0.17 parts of dye of formula (4)
0.03 parts of dye of formula (5)
Yellow reactive dye
Dye of formula (6) 0.30 part
Example 10 :
Red reactive dye
0.23 parts of dye of formula (A)
0.08 parts of dye of formula (3)
Blue reactive dye
0.17 parts of dye of formula (4)
0.03 parts of dye of formula (5)
Yellow reactive dye
Dye of formula (6) 0.30 part
Example 11 :
Red reactive dye
0.23 parts of dye of formula (A)
0.06 part of dye of formula (1)
Dye of formula (2) 0.02 part
Blue reactive dye
0.17 parts of dye of formula (4)
0.03 parts of dye of formula (5)
Yellow reactive dye
Dye of formula (6) 0.30 part
Example 12 :
Red reactive dye
0.23 parts of dye of formula (A)
0.06 part of dye of formula (1)
Dye of formula (2) 0.02 part
Blue reactive dye
0.20 parts of dye of formula (4)
Yellow reactive dye
Dye of formula (6) 0.30 part

As for the hue of the obtained dyeing | staining, Example 2-5 was red, Example 6 was purple, Example 7 was amber, and Examples 8-12 were brown.
In any combination of reactive dyes of Examples 2 to 12, the leveling and reproducibility are extremely good, and the various dyeing properties such as good build-up properties are excellent, and light resistance, sweat light resistance, Various fastnesses such as chlorine water were also excellent. In particular, the excellent light fastness of sweat is noted.

Examples 13-17
Using the reactive dye combinations and usage amounts (parts) shown in Examples 8 to 12, water was added to 40 parts of anhydrous sodium sulfate to prepare a total amount of 980 parts of dye bath. 50 parts of rayon muslin was added to this dye bath and the temperature was raised to 60 ° C. in 20 minutes. After treatment at 60 ° C. for 20 minutes, 20 parts of sodium carbonate was added and dyed at the same temperature for 60 minutes.
Subsequently, after washing with water and hot water, soaping was performed in 1000 parts of an aqueous solution containing the soaping agent at 100 ° C. for 15 minutes, followed by washing with water and drying to obtain dyed products. As for the hue of the obtained dyeing | staining, all of Examples 13-17 were brown.
Even in rayon muslin dyeing, the leveling and reproducibility are extremely good, and various dyeing properties such as good build-up properties are excellent, and various fastnesses such as light resistance, sweat light resistance, and chlorine water are also excellent. It was. In particular, it was excellent in light fastness to sweat.

Example 18
In the combination of reactive dyes shown in Example 11, using 20 times their ratio, water was added to 10 parts of sodium metanitrobenzenesulfonate, 20 parts of sodium bicarbonate, and 1 part of sodium alginate, and a 1000 parts total pad bath was prepared. Produced. After padding cotton in this pad bath, it was squeezed with a mangle at a squeezing rate of 60%. The squeezed cloth was dried at 100 ° C. for 5 minutes and then steamed at 100 ° C. for 5 minutes to fix the dye. Next, after washing with water and hot water, soaping was performed in 1000 parts of an aqueous solution containing the soaping agent at 100 ° C. for 15 minutes, followed by washing with water and drying to obtain a dyed product. The hue of the dyed product obtained was brown.
Excellent leveling and reproducibility in continuous dyeing, excellent dyeing properties such as good build-up properties, and excellent fastnesses such as light resistance, sweat resistance, and chlorine water . In particular, it was excellent in light fastness to sweat.

Example 19
In the combination of dyes shown in Example 11, using 20 times their ratio, water was added to 100 parts of urea, 20 parts of sodium hydrogen carbonate, 10 parts of sodium metanitrobenzenesulfonate, and 25 parts of sodium alginate. A color paste for printing was prepared. This color paste was printed on cotton, dried at 100 ° C. for 5 minutes, and then steamed at 100 ° C. for 5 minutes to fix the dye. Subsequently, after washing with water and hot water, soaping was performed in 1000 parts of an aqueous solution containing a commercially available soaping agent at 100 ° C. for 15 minutes, followed by washing with water and drying to obtain a dyed product.
The hue of the dyed product obtained was brown. In textile printing, leveling and reproducibility were extremely good, and various dyeing properties such as good build-up property were also obtained, and various fastnesses such as light resistance, sweat light resistance, and chlorine water were also excellent. In particular, it was excellent in light fastness to sweat.

Claims (9)

Any of the red reactive dye whose free acid form is represented by formula (A) and the red reactive dye whose free acid form is represented by formula (B-1), formula (B-2) and formula (B-3) Or a red reactive dye composition containing one or more.

(Formula (B-1), the (B-2) and (B-3), the substituent _{-SO 2 CH 2 CH 2 OSO 3} H , This is met -SO ₂ CH = CH ₂ which is formed by decomposition May be.) The red reactive dye composition according to claim 1, a blue reactive dye having a free acid form represented by formula (C-1) and / or a blue reactive dye having a free acid form represented by formula (C-2) A reactive dye composition containing

(In the formula (C-1) and (C-2), the substituents _{-SO 2 CH 2 CH 2 OSO 3} H , this may be a -SO ₂ CH = CH ₂ which is formed by decomposition.) A reactive dye composition comprising the red reactive dye composition according to claim 1 and a yellow reactive dye having a free acid form represented by formula (D).

(In the formula (D), the substituent _{-SO 2 CH 2 CH 2 OSO 3} H , this may be a -SO ₂ CH = CH ₂ which is formed by decomposition.)   The red reactive dye composition according to claim 1 and the blue reactive dye and / or free acid form represented by formula (C-1) according to claim 2 wherein the free acid form is represented by formula (C-2) A reactive dye composition comprising a blue reactive dye represented by formula (1) and / or a yellow reactive dye represented by formula (D) wherein the free acid form according to claim 3 is represented by formula (D).   2. The red reactive dye composition according to claim 1, wherein the free reactive acid form is 95 wt% to 5 wt% and the free acid form is the formula (B-1), 5. The composition according to claim 1, wherein one or more of the red reactive dyes represented by formula (B-2) and formula (B-3) are contained at a composition ratio of 5 wt% to 95 wt%. The reactive dye composition as described.   The free acid form contains both blue reactive dyes represented by formulas (C-1) and (C-2), and the free acid form contains 95 blue reactive dyes represented by formula (C-1). The reactive dye composition according to claim 2 or 4, wherein the reactive dye composition comprises 5% by weight to 5% by weight of a blue reactive dye represented by the formula (C-2) at a composition ratio of 5% by weight to 95% by weight.   A method for dyeing a cellulose fiber or a fiber material containing cellulose fiber, wherein the reactive dye composition according to any one of claims 1 to 6 is used.   A method for dyeing cellulose fibers or cellulose fiber-containing fiber materials, comprising treating cellulose fibers or cellulose fiber-containing fiber materials in a dye bath containing the red reactive dye composition according to claim 1.   The red reactive dye composition according to claim 1, a blue reactive dye having a free acid form represented by formula (C-1) and / or a blue reactive dye having a free acid form represented by formula (C-2) And / or treating the cellulose fiber or the cellulose fiber-containing fiber material in a dye bath containing a yellow reactive dye represented by the formula (D) in the form of a free acid. Dyeing method.