JP4614671B2 - Reactive dye composition and dyeing method using the same - Google Patents

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.

  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, if the affinity, reactivity, dyeing speed, and temperature dependency of each dye used as the three primary color dyes are different, there is a problem of leveling that causes spotting in the middle of dyeing, and color differences 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. 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 Japanese Patent Publication No. 1-282626 Japanese Patent Publication No. 1-1787 JP-A-56-128380 European Patent No. 22575 Japanese Patent Laid-Open No. 56-15548

  The present invention solves the above problems and dyes cellulose fibers or cellulose fiber-containing fiber materials with excellent reproducibility and cleanability, good levelness and high fastness with good reproducibility. The purpose is to develop reactive dye compositions and dyeing methods.

  In order to solve the problems of the prior art, as a result of intensive studies, the inventors have studied a blue reactive dye composition containing a specific blue reactive dye, or a specific red reactive dye and / or a specific yellow color. By using reactive dye compositions containing reactive dyes, it has been found that the affinity and dyeing speed of each dye constituting the dye compositions are the same, and that cellulose fibers can be dyed with good leveling and reproducibility. The present invention has been completed.

That is, the present invention
1. A blue reactive dye composition comprising, in the form of a free acid, a blue reactive dye represented by formula (A) and a blue reactive dye also represented by formula (1):

(In the formula (A), R represents a hydrogen atom, a halogen atom or a C1-C4 alkoxy group. The —SO ₂ CH ₂ CH ₂ OSO ₃ H group is formed by decomposition of —SO ₂ CH═CH. it may be _two groups.)
Formula (1)

(In Formula (1), m ₁ is an integer of 0 to 2, R ₁ and R ₂ are each independently a hydrogen atom or an optionally substituted alkyl group, X ₁ is a halogen atom, and Y ₁ is — SO ₂ CH═CH ₂ or SO ₂ CH ₂ CH ₂ Z ₁ (Z ₁ represents a group capable of leaving by the action of an alkali).
2. Above 1. A yellow reaction represented by the formula (4) in the form of a red reactive dye and / or a free acid represented by the formula (2) and / or the formula (3) A reactive dye composition containing a dye.
Formula (2)

(In Formula (2), m ₂ is an integer of 0 to 2, n ₁ is 0 or 1, R ₃ and R ₄ are each independently a hydrogen atom or an optionally substituted alkyl group, X ₂ is A halogen atom, Y ₂ represents —SO ₂ CH═CH ₂ or SO ₂ CH ₂ CH ₂ Z ₂ (Z ₂ represents a group capable of leaving by the action of an alkali).
Formula (3)

(In Formula (3), m ₃ is an integer of 0 to ₂ , n ₂ is 0 or 1, R ₅ and R ₆ are each independently a hydrogen atom or an optionally substituted alkyl group, and X ₃ is A halogen atom, Y ₃ represents —SO ₂ CH═CH ₂ or SO ₂ CH ₂ CH ₂ Z ₃ (Z ₃ represents a group capable of leaving by the action of an alkali).
Formula (4)

(In the formula (4), m ₄ is an integer of 1 to 3, R ₇ and R ₈ are each independently a hydrogen atom, alkyl group, alkoxy group, acylamino group or ureido group, and R ₉ and R ₁₀ are each independently X ₄ represents a halogen atom, Y ₄ represents —SO ₂ CH═CH ₂ or SO ₂ CH ₂ CH ₂ Z ₄ (Z ₄ is eliminated by the action of an alkali) Each represents a group that represents
3. 1. The composition ratio of the blue reactive dye represented by the formula (A) and the blue reactive dye represented by the above formula (1) is 95 to 5% by mass: 5 to 95% by mass. 3. Blue reactive dye composition as described Above 1. Or 3. 4. A reactive dye composition comprising the blue reactive dye composition described in 1 and a red reactive dye represented by the above formula (2) and / or formula (3). Above 1. Or 3. 4. The composition ratio of the blue reactive dye composition described in 1. and the red reactive dye represented by the above formula (2) and / or formula (3) is 99 to 50% by mass: 1 to 50% by mass. 5. Reactive dye composition described in 6. 4. The composition ratio of the red reactive dye represented by the above formulas (2) and (3) is 90 to 10% by mass: 10 to 90% by mass. 6. Reactive dye composition described in 7. Above 1. ~ 6. 7. A method for dyeing cellulose fiber or a fiber material containing cellulose fiber, wherein the reactive dye composition according to any one of the above is used. Treating cellulose fibers or cellulose fiber-containing fiber materials in a free acid form in a dye bath containing a blue reactive dye of formula (A) and a blue reactive dye of formula (1) 8. Method for dyeing cellulose fiber or cellulose fiber-containing fiber material In the form of the free acid, the blue reactive dye represented by formula (A) and the blue reactive dye represented by formula (1) and the red acid represented by formula (2) and / or formula (3) Cellulose fiber or cellulose fiber-containing material characterized by treating cellulose fiber or cellulose fiber-containing fiber material in a dye bath containing a yellow reactive dye represented by formula (4) in the form of reactive dye and / or free acid A method for dyeing textile materials is provided.

  The blue reactive dye composition, reactive dye composition, and dyeing method of the present invention have extremely good leveling and reproducibility in dyeing cellulose fibers and fiber materials containing the same, and have good build-up properties, etc. Thus, a dyed product excellent in various dyeing properties and excellent in fastness can be obtained.

In the blue reactive dye represented by the formula (A), R is preferably a hydrogen atom, and a particularly preferred specific example of the blue reactive dye represented by the formula (A) is a blue reactive dye represented by the following formula (B) It is. In the following formula, the —SO ₂ CH ₂ CH ₂ OSO ₃ H group may be a —SO ₂ CH═CH ₂ group formed by decomposition thereof.
(same as below)

  The blue reactive dye represented by the formula (A) is described in Patent Document 2, and can be synthesized, for example, as follows.

  First, a hydrazone compound represented by the formula (a-3) is synthesized from the compounds of the following formulas (a-1) and (a-2). Next, the compound represented by the formula (a-4) is diazotized by a conventional method and coupled to the compound represented by the formula (a-3) to obtain a compound represented by the formula (a-5), and then copper sulfate. A compound represented by the formula (A) is obtained by reacting with a copper complexing agent such as sulfuric acid and finally esterifying with sulfuric acid or the like.

(In the above formula (A), the sulfone group and the carboxyl group are in the form of a free acid, and R represents a hydrogen atom, a halogen atom or a C1-C4 alkoxy group.) About the blue reactive dye represented by the above formula (B) Is synthesized according to the above.

In the above formulas (1) to (4), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₉ and R ₁₀ are a hydrogen atom or an optionally substituted alkyl group. is there. Preferably they are a hydrogen atom, a methyl group, and an ethyl group, and a hydrogen atom is especially preferable. Examples of the optionally substituted alkyl group include an alkyl group, hydroxy, cyano, C1-C4 alkoxy, carboxy, carbamoyl, C1-C4 alkoxycarbonyl, C1-C4 alkylcarbonyloxy, sulfo, sulfamoyl, or halogen. The C1-C4 alkyl group which may be sufficient is mentioned.

  Examples of the alkyl group include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and the like, and as a C1-C4 alkyl group substituted with hydroxy or C1-C4 alkoxy Is, for example, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, 2,3-dihydroxybutyl, 3,4-dihydroxybutyl, methoxymethyl, Examples include ethoxymethyl, 2-methoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 2-hydroxy-3-methoxypropyl, 3-ethoxypropyl, 2-hydroxy-3-methoxypropyl and the like.

  Examples of the C1-C4 alkyl group substituted with cyano include cyanomethyl, 2-cyanoethyl, 3-cyanopropyl, and the like. Examples of the C1-C4 alkyl group substituted with halogen include chloromethyl, bromomethyl, 2-cyano. Chloroethyl, 2-bromoethyl, 3-chloropropyl, 3-bromopropyl, 4-chlorobutyl, 4-bromobutyl and the like. Examples of the C1-C4 alkyl group substituted with carboxy include carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 3-carboxybutyl, 1,2-dicarboxyethyl, and the like. Examples of the C1-C4 alkyl group substituted with carbamoyl include, for example, carbamoylmethyl, 2-carbamoylethyl, 3-carbamoylpropyl, 4-carbamoylbutyl, etc. And the like.

Examples of the C1-C4 alkyl group substituted with C1-C4 alkoxycarbonyl include, for example, methoxycarbonylmethyl, ethoxycarbonylmethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 3-methoxycarbonylpropyl, 3-ethoxycarbonylpropyl, 4-methoxycarbonylbutyl, 4-ethoxycarbonylbutyl and the like can be mentioned. Examples of the C1-C4 alkylcarbonyloxy include methylcarbonyloxymethyl, 2-methylcarbonyloxyethyl, 2-ethylcarbonyloxyethyl, 3-methylcarbonyloxy And propyl, 3-ethylcarbonyloxypropyl, 4-ethylcarbonyloxybutyl and the like.
Examples of the C1-C4 alkyl group substituted with sulfo include sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl and the like, and examples of the C1-C4 alkyl group substituted with sulfamoyl include sulfamoyl. Examples include methyl, 2-sulfamoylethyl, 3-sulfamoylpropyl, 4-sulfamoylbutyl and the like.

In the above formula (4), examples of the alkyl group represented by R ₇ and R ₈ include C1 to C4 alkyl such as methyl and ethyl, and examples of the alkoxy group include C1 to C4 alkoxy such as methoxy and ethoxy. , A methyl group and a methoxy group are preferable. Examples of the acylamino group represented by R ₇ and R ₈ include acetylamino and propionylamino. A particularly preferred combination of R ₇ and R ₈ includes the case where one is a hydrogen atom and the other is a ureido group.

In addition, examples of the group that is eliminated by the action of an alkali represented by Z ₁ , Z ₂ , Z _3, and Z ₄ include a sulfate ester group, a thiosulfate ester group, a phosphate ester group, an acetate ester group, and a halogen atom. Can be mentioned. A sulfate group is preferred. These ester groups are easily removed in the presence of an alkali such as sodium carbonate, sodium bicarbonate, or caseoid, preferably in water.

  The reactive dye represented by the formula (1) is disclosed in Patent Document 3, Patent Document 4, etc. The reactive dye represented by the formula (2) and the formula (3) is represented in Patent Document 5, etc., and the reactive dye represented by the formula (4). Are described in Patent Literature 6 and the like, and can be produced according to the methods described therein.

  The dye represented by the formula (1) as the blue reactive dye is preferably a dye represented by the following formula (5) or (6) in the form of a free acid, but is not limited thereto.

   The red reactive dye represented by the formula (2) is not particularly limited, but a dye represented by the following formula (7) in the form of a free acid is preferable.

   The red reactive dye represented by the formula (3) is not particularly limited, but a dye represented by the following formula (8) in the form of a free acid is preferable.

In the present invention, the blue reactive dye composition contains the reactive dye represented by the formula (A) and the reactive dye represented by the formula (1) as essential components. The composition ratio of the reactive dye represented by the formula (A) and the reactive dye represented by the formula (1) is usually 95% by mass to 5% by mass: 5% by mass to 95% by mass, preferably 85% by mass to 15% by mass. : 15% by mass to 85% by mass, more preferably 75% by mass to 55% by mass: 25% by mass to 45% by mass. Furthermore, a reactive dye other than the reactive dye represented by the formula (1) and the reactive dye represented by the formula (1) can be used in combination. The reactive dye that can be used in combination is preferably a reactive dye having the same type of reactive group, and a red or other hue reactive dye for color matching (mixing several dyes to obtain the desired hue) Can also be used together.
In this case, the red reactive dye that can be used in combination is preferably a reactive dye represented by formula (2) and / or formula (3), more preferably a reaction represented by formula (7) and / or formula (8). It is a dye. The composition ratio of the blue reactive dye composition to the red reactive dye represented by formula (2) and / or formula (3) is usually 99% by mass to 50% by mass: 1% by mass to 50% by mass, preferably Is 99 mass% to 70 mass%: 1 mass% to 30 mass%, more preferably 99 mass% to 80 mass%: 1 mass% to 20 mass%.

  The red reactive dye preferably used in the present invention is composed of dyes represented by the formulas (2) and (3), and preferably a combination of the dyes represented by the formulas (7) and (8). The composition ratio is usually 90% by mass to 10% by mass: 10% by mass to 90% by mass, preferably 80% by mass to 20% by mass: 20% by mass to 80% by mass, and more preferably 70% by mass to 40% by mass. : 30% by mass to 60% by mass. Furthermore, reactive dyes other than the reactive dyes represented by formula (2) and formula (3) can be used in combination.

  It is also possible to use the reactive dyes represented by the formulas (2) and (3) as a shading (finely adjusting hue) component of the blue reactive dye composition of the present invention. In such a case, 1% by mass to 3% by mass is used with respect to the blue reactive dye composition of the present invention. Among other reactive dyes that can be used in combination, examples of the yellow dye include reactive dyes represented by the formula (4). As the reactive dye represented by the formula (4), preferred is a dye represented by the following formula (9) and / or formula (10) in the form of a free acid, but is not limited thereto.

   All of the reactive dyes represented by the above formulas (1) to (10) are present in the form of a free acid or a salt thereof, and an alkali metal salt or an alkaline earth metal salt is preferable, particularly a sodium salt, a potassium salt, Lithium salts are preferred.

In the blue reactive dye composition and reactive dye composition of the present invention, the method for blending each dye is not particularly limited. For example, each dye is produced separately, then blended in the reaction solution at the time of production, then dried to form a composition, and each dye is dissolved in the dye bath, The method of making it the same composition as each said composition can be taken. The mixing ratio of the blue reactive dye composition and the red 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, a reducing agent and the like. .
In the above, the dyeing bath, padding liquid, and printing paste are directly dyed with the dyes constituting the blue reactive dye composition or reactive dye composition of the present invention and the additives as described above, and the dyeing bath is prepared and dyed. The order of dissolving the respective dyes and additives may be any order. The amount of each drug used is also appropriately determined according to the above.

  In the blue reactive dye composition and the dyeing method using the reactive dye composition of the present invention, the amount used is usually 0.005 to 15% (vs. fiber mass,% owf) based on the fiber.

  The blue reactive dye composition and reactive dye composition of the present invention are useful for dyeing cellulose fiber materials and fiber materials containing them. Examples of the target fiber include cellulose fibers such as cotton, hemp, rayon, polynosic, cupra, and lyocell, or a mixed fiber of these. 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 the dyeing of cellulose fibers such as cotton, the blue reactive dye composition of the present invention corresponding to a desired hue and concentration, the reactive dye composition 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 bath ratio is usually 1: 5 to 1:50 (substance to be dyed: dyeing bath).

  In the continuous dyeing method, an acid binder, for example, sodium carbonate, sodium bicarbonate, caustic soda, etc. is added to the dye padding solution alone or in combination, and after padding by a known method, it is dried and then dried by a known method. Alternatively, a one-bath padding method for dyeing by steaming and drying after padding the dye, a known inorganic neutral salt such as anhydrous sodium sulfate, sodium chloride, and an acid binder such as caustic soda and sodium silicate, The two-bath padding method is exemplified in which paddy is dyed by dry heat or steam with a known method, 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 blue reactive dye composition, reactive dye composition, and dyeing method of the present invention have extremely good leveling and reproducibility in dyeing cellulose fibers and fiber materials containing the same, and have good build-up properties, etc. Thus, a dyed product excellent in various dyeing properties and excellent in fastness can be obtained.

  Hereinafter, the present invention will be described in more detail with reference to examples. In the text, “part” means part by mass unless otherwise specified.

Example 1
Table 1 shows the combinations of reactive dyes and the amounts used. In Table 1, C.I. I. Reactive means a color index generic name.

Table 1 (Composition composition)
Formulation Example 1 (present invention)
Blue reactive dye
0.23 parts of dye of formula (B)
Dye of formula (5) 0.13 part Red reactive dye
Dye of formula (7) 0.11 part
Dye of formula (8) 0.09 part Yellow reactive dye
Dye of formula (9) 0.54 parts Formulation Example 2 (for comparison)
Blue reactive dye C.I. I. Reactive Blue 221 0.39 parts Red reactive dye C.I. I. Reactive Red 195 0.20 part Yellow reactive dye C.I. I. Reactive Yellow 145 0.59 part formulation example 3 (for comparison)
Blue reactive dye C.I. I. Reactive Blue 222 0.25 part Red reactive dye C.I. I. Reactive Red 195 0.14 parts Yellow reactive dye C.I. I. Reactive Yellow 145 0.49 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 each dye shown in Table 1 and 20 parts of 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 (Scoreol C-1200 Kitahiro Chemical Co., Ltd. 1 g / L). Dried to give a brown dyeing.
(2) Dyeing at a bath ratio of 1:30 A dye bath having a total amount of 1470 parts was prepared by adding water to each dye shown in Table 1 and 60 parts of 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 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 brown dyed product.
(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.
○: Small hue difference ×: Large hue difference

○ Temperature dependency test (1) Dyeing at 55 ° C. A dyeing bath having a total amount of 980 parts was prepared by adding water to each dye shown in Table 1 and 40 parts of anhydrous sodium sulfate. 50 parts of cotton knitted fabric was added to this dye bath, and the temperature was raised to 55 ° C. over 20 minutes. After treatment at 55 ° 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 a brown dyed product.
(2) 65 degreeC dyeing | staining dye | stained by the method similar to the said 55 degreeC dyeing | staining except having changed the dyeing | staining temperature to 65 degreeC.
(3) Judgment method The hue difference of the dyed product obtained by 65 ° C. dyeing was visually judged on the basis of the dyed product obtained by 55 ° C. dyeing.
○: Hue difference small △: Hue difference slightly large

Absorption and fixation behavior test Water was added to the reactive dyes shown in Table 1 and 40 parts of anhydrous sodium sulfate to prepare four dye baths having a total amount of 980 parts. 50 parts of cotton knitted fabric was added to each dye bath, and after heating to 60 ° C. in 20 minutes, each dye bath was treated by the following methods (1) to (4) to test absorption and fixing behavior. .
(1) After the temperature was raised to 60 ° C. and kept at 60 ° C. for 20 minutes, the dyed fabric was taken out from one dye bath, and this was 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 100 parts of an aqueous solution containing the soaping agent at 100 ° C. for 15 minutes, washed with water and dried (fixed cloth).
(2) Add 20 parts of sodium carbonate (a total of 1000 parts of dye bath), and after dyeing at the same temperature for 5 minutes, take out one dyed cloth and divide it into two equal parts, respectively (A) or (B) After-treatment was performed.
(3) After adding 20 parts of sodium carbonate (a total of 1000 parts of dye bath), after dyeing at the same temperature for 10 minutes, one dyed cloth is taken out and divided into two equal parts, respectively (A) or (B) After-treatment was performed.
(4) Add 20 parts of sodium carbonate (1000 parts total dye bath), dye for 40 minutes at the same temperature, take out one dyed cloth, divide it into two equal parts, respectively (A) or (B) After-treatment was performed.

Judgment method (a)
In each of (1) to (4), the hue difference of the (B) treated cloth was visually determined on the basis of the (A) treated cloth.
○: (1) to (4) all have small hue difference ×: (1) to (4) any hue difference is large Judgment method (b)
The degree of hue change in the order of (1), (2), (3), and (4) in the (B) treated cloth was visually determined.
○: (1) to (4) hues of the same system (good balance of fixing speeds of the three primary colors)
×: Large change in hue in (1) to (4) (adequate fixing speed balance of the three primary colors)
Table 2 shows the comparison results of the bath ratio dependency, temperature dependency, absorption, and fixing behavior for Formulation Example 1 (present invention) and Formulation Examples 2 to 3 (for comparison).

Table 2 Test results
Bath ratio dependence Temperature dependence Absorption and adsorption behavior
Judgment method (a) Judgment method (b)
Formulation Example 1 ○ ○ ○ ○
Formulation Example 2 × △ × ×
Formulation Example 3 × △ × ×

  Only when dyeing is performed in combination with Formulation Example 1 (present invention), the dyeing properties of the yellow reactive dye, red reactive dye, and blue reactive dye are the same, and the dyeing conditions such as bath ratio, dyeing temperature, dyeing time, etc. Even when the color fluctuates, the hue change is small, the fixing speeds are almost the same, and the dyeing reproducibility is excellent.

Examples 2-15
In place of the combination and the amount used in Formulation Example 1 of Example 1, using the dye combinations and amounts (parts) shown in Table 3, water was added to 40 parts of anhydrous sodium sulfate to prepare a total amount of 980 parts of dyeing bath. Each 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.
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.

Table 3
Example 2
Blue reactive dye
0.28 parts of dye of formula (B)
Dye of formula (5) 0.15 parts Example 3
Blue reactive dye
0.55 parts of the dye of formula (B)
Dye of formula (5) 0.31 part Red reactive dye (for hue adjustment)
Dye of formula (7) 0.05 part

Example 4
Blue reactive dye
0.60 parts of the dye of formula (B)
Dye of formula (5) 0.28 part Red reactive dye (hue adjustment)
Dye of formula (8) 0.04 parts Example 5
Blue reactive dye
0.23 parts of dye of formula (B)
Dye of formula (5) 0.13 part Red reactive dye
Dye of formula (7) 0.11 part
Dye of formula (8) 0.09 part Yellow reactive dye
Dye of formula (9) 0.54 parts Example 6
Blue reactive dye Dye of formula (B) 0.38 part Dye of formula (5) 0.22 part Red reactive dye Dye of formula (7) 0.22 part Dye of formula (8) 0.18 part

Example 7
Blue reactive dye Dye of formula (B) 0.45 part Dye of formula (5) 0.25 part Red reactive dye Dye of formula (7) 0.06 part Dye of formula (8) 0.04 part Yellow reactive dye Formula Dye of (9) 0.20 part Example 8
Blue reactive dye Dye of formula (B) 0.13 part Dye of formula (6) 0.07 part Red reactive dye Dye of formula (7) 0.39 part Dye of formula (8) 0.32 part Yellow reactive dye Formula Dye of (9) 0.10 parts Example 9
Blue reactive dye Dye of formula (B) 0.23 part Dye of formula (6) 0.13 part Red reactive dye Dye of formula (7) 0.11 part Dye of formula (8) 0.09 part Yellow reactive dye Formula 0.57 parts of the dye of (10)

Example 10
Blue reactive dye Dye of formula (B) 0.23 part Dye of formula (5) 0.13 part Red reactive dye Dye of formula (7) 0.20 part Yellow reactive dye Dye of formula (9) 0.54 part Example 11
Blue reactive dye Dye of formula (B) 0.23 part Dye of formula (6) 0.13 part Red reactive dye Dye of formula (7) 0.11 part Dye of formula (8) 0.09 part Yellow reactive dye Formula Dye of (9) 0.54 parts Example 12
Blue reactive dye Dye of formula (B) 0.23 part Dye of formula (5) 0.13 part Red reactive dye Dye of formula (7) 0.08 part Dye of formula (8) 0.12 part Yellow reactive dye Formula Dye of (9) 0.54 parts

Example 13
Blue reactive dye Dye of formula (B) 0.23 part Dye of formula (5) 0.13 part Red reactive dye Dye of formula (7) 0.14 part Dye of formula (8) 0.06 part Yellow reactive dye Formula Dye of (9) 0.54 parts Example 14
Blue reactive dye Dye of formula (B) 0.27 part Dye of formula (5) 0.09 part Red reactive dye Dye of formula (7) 0.11 part Dye of formula (8) 0.09 part Yellow reactive dye Formula Dye of (9) 0.54 parts Example 15
Blue reactive dye Dye of formula (B) 0.16 part Dye of formula (5) 0.20 part Red reactive dye Dye of formula (7) 0.11 part Dye of formula (8) 0.09 part Yellow reactive dye Formula Dye of (9) 0.54 parts

  As for the hue of the obtained dyed product, Example 2 is blue, Examples 3 and 4 are dark blue, Example 6 is purple, Example 7 is green, Example 8 is orange, Examples 5 and 9 ~ 15 was brown. In any combination of Examples 2 to 15, the leveling and reproducibility are extremely good, and the various dyeing properties such as good build-up properties are excellent, and the light resistance, sweat light resistance, chlorine water, etc. The fastnesses were also excellent.

Examples 16-21
Using the dye combinations shown in Table 4, 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.
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.

Table 4
Example 16
Blue reactive dye Dye of formula (B) 0.23 part Dye of formula (5) 0.13 part Red reactive dye Dye of formula (7) 0.11 part Dye of formula (8) 0.09 part Yellow reactive dye Formula Dye of (9) 0.54 parts Example 17
Blue reactive dye Dye of formula (B) 0.23 part Dye of formula (6) 0.13 part Red reactive dye Dye of formula (7) 0.13 part Dye of formula (8) 0.07 part Yellow reactive dye Formula Dye of (10) 0.57 parts Example 18
Blue reactive dye Dye of formula (B) 0.27 part Dye of formula (5) 0.09 part Red reactive dye Dye of formula (7) 0.12 Part Dye of formula (8) 0.10 part Yellow reactive dye Formula Dye of (9) 0.54 parts

Example 19
Blue reactive dye Dye of formula (B) 0.23 part Dye of formula (5) 0.13 part Red reactive dye Dye of formula (7) 0.14 part Dye of formula (8) 0.06 part Yellow reactive dye Formula Dye of (9) 0.54 parts Example 20
Blue reactive dye Dye of formula (B) 0.45 part Dye of formula (5) 0.25 part Red reactive dye Dye of formula (7) 0.06 part Dye of formula (8) 0.04 part Yellow reactive dye Formula Dye of (9) 0.20 part

Example 21
Blue reactive dye Dye of formula (B) 0.13 part Dye of formula (5) 0.07 part Red reactive dye Dye of formula (7) 0.39 part Dye of formula (8) 0.32 part Yellow reactive dye Formula Dye of (9) 0.10 parts

As for the hue of the obtained dyeing | staining, Example 16-19 was brown, Example 20 was green, and Example 21 was an engine color.
In any combination of Examples 16 to 21, the leveling property and reproducibility are extremely good, and the various dyeing properties such as good build-up property are excellent, and light resistance, sweat light resistance, chlorine water, etc. Various fastnesses were also excellent.

Example 22
Dye of formula (B) as blue reactive dye 3.30 parts, dye of formula (5) 1.85 parts, dye of formula (7) as red reactive dye 7.20 parts, dye of formula (8) 5.06 Using 12.00 parts of the dye of the formula (9) as a yellow reactive dye, water is 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 is 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 reddish 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 .

Example 23
6.33 parts of a dye of formula (B) as a blue reactive dye, 3.55 parts of a dye of formula (5), 10.25 parts of a dye of formula (7) as a red reactive dye, a dye of formula (8) 7.33 Using 17.00 parts of the dye of the formula (9) as a yellow reactive dye, water is added to 100 parts of urea, 20 parts of sodium bicarbonate, 10 parts of sodium metanitrobenzenesulfonate, and 25 parts of sodium alginate, and a total amount of 1000 parts 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 reddish 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.

  By using the blue reactive dye composition, reactive dye composition or dyeing method of the present invention, reproducibility, leveling and fastness based on balanced affinity and reactivity of cellulose fibers or cellulose-containing fibers. Can be dyed well.

Claims (7)

A reactive dye composition comprising, in the form of a free acid, a blue reactive dye represented by formula (A) and a blue reactive dye represented by formula (1) at a composition ratio of 95 to 5% by mass: 5 to 95% by mass.
Formula (A)

(In the formula (A), R represents a hydrogen atom, a halogen atom or a C1-C4 alkoxy group. The —SO ₂ CH ₂ CH ₂ OSO ₃ H group is formed by decomposition of —SO ₂ CH═CH. _Two groups may be used.)
Formula (1)

(In formula (1), m ₁ is an integer of 0 to 2, R ₁ and R ₂ are each independently a hydrogen atom or an optionally substituted alkyl group, X ₁ is a halogen atom, and -Y ₁ is —SO ₂ CH═CH ₂ or —SO ₂ CH ₂ CH ₂ Z ₁ (Z ₁ represents a group capable of leaving by the action of an alkali), respectively. A reactive dye composition according to claim 1, in the form of a free acid, in the form of a red reactive dye of formula (2) and / or formula (3), and / or in the form of a free acid, in formula (4) Reactive dye composition containing the indicated yellow reactive dye.
Formula (2)

(In Formula (2), m ₂ is an integer of 0 to 2, n ₁ is 0 or 1, R ₃ and R ₄ are each independently a hydrogen atom or an optionally substituted alkyl group, and X ₂ is -Y ₂ represents —SO ₂ CH═CH ₂ or —SO ₂ CH ₂ CH ₂ Z ₂ (Z ₂ represents a group capable of leaving by the action of an alkali).
Formula (3)

(In Formula (3), m ₃ is an integer of 0 to ₂ , n ₂ is 0 or 1, R ₅ and R ₆ are each independently a hydrogen atom or an optionally substituted alkyl group, and X ₃ is -Y ₃ represents —SO ₂ CH═CH ₂ or —SO ₂ CH ₂ CH ₂ Z ₃ (Z ₃ represents a group capable of leaving by the action of an alkali).
Formula (4)

(In Formula (4), m ₄ is an integer of 1 to 3, R ₇ and R ₈ are each independently a hydrogen atom, alkyl group, alkoxy group, acylamino group or ureido group, and R ₉ and R ₁₀ are each independently. X ₄ represents a halogen atom, —Y ₄ represents —SO ₂ CH═CH ₂ or —SO ₂ CH ₂ CH ₂ Z ₄ (Z ₄ represents an alkali action). Each represents a leaving group). A reactive dye composition comprising the reactive dye composition according to claim 1 and the red reactive dye represented by formula (2) and / or formula (3) according to claim 2 . The composition ratio of the reactive dye composition according to claim 1 and the red reactive dye represented by formula (2) and / or formula (3) is 99 to 50% by mass: 1 to 50% by mass. Reactive dye composition. The reactive dye composition according to claim 3, wherein the composition ratio of the red reactive dye represented by the formulas (2) and (3) is 90 to 10% by mass: 10 to 90% by mass. A method for dyeing cellulose fibers or cellulose fiber-containing fiber materials, wherein the reactive dye composition according to any one of claims 1 to 5 is used. The free acid form of claim 1, the blue reactive dye of formula (A) and the blue reactive dye of formula (1), and the free acid form of claim 2, Cellulose fibers in a dye bath containing a red reactive dye represented by 2) and / or formula (3) and / or a yellow reactive dye represented by formula (4) in the form of a free acid according to claim 2 Alternatively, a method for dyeing a cellulose fiber or a fiber material containing cellulose fiber, which comprises treating the fiber material containing cellulose fiber.