JPH083050B2 - Reactive dye composition and dyeing or printing method using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a reactive dye composition and an industrially advantageous dyeing or printing method for cellulosic fibers using the same.

<Prior Art> It is well known that dyeing a cellulosic fiber with a reactive dye, but usually the intended color tone and fastness are the first priority, and a dye that meets this purpose is selected. Has been done. In this case, in order to improve the leveling and reproducibility defects caused by the difference in the reactivity of the respective dyes with the cellulosic fibers, or due to the uneven temperature of the dyeing liquid that often occurs in the dyeing device. In the exhaust dyeing process, especially, the inorganic salt or alkali agent to be added in the dyeing bath is appropriately divided into fine particles, and the dyeing device is equipped with a special dyeing liquid stirring device to reduce temperature unevenness. It takes a lot of work. Alternatively, as described in JP-A-60-259687, a fine work of adding an inorganic salt or an alkaline agent according to a positive or negative exponent, a logarithm or a power function is known.

Further, in the continuous dyeing process and the cold batch-up dyeing process, in order to prevent a so-called tailing phenomenon, which is a phenomenon of color difference between the anti-start portion and the anti-end portion, depending on the affinity of the reactive dye and the cellulosic fiber. In addition, a complicated operation of adding a dye consumed during the processing process or creating a new dyeing bath is performed.
It is also known that due to the difference in the reactivity of the reactive dyes used, the desired color and density cannot often be obtained due to slight fluctuations in the fixing treatment time and the treatment temperature.

In the printing process, it is known that the target color and density are often not obtained due to the difference in the reactivity of the reactive dyes used and the slight fluctuations in the processing time and processing temperature during the fixing process. There is.

<Problems to be Solved by the Invention> However, in the conventionally known publicly-known technique, a great deal of time and work are spent on the dyeing processing operation, and further, dyeing or dyeing that is always satisfactory in terms of levelness and reproducibility. Printing was rarely done.

The present inventors, in a method of dyeing or printing a cellulosic fiber with a reactive dye, simplify the dyeing or printing operation to solve the above problems, improve the reproducibility and levelness in dyeing or printing. As a result of intensive studies on the method, it was found that a reactive dye composition containing a specific different dye achieves the object, and the present invention has been completed.

<Means for Solving Problems> The present invention has the following general formula (I). [In the formula, D ₁ is a residue of an organic dye having a sulfonic acid group,
R ₁ , R ₂ and R ₃ are independently of each other hydrogen or lower alkyl which may have a substituent, B ₁ and B ₂ are independently of each other, methyl, ethyl, methoxy, ethoxy, chloro, bromo, nitro, 1 or 2 selected from the group of carboxy and sulfo
Phenylene which may be substituted with one substituent, or naphthylene which may be substituted with sulfo, Z ₁ and Z ₂
Are each independently vinyl or --CH ₂ CH ₂ L (L is a group capable of leaving by the action of an alkali), and n is 1 to 3. ] And a reactive dye represented by the following general formula (II) [In the formula, D ₂ is a residue of an organic dye having a sulfonic acid group, R ₄
And R ₅ are each independently hydrogen or lower alkyl optionally having a substituent, B ₃ is 1 or 2 selected from the group of methyl, ethyl, methoxy, ethoxy, chloro, bromo, nitro, carboxy and sulfo. Phenylene optionally substituted with one substituent, or naphthylene optionally substituted with sulfo, Z ₃ is vinyl or —CH ₂ CH ₂ L (L has the above meaning), X is chlorine, It represents a non-aromatic or aromatic tertiary nitrogen compound residue having bromine, fluorine or a quaternary nitrogen atom, and n has the above-mentioned meaning. ] And / or the following general formula (III), [In the formula, D ₃ is a residue of an organic dye having a sulfonic acid group,
R ₆ , R ₇ and R ₈ are independently of each other hydrogen or lower alkyl which may have a substituent, B ₄ is methyl, ethyl, methoxy, ethoxy, chloro, bromo, nitro, carboxy and sulfo. Phenylene optionally substituted by one or two selected substituents, or naphthylene optionally substituted by sulfo, B ₅ is selected from the group of lower alkyl, lower alkoxy, nitro, cyano, carboxy and sulfo. Phenyl optionally substituted by at least one substituent represented by the following, or naphthyl optionally substituted by sulfo, Z ₄ represents vinyl or —CH ₂ CH ₂ L (L has the above meaning). , N have the meanings given above. ]
The present invention provides a reactive dye composition containing a reactive dye represented by the above and a method for dyeing or printing a cellulosic fiber using the same.

According to the present invention, in exhaustion dyeing, there is a simple method of workability in which a dye, an inorganic salt or an alkaline agent used, and a known dyeing auxiliary agent optionally used are added to the dyeing bath from the beginning of the dyeing process. It is possible to provide a dyed product which can be used and has extremely good levelness, reproducibility and temperature sensitivity. Also, in continuous dyeing and cold batch-up dyeing, it is necessary to add consumed dye into the dyeing bath or create a new dyeing bath and create a single dyeing bath from the beginning to end. A so-called tailing phenomenon-free dyeing having the same shade and having the same density throughout the entire part is provided. Furthermore,
In the printing, a printed material having a uniform hue and a uniform hue even with respect to fluctuations in processing time and processing temperature in the fixing step is provided.

In the present invention, the lower alkyl group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ is preferably an alkyl group having 1-4 carbon atoms, As the group which may be substituted, a hydroxy group, a cyano group, an acoxy group, a halogen, a carboxy group, a carbamoyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a sulfonic acid group,
A sulfamoyl group is preferred.

Examples of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ include hydrogen atom, methyl group, ethyl group, n-propyl group, iso-propyl group, and n-butyl. Group, iso-butyl group, sec-butyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, 2, 3-dihydroxypropyl group, 3,4-dihydroxybutyl group, cyanomethyl group, 2-cyanoethyl group, 3-
Cyanopropyl group, methoxythymer group, ethoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 3
-Methoxypropyl group, 3-ethoxypropyl group, 2-
Hydroxy-3-methoxypropyl group, chloromethyl group, bromomethyl group, 2-chloroethyl group, 2-bromoethyl group, 3-chloropropyl group, 3-bromopropyl group, 4-chlorobutyl group, 4-bromobutyl group, carboxymethyl group , 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 1,2-dicarboxyethyl group, carbamoylmethyl group, 2-carbamoylethyl group, 3-carbamoylpropyl group, 4-carbamoylbutyl group, Methoxycarbonylmethyl group, ethoxycarbonylmethyl group, 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 3-methoxycarbonylpropyl group, 3-ethoxycarbonylpropyl group, 4-methoxycarbonylbutyl group, 4-ethoxycarbonylbutyl group Base, Chill carbonyloxy methyl group, ethyl carbonyloxy methyl group, 2-methyl-carbonyloxy ethyl group, 2-ethyl-carbonyloxy ethyl group, 3-methyl-carbonyloxy propyl group, 3-
Ethylcarbonyloxypropyl group, 4-methylcarbonyloxybutyl group, 4-ethylcarbonyloxybutyl group, sulfomethyl group, 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, sulfamoylmethyl group, 2-sulfur Examples thereof include a famoylethyl group, a 3-sulfamoylpropyl group, a 4-sulfamoylbutyl group and the like, and a hydrogen atom, a methyl group and an ethyl group are particularly preferable.

In the present invention, the group represented by B ₁ , B ₂ , B ₃ , and B ₄ ,
For example (In the formula, the bonds shown by an asterisk mean the bonds leading to —SO ₂ —Z ₁ to ₄ , respectively.) And the like.

In the present invention, the group represented by B ₅ includes, for example, a phenyl group which is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a sulfonic acid group and a carboxylic acid group. A phenyl group which may be substituted with 1 or 2 substituents selected from the group consisting of a cyano group, a nitro group and a chlorine atom is preferred. The naphthyl group is a naphthyl group which may be substituted with 1, 2 or 3 sulfonic acid groups, and particularly preferably 2
-, 3-, 4-, 5-, 6-, 7- or 8-sulfo-1-naphthyl group, 1-, 5-, 6-, 7- or 8-sulfo-2-naphthyl group, 2,4 −, 5,7−, 6,8−, 4,8−, 4,7−, 3,8−, 4,6
-, 3,7- or 3,6-disulfo-2-naphthyl group, 4,6,8
-, 2,4,7- or 3,6,8-trisulfo-1-naphthyl group,
Examples include 1,5,7-, 4,6,8- or 3,6,8-trisulfo-2-naphthyl group.

In the present invention, as the organic dye having a sulfonic acid group represented by D ₁ , D ₂ and D ₃ , a mono- or polyazo-based dye,
Examples thereof include dyes having a metal complex salt type, formazan type, anthraquinone type, phthalocyanine type, stilbene type, oxazine type, dioxazine type, triphenylmethane type, nitro type or azomethine type sulfonic acid group.

Among these, mono- or polyazo dyes, metal complex salt dyes, formazan dyes, and phthalocyanine dyes can be present in the form having Cu, Cr, Co, Ni, or Fe as a complex compound-forming central atom.

In the general formulas (I), (II), and (III), L
Examples of the group that is eliminated by the action of an alkali represented by, for example, a sulfate ester group, a thiosulfate group,
A phosphoric acid ester group, an acetic acid ester group, a halogen atom, etc. correspond to this.

The reactive dye represented by the general formula (I) is represented by the following formula: (In the formula, D ₁ , R ₁ , R ₂ , R ₃ , B ₁ , B ₂ , Z ₁ , Z ₂ and n have the above meanings.), A compound represented by the general formula (II) The reactive dye is the following formula (Wherein D ₂ , R ₄ , R ₅ , B ₃ , Z ₃ and n have the above-mentioned meanings) and a non-aromatic or tertiary nitrogen optionally having a quaternary nitrogen atom. Aromatic compounds having atoms,
The reactive dye represented by the general formula (III) is (Wherein D ₃ , R ₆ , R ₇ , R ₈ , B ₄ , B ₅ , Z ₄ and n have the above-mentioned meanings), 1,3, such as cyanuric chloride is used. Five
-Trihalogeno-s-triazine can be easily produced by successively condensing them in a conventional manner.

The reactive dye composition of the present invention is prepared by mixing the reactive dye represented by the general formula (I) with the reactive dye represented by the general formula (II) and / or the reactive dye represented by the general formula (III). can get.

The mixing ratio of the reactive dyes represented by the general formulas (I), (II) and (III) is not particularly limited, but one component to be mixed is preferably 5% by weight or more.

In the present invention, the reactive dye composition is a known reactive dye other than the general formulas (I), (II) and (III) as well as a dye improving agent such as a solubilizing agent and a dyeing assistant, as long as the dyeing property is not affected. Can be included.

The cellulosic fiber in the method of the present invention is not particularly limited, but examples thereof include regenerated cellulose such as cotton, linen, hemp, jute, ramie fiber, viscose, and a mixture thereof with other fibers. To be done.

The dyeing or printing method in the method of the present invention may be a known method, but the exhaust dyeing method is a known inorganic neutral salt such as anhydrous Glauber's salt and salt, and known sodium carbonate, caustic soda, sodium triphosphate, etc. A method of dyeing with an acid binder is exemplified. In the cold batching up dyeing method,
Examples include a method of dyeing by leaving a known inorganic neutral salt such as anhydrous Glauber's salt and salt and a known acid binder such as caustic soda and sodium silicate, and then leaving it at a constant temperature in a hermetically sealed packaging material. . In the continuous dyeing method, a known acid binder such as sodium carbonate or sodium bicarbonate is mixed with a dye padding solution, and after padding by a known method, a one-bath padding method of dyeing by dry heat or steam, and after dye padding, anhydrous sodium sulfate An example is a two-bath padding method in which a known inorganic neutral salt such as sodium chloride and salt and a known acid binder such as caustic soda and sodium silicate are padded and dyed by dry heat or steam by a known method.
In the printing method, after printing a printing paste containing a known acid binder such as sodium bicarbonate, a one-phase printing method of printing by drying or steaming, and after printing the printing paste, an inorganic neutral salt such as salt and caustic soda or An example is a two-phase printing method in which a known acid binder such as sodium silicate is put into a high temperature of 90 ° C. or higher for printing.

According to the present invention, a dyeing product or a printing product can be obtained which is extremely easy to work as compared with a method which is usually carried out industrially, and which has good reproducibility and good levelness in dyeing and printing.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. still,
In the examples, parts and% mean parts by weight and% by weight, respectively.

Example 1 Formula (1-1) in the form of free acid 50 parts of the dye represented by the formula (1-2) in the form of free acid 50 parts of the dye represented by 1 was thoroughly mixed.

100 parts of a knitted fabric made of cellulose fibers was set in a Wins type dyeing apparatus, and the bath ratio was 1:15 and the water temperature was 30 ° C.

3 parts of the dye obtained above pre-dissolved, anhydrous sodium sulfate 75
Parts and 30 parts of sodium carbonate are put into the bath by a known method all together, then the temperature is raised to 60 ° C. in 30 minutes, and at this temperature 40
The knitted fabric was processed for a minute, and the dyeing was completed. The obtained dyed product was washed and finished by a conventional method. The dyed product thus obtained was yellow with a uniform deep greenish green color without spots.

Comparative Example 1 A knitted fabric made of the same cellulose fiber as in Example 1 was dyed by the same procedure as in Example 1 using the dye represented by the formula (1-2) in Example 1 and washed by a conventional method to finish. . The dyed product thus obtained had a greenish yellow color with spots.

Example 2 Formula (2-1) in the form of free acid 60 parts of the dye represented by formula (2-2) in the form of free acid 20 parts of the dye represented by formula (2-3) in the form of free acid 20 parts of the dye represented by

50 parts of the obtained dye is dissolved in hot water and cooled to 25 ° C. To this, add 15 parts by volume of a 32.5% caustic soda aqueous solution and 150 parts of water glass at 50 degrees Baume, and further add water to bring the total amount to 1 at 25 ° C.
Immediately after 000 parts by volume, a mercerized cotton fabric is padded using this solution as a padding solution. The padded cotton fabric was rolled up, sealed with a polyethylene film, allowed to stand at room temperature of 20 ° C. for 20 hours, and then the dyed product was washed and dried by a conventional method to finish. The obtained dyed product was a uniform deep red color having the same hue and the same density throughout from the beginning to the end.

Comparative Example 2 The same mercerized cotton fabric as in Example 2 was used by using the dyes represented by the formulas (2-1), (2-2), and (2-3) in Example 2 alone, respectively. It dye | stained by the same operation as 2 and was wash | cleaned and finished by the conventional method. The dyed product thus obtained was red with a difference in density between the anti-starting part and the anti-ending part.

Example 3 Formula (3-1) in the form of free acid 20 parts of the dye represented by formula (3-2) in the form of free acid 40 parts of the dye represented by the formula (3-3) in the form of free acid 40 parts of the dye shown by 1 was thoroughly mixed.

100 parts of the obtained dye is dissolved in hot water and cooled to 25 ° C.
To this, 1 part of sodium alginate, 10 parts of sodium metanitrobenzene sulfonate and 20 parts of sodium hydrogencarbonate were added, and further water was added to make 1000 parts by volume at 25 ° C. Immediately after using this solution as a padding solution, rayon was added. The fabric was bagged. The padded rayon fabric was dried at 120 ° C for 2 minutes and then steamed at 100 ° C for 5 minutes to fix the dye. The obtained dyed product was washed by a conventional method and dried to finish. The dyed product thus obtained was a uniform deep blue color which had the same hue and the same density throughout from the beginning to the end.

Comparative Example 3 The same rayon fabric as in Example 3 was used as Example 3 except that the dyes represented by the formulas (3-1), (3-2) and (3-3) in Example 3 were used alone. It dye | stained by the same operation and wash | cleaned and finished it by the conventional method. The dyed product thus obtained was blue with a difference in density between the anti-starting part and the anti-end part.

Example 4 Formula (4-1) in the form of free acid 40 parts of the dye represented by the formula (4-2) in the form of free acid 60 parts of the dye represented by

(B) 50 parts of the obtained dye is dissolved in hot water, then 20 parts of sodium alginate and sodium metanitrobenzene sulfonate.
Immediately after adding 10 parts and 20 parts of sodium hydrogen carbonate and further adding water to make 1000 parts at 20 ° C., a mercerized cotton fabric was printed using this as a printing paste and dried. Next, steaming was carried out at 100 ° C. for 5 minutes to fix the dye. The obtained print was washed by a conventional method and dried to finish. The print thus obtained was of uniform and deep scarlet red color.

(B) A uniform dark scarlet print having the same density and the same hue as in (a) above, whether it is steamed at 100 ° C for 10 minutes or steamed at 110 ° C for 5 minutes. Met.

Comparative Example 4 The same mercerized cotton fabric as in Example 4 was printed by the same procedure as in Example 4, using the dyes represented by the formulas (4-1) and (4-2) in Example 4 respectively. , Finished in the usual way.
When the concentration of the print thus obtained was examined, it was 100 ° C.
There was a marked difference in the density between the prints steamed for 5 minutes at 100 ° C., the prints steamed at 100 ° C. for 10 minutes, and the prints steamed at 110 ° C. for 5 minutes.

Examples 5 to 22 Example 1 using the dyes shown in Tables 1 to 9 in the form of the free acid
Dyeing and printing were performed according to the methods described in Nos. 4 to 4.

Each of the dyes alone was a dyeing and printing product which was uneven in dyeing and printing and had poor density and reproducibility.

However, when the dyes shown in Tables 1 to 9 were mixed in the proportions shown in Tables 1 to 9, the dyed and printed products had extremely good levelness and reproducibility in dyeing and printing.

Claims (2)

[Claims] 1. The following general formula (I): [In the formula, D ₁ is a residue of an organic dye having a sulfonic acid group,
R ₁ , R ₂ and R ₃ are independently of each other hydrogen or lower alkyl which may have a substituent, B ₁ and B ₂ are independently of each other, methyl, ethyl, methoxy, ethoxy, chloro, bromo, nitro, 1 or 2 selected from the group of carboxy and sulfo
Phenylene which may be substituted with one substituent, or naphthylene which may be substituted with sulfo, Z ₁ and Z ₂
Are each independently vinyl or --CH ₂ CH ₂ L (L is a group capable of leaving by the action of an alkali), and n is 1 to 3. ] And a reactive dye represented by the following general formula (II) [In the formula, D ₂ is a residue of an organic dye having a sulfonic acid group, R ₄
And R ₅ are each independently hydrogen or lower alkyl which may have a substituent, B ₃ is 1 or 2 selected from the group of methyl, ethyl, methoxy, ethoxy, chloro, bromo, nitro, carboxy and sulfo. Phenylene optionally substituted by a substituent of naphthylene, naphthylene optionally substituted by sulfo, Z ₃ is vinyl or —CH ₂ CH ₂ L (L has the above meaning), X is chlorine or bromine. , Fluorine or a non-aromatic or aromatic tertiary nitrogen compound residue having a quaternary nitrogen atom, and n has the above-mentioned meaning. ] And / or the following general formula (II
I), [In the formula, D ₃ is a residue of an organic dye having a sulfonic acid group,
R ₆ , R ₇ and R ₈ are independently of each other hydrogen or lower alkyl which may have a substituent, B ₄ is a group of methyl, ethyl, methoxy, ethoxy, chloro, bromo, nitro, carboxy and sulfo. Phenylene optionally substituted by one or two selected substituents, or naphthylene optionally substituted by sulfo, B ₅ is selected from the group of lower alkyl, lower alkoxy, nitro, cyano, carboxy and sulfo. A phenyl optionally substituted by at least one substituent or a naphthyl optionally substituted by sulfo, Z ₄ represents vinyl or —CH ₂ CH ₂ L (L has the above meaning). , N have the meanings given above. ] A reactive dye composition comprising a reactive dye represented by 2. The following general formula (I) [In the formula, D ₁ is a residue of an organic dye having a sulfonic acid group,
R ₁ , R ₂ and R ₃ are independently of each other hydrogen or lower alkyl which may have a substituent, B ₁ and B ₂ are independently of each other, methyl, ethyl, methoxy, ethoxy, chloro, bromo, nitro, 1 or 2 selected from the group of carboxy and sulfo
Phenylene which may be substituted with one substituent, or naphthylene which may be substituted with sulfo, Z ₁ and Z ₂
Are each independently vinyl or --CH ₂ CH ₂ L (L is a group capable of leaving by the action of an alkali), and n is 1 to 3. ] And a reactive dye represented by the following general formula (II) [In the formula, D ₂ is a residue of an organic dye having a sulfonic acid group, R ₄
And R ₅ are each independently hydrogen or lower alkyl which may have a substituent, B ₃ is 1 or 2 selected from the group of methyl, ethyl, methoxy, ethoxy, chloro, bromo, nitro, carboxy and sulfo. Phenylene optionally substituted by a substituent of naphthylene, naphthylene optionally substituted by sulfo, Z ₃ is vinyl or —CH ₂ CH ₂ L (L has the above meaning), X is a base, bromine. , Fluorine or a non-aromatic or aromatic tertiary nitrogen compound residue having a quaternary nitrogen atom, and n has the above-mentioned meaning. ] And / or the following general formula (III) [In the formula, D ₃ is a residue of an organic dye having a sulfonic acid group,
R ₆ , R ₇ and R ₈ are independently of each other hydrogen or lower alkyl which may have a substituent, B ₄ is a group of methyl, ethyl, methoxy, ethoxy, chloro, bromo, nitro, carboxy and sulfo. Phenylene optionally substituted by 1 or 2 substituents selected, or naphthylene optionally substituted by sulfo, B ₅ is selected from the group of lower alkyl, lower alkoxy, nitro, cyano, carboxy and sulfo. A phenyl optionally substituted by at least one substituent or a naphthyl optionally substituted by sulfo, Z ₄ represents vinyl or —CH ₂ CH ₂ L (L has the above meaning). , N have the meanings given above. ] A method for dyeing or printing a cellulosic fiber, which comprises using a reactive dye composition containing a reactive dye represented by: