JPH04108868A - Reactive dye-containing composition and method for dyeing or printing using the same composition - Google Patents

Abstract

PURPOSE:To obtain the title composition containing a specific dye and condensed product of alkylnaphthalene sulfonic acid with formaldehyde, and capable of uniformly dyeing a cellulosic fiber into dark color in an aqueous alkali. CONSTITUTION:The objective composition containing (A) a dye expressed by formula I {A1 and A2 are (substituted)phenylene or naphthylene; R1 and R2 are H or (substituted)lower alkyl; X is formula II or OR5 [R3 to R5 are H, (substituted)alkyl, phenyl or naphthyl]; either one of B1 and B2 is (substituted) phenylene and the other is (sulfo-substituted)naphthylene; Z1 and Z2 are vinyl or CH2CH2L (L is group capable of eliminating by the action of alkali)} and (B) a condensed product obtained condensing alkylnaphthalene sulfonic acid with formaldehyde, preferably at a weight ratio of 0.25:1 to 9:1.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Field of Application> This invention relates to reactive dye compositions which are extremely well soluble in lukewarm liquids.

<Prior Art> Padding liquids or phase printing, such as one-bath padding winding, bath padding drying and bath padding steaming, which are effective for dyeing natural and male cellulose fibers using reactive dyes. The preparation of printing pastes according to the process requires that the dyes used have sufficient solubility in aqueous alkaline solutions.

For example, dyeing by the -bath padding method is carried out using a dye bath in which up to about 100 parts by weight of dye is dissolved in 1000 parts by weight of an aqueous solution consisting of caustic soda, soda carbonate, or 8th sodium phosphate, and an electrolyte. It is being said.

Furthermore, when exhaust dyeing cellulose fibers, a dye is required that has sufficient solubility in a solution containing a large amount of electrolyte and alkali.

<Problem to be solved by the invention> However, although reactive dyes obtained from the manufacturing process show high solubility in water, many of them have difficulty in dissolving in aqueous alkali, resulting in uniform and spotty dyes. It is difficult to obtain dark dyeings.

Means for Solving the Problems> As a result of intensive study by the present inventors on dye compositions that can satisfy the high demands for these reactive dyes,
The present invention has now been completed.

That is, the present invention provides general formula (I) 5 in which A] and A2 are phenylene or naphthylene groups which may independently have substituents, R1 (in the formula, R
a, Ra and R5 each independently represent hydrogen, an alkyl group which may have a substituent, a phenyl group or a naphthyl group. ), and either Bl or B2 is 1 or 2 selected from the group of methyl, ethyl, methoxy, ethoxy, chloro, bromo, nitro, carboxy, and sulfo.
One represents a phenylene group which may be substituted with one substituent, and the other represents a naphthylene group which may be substituted with sulfo. zl and Z2 are each independently vinyl or -C
H2CH2L (in the formula, L represents a group that is eliminated by the action of an alkali). A reactive dye composition comprising a dye represented by the following and a condensate of at least one alkylnaphthalene sulfonic acid and formaldehyde, and a cellulose fiber material or a fiber material containing cellulose fibers characterized by using the same. Provides a method for dyeing or printing.

In the dye composition of the present invention, the overlapping composition ratio of the dye represented by general formula (I) and the condensate of at least one alkylnaphthalene sulfonic acid and formaldehyde is 0.2
5:1 to 9:1 degree is preferable, more preferably 8:2
~8:2.

In the present invention, examples of the group represented by A1 include the following general formulas (n), (a), (IV), M and (VI).

(In the formula, m is 1 or 2, n is 0 or 1, l is 0 or 1, R6 is hydrogen, methoxy, ethoxy, sulfo, methyl or ethyl, R7 is hydrogen, methoxy, ethoxy, methyl, ethyl, Represents acetylamino, propionylamino or ureido. Bonds marked with an asterisk are represented by the general formula (
1) means the bond leading to 21-028-B s -N==N-. ) Also, examples of the group represented by A2 include the general formula (BO), (1) and (■) (wherein, Rs and R7 have the above-mentioned meanings, and the sita bond indicated by an asterisk is represented by the general formula ( I) Nioite Z 1-02S-B
It has a bond that leads to 1-N=N-AI-N-N-. ) is exemplified.

Specifically, the group represented by AI is (wherein, the bond indicated by an asterisk is Zl
-02S-Bt -N=N- means the same tail bond. ) etc. are exemplified.

In addition, as a group represented by Affi, specifically, (in the formula, the bond indicated with an asterisk is Zt-0 in the general formula (I)
2S -B 1-N=N-A means a bond that leads to 1-N=N-. ) etc. are exemplified.

In the present invention, the lower alkyl group represented by R1 and R2 is preferably an alkyl group having 1 to 4 carbon atoms, and the optionally substituted groups include a hydroxy group, a cyano group, an alkoxy group, Preferred are halogen, carboxy group, carbamoyl group, alkoxycarbonyl group, alkylcarbonyloxy group, sulfo group, and sulfamoyl group.

R1 and R2 are each independently, for example, a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, a 1so-propyl group, an n-butyl group, a 1so-butyl group, 5ec
-butyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 8-hydroxypropyl group, 2-hydroxybutyl group, 8-hydroxybutyl group, 4-hydroxybutyl group, 2.8-dihydroxypropyl group, 3. 4-
dihydroxybutyl group, cyanomethyl group, 2-cyanoethyl group, 8-cyanopropyl group, methoxymethyl group, ethoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 8-methoxypropyl group, 3-ethoxypropyl group, 2-hydroxy-8-methoxypropyl group, chloromethyl group, bromomethyl group, 2-chloroethyl group,
2-bromoethyl group, 8-chloropropyl group, 8-bromopropyl group, 4chlorobutyl group, 4-bromobutyl group, carboxymethyl group, 2-carboxyethyl group, 8-
Carboxypropyl group, 4-carboxybutyl group, 1.
2-dicarboxyethyl group, carbamoyl group, 2
-Carbamoylethyl group, 8-carbamoylpropyl group, 4-carbamoylbutyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 8
-methoxycarbonylpropyl group, 8-ethoxycarbonylpropyl group, 4-methoxycarbonylbutyl group, 4
-Ethoxycarbonylbutyl group, methylcarbonyloxymethyl group, ethylcarbonyloxymethyl group, 2-methylcarbonyloxyethyl group, 2-ethylcarbonyloxyethyl group, 8-methylcarbonyloxypropyl group, 8-ethylcarbonyloxypropyl group , 4-methylcarbonyloxybutyl group, 4-ethylcarbonyloxybutyl group, sulfomethyl group, 2-sulfoethyl group,
8-sulfopropyl group, 4-sulfobutyl group, sulfo 7
Examples include a moylmethyl group, a 2-sulf7moylethyl group, an 8-sulf7moylpropyl group, and a 4-sulfamoylbutyl group, with hydrogen atoms, methyl groups, and ethyl groups being particularly preferred.

In the present invention, the groups represented by B1 and B2 are:
For example, (wherein, the bond indicated with an asterisk is S in general formula (I)
It means a bond leading to Og. ), etc. One of B1 and B2 is phenylene, and the other is naphthylene.

Examples of the group represented by L which is eliminated by the action of an alkali include a sulfate ester group, a thiosulfate ester group, a phosphoric ester group, an acetate ester group, and a halogen atom. Particularly preferred is a sulfate ester group.

In general formula (I), when X is 0R6 and R5 is an alkyl group which may have a substituent, such X is preferably an alkoxy group having 1 to 4 carbon atoms, For example, methoxy group, ethoxy group, n-propoxy group, 1so-propoxy group, n-butoxy group, β
-methoxyethoxy group, 1so-butoxy group and the like. Particularly preferred among these are methoxy and ethoxy groups.

On the other hand, when X is 0R5 and R5 is a phenyl or naphthyl group which may have a substituent, such
For example, one or two alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, nitro groups, sulfo groups, carboxy groups, and chlorine atoms. A phenoxy or naphthoxy group which may be substituted with a substituent is preferred. Among these, particularly preferred examples include 2-8- or 4-chlorophenoxy group, 2-8= or 4-methoxyphenoxy group, and the optionally substituted alkyl group represented by R4, for example, 1 an alkoxy group, a sulfo group, a carboxy group, a hydroxy group, a chlorine atom, having ~4 carbon atoms,
1 to 1 carbon atom optionally substituted with 1 or 2 substituents selected from the group of phenyl group and sulfate group
Preferred are alkyl groups having 4 alkyl groups. Among them, methyl group, ethyl group, n-propyl group, iSO-
Probyl group, n-butyl group, 1so-butyl group, 5eC
-butyl group, β-hydroxyethyl group, β-sulfatoethyl group, β-sulfoethyl group, β-methoxyethyl group, β-carboxyethyl group, and the like.

Further, the phenyl group which may have a substituent represented by R8 and R4 includes, for example, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a carboxy group, and 1 selected from the group of chlorine atoms
Or a phenyl group which may be substituted with two substituents is preferred.

Among them, phenyl group, 2-8- or 4-
Sulfophenyl group, 2-8- or 4-chlorophenyl group, 2-8- or 4-methylphenyl group, 2-8- or 4
-methoxyphenyl group and the like.

Further, the naphthyl group which may have a substituent represented by R8wR4 includes, for example, a hydroxy group, a carboxy group, a sulfo group, an alkyl group having 1 to 4 carbon atoms, and a 1 to 4 carbon atom group. A naphthyl group optionally substituted with 1, 2 or 8 substituents selected from the group consisting of an alkoxy group and a chlorine atom is preferred. Among them, 2-8-4-5-6-7- or 8-sulfo-1-naphthyl group, 1-5-6-7-
or 8-sulfonaphthyl group, 5.7-6°8-4.
8- 4.7- 8.8- 4.68.7- or 8.6
-disulfo-2-naphthyl group, 4.6.8- 2.4.
7- or 8.6.8-) disulfo-1-naphthyl group, 1
, 5.7-4°6.8- or 8.6.8-) disulfo-2-naphthyl group, and the like. Particularly preferred is 6-sulfo-1-naphthyl group.

The dye of general formula (I) can be produced, for example, as follows.

The compound represented by the general formula (■) Zl-028-B1-NH2 (■) (wherein Zl and B1 have the above-mentioned meanings) is diazotized by a conventional method, and this is converted into the compound represented by the general formula (IX
) ■ H-f+-N=N-A2-N-H(IX) (in the formula, AI
, A2 and R1 have the meanings given above. ) to obtain a disazo compound.

The disazo compound obtained here, general formula) H-N-B
2-802-Z2 (x) (wherein, R2, B
2 and z2 have the meanings given above. ) and a compound represented by the general formula (XI)-X (Xi) (wherein, 2,4,6-dolyhalogeno (representing an atom) is condensed with 1,8°5-triazine in any order. The condensation is carried out in an aqueous medium - then -10 to 50°C.
While adjusting the pH to 1-1O with
while adjusting the pH to 2 to 9, and thirdly to 50 to 1.
Each reaction is carried out at 00°C while adjusting the pH to 2 to 9. In this way, a dye represented by general formula (I) can be obtained.

The condensate of at least one alkylnaphthalene sulfonic acid and formaldehyde contained in the composition of the present invention can be produced by a known method.

Examples of the alkylnaphthalene sulfonic acid include mono- or dimethylnaphthalene sulfonic acid, mono- or diethylnaphthalene sulfonic acid, mono- or dibutylnaphthalene sulfonic acid, and mono- or dipropylnaphthalene sulfonic acid, and at least one selected from these is used. However, preferably a mixture of two or more types is used. The average degree of sulfonation of alkylnaphthalene sulfonic acid (1 mole of sulfonic acid group substituted for 1 mole of alkylnaphthalene is defined as 100% degree of sulfonation) is %50 to 1
Approximately 50% is preferable, more preferably 80 to 120%.
%.

The condensate of alkylnaphthalene sulfonic acid and formaldehyde can be used in the form of an alkali metal salt, and the average degree of condensation is preferably about 1.1 to 8, more preferably 15 to 2.5. It is.

The dye composition of the present invention contains urea and anthraquinone. In addition, electrolytes such as sodium chloride and anhydrous sodium sulfate may be added within a small amount that does not adversely affect the solubility of the dye composition, anti-scattering agents such as mineral oil emulsion, pH stabilizers such as disodium phosphate, and polymers. It is permissible to add water softeners such as phosphates.

The dye composition of the present invention can be applied to cotton and other vegetable fibers, such as natural cellulose fibers such as linen, hemp, pseudo and ramie fibers, as well as regenerated cellulose fibers, such as viscose stable and filament viscose fibers, by various dyeing methods. It is possible to effectively dye course or a mixture of these and other thin pongee such as polyester.

The dyeing or printing method in the method of the present invention may be any known method, but in the exhaust dyeing method, known inorganic neutral salts such as anhydrous sodium sulfate and common salt, and known inorganic neutral salts such as sodium carbonate, caustic soda, and sodium phosphate 8 are used. An example is a method of dyeing using an acid binder at a temperature of 80 to 95°C, preferably 40 to 70°C. In the cold pad patch dyeing method, the dye is padded using a known inorganic neutral salt such as anhydrous sodium sulfate or common salt, and a known acid binder such as caustic soda or sodium silicate, and then left in a sealed packaging material at a constant temperature. A method of staining is exemplified. Continuous dyeing methods include a one-bath padding method in which a known acid binder such as soda carbonate or bicarbonate is mixed with a dye padding solution, and after padding in a known method, dyeing is carried out by dry heat or steam heat; Examples include a two-bath padding method in which Hang is applied using a known inorganic neutral salt such as salt or common salt, and a known acid binder such as caustic soda or sodium silicate, and then dyed by dry heat or steam heat using a known method. . Printing method Example 1 (a) In the form of a free acid, the formula (1) is poured into a high temperature solution of 90°C or higher containing an inorganic neutral salt such as common salt and a known acid binder such as caustic soda or sodium borate. An example is a two-phase textile printing method.

Since the dye composition of the present invention exhibits extremely excellent solubility in various aqueous alkaline solutions, it is possible to obtain uniform and deep dyed products without spots even when dyed by the -bath padding method. Further, even in -phase printing, a thick and stable printing paste can be produced, and uniform printed products can be obtained. Furthermore, a uniform and deep dyed product without spots can also be obtained by dyeing by the cold pad patch dyeing method. or,
Dyeing by the exhaust dyeing method also makes it possible to obtain a uniform and deep dyed product without spots.

EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples. In the text,
Parts and % represent parts by weight and % by weight, respectively.

A condensate (sodium salt) of dimethylnaphthalene sulfonic acid and formaldehyde having a degree of sulfonation of 110% and an average degree of condensation of 1.8 and 1 part of mineral oil emulsion were added to 60 parts of the dye represented by and thoroughly mixed.

(b) Cellulose [850% and polyester fiber 5
One part of the mixed fabric consisting of 0% was set in a high-pressure circuit dyeing machine, the bath ratio was 1:8, the water temperature was 80° C., and the pH was adjusted to 5 using acetic acid.

1 in 40 minutes using a dispersion containing 0.2 parts of the disperse dye of formula (2) that had been sufficiently dispersed in advance.
The temperature was raised to 80°C and the polyester side was dyed for 40 minutes.

(/i, (-()) Dye composition obtained in section 0.8
2 was dissolved in boiling water, water was added thereto, and 200% of the solution was dissolved.

1 of anhydrous Glauber's salt was added to this dye solution, 10 f of the dyed product obtained in the section (-) was immersed, and the temperature was raised to 60°C while stirring. After raising the temperature, the fabric was treated at this temperature for 20 minutes,
Then 4v of soda ash was added and dyeing was carried out at this temperature for 60 minutes.

The fabric was then washed and dried in the usual manner.

The cotton-polyester blend fabric was uniform and dark blue in color.

Example 2 70 parts of a dye represented by the formula (8) in the form of a free acid were added with a sulfonation degree of 100% and 10
19 parts of a condensate of monomethylnaphthalenesulfonic acid and formaldehyde (sodium salt) and 1 part of mineral oil emulsion were added and thoroughly mixed.

Using the obtained dye composition, a printing paste having the following formulation was prepared.

Dye composition 80 parts Urea 50 parts Sodium alginate 550 parts Boiling water
800 parts bicarbonate of soda 20 parts After printing the obtained printing paste on cotton boblin in the usual manner,
Steaming treatment was performed at 100°C for 5 minutes. Then, I washed it with water, hot water, soaped it, washed it with hot water, washed it with water, and dried it.

The cotton boblin was uniform and extremely dark blue in color.

Example 8 0.8F of the obtained dye composition of formula (4) in the form of free acid was dissolved in boiling water, and water was added thereto to make 2001 nl. 10f in this dye solution
of anhydrous sodium sulfate was added, 10 f of unmercerized cotton knit was immersed, and the temperature was raised to 60C without stirring. After raising the temperature, the cotton knit was treated at this temperature for 20 minutes, then 42 soda ash was added and dyeing was carried out at this temperature for 60 minutes.

The cotton knit was then washed and dried in a conventional manner. The unmercerized cotton knit was a uniform and deep bright brown color.

Example 4 To 65 parts of a dye represented by formula (5) in the form of a free acid, 20 parts of a condensate (sodium salt) of methylnaphthalenesulfonic acid and formaldehyde having a degree of sulfonation of 110% and an average degree of condensation of 1.8, 14 parts of a condensate of ethylnaphthalene sulfonic acid and formaldehyde (sodium salt) and 1 part of a mineral oil emulsion were added and thoroughly mixed.

To 60 parts of the dye represented by, 14 parts of a condensate (sodium salt) of dimethylnaphthalenesulfonic acid and formaldehyde with a degree of sulfonation of 11o% and an average degree of condensation i, s, and a condensate (sodium salt) of monomethylnaphthalenesulfonic acid and formaldehyde. 15 parts of salt), 10 parts of sodium sulfate, and 1 part of mineral oil emulsion were added and thoroughly mixed.

The obtained dye composition 100F was dissolved in hot water and cooled to 26°C. Immediately after adding 82.5% caustic soda aqueous solution 15 - and 50 degrees Baume water glass 150 f and further adding water to bring the total volume to 11 at 25°C, this liquid was used as a padding liquid to pad cotton fabric. did. The padded cotton fabric is rolled up, sealed with polyethylene film, and left in a room at 20°C for 20 hours.
It was then washed in hot water, soaped in boiling detergent, washed in cold water and dried. This gave a very deep dark blue, spot-free dyeing.

Example 5 To 75 parts of the dye represented by the formula (6) in the form of a free acid, 6.5 parts of a condensate (sodium salt) of dimethylnaphthalene sulfonic acid and formaldehyde having a degree of sulfonation of 110% and an average degree of condensation of 1.8 was added. 1 part, 17.5 parts of a condensate of naphthalene sulfonic acid and formaldehyde (sodium salt), and 1 part of mineral oil emulsion were added and thoroughly mixed.

The resulting dye composition 80F was dissolved in hot water and cooled to 25°C. Immediately after adding sodium alginate IF, 1 or of sodium metanitrobenzenesulfonate, and 20 f of sodium bicarbonate, and further adding water to make the total amount into IJ at 25°C, this liquid was used as a padding liquid to pad cotton fabric. The padded cotton fabric was dried at 120°C for 2 minutes and then steamed at 100°C for 5 minutes to fix the dye. The dyeings obtained were finished by washing with cold water, then hot water, soaping in boiling detergent, washing with cold water and drying. This gave a very deep, sharp, spotless brown dyeing.

Examples 6 to 20 Example 1 was prepared using each of the reactive dye compositions shown in Table 1.
Dyeing and printing were performed according to each method described in 5 to 5. All of the reactive dye compositions shown in Table 1 had good solubility, and it was possible to obtain industrially useful uniform, spotless, and sufficiently deep dyed and printed products.

(Margin below) (37 completed)

Claims (6)

[Claims] (1) The following general formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, A_1 and A_2 are phenylene or naphthylene groups that may independently have substituents, R_1 and R_2 are independently hydrogen or lower alkyl which may have a substituent;
independently represent hydrogen, an alkyl group which may have a substituent, a phenyl group or a naphthyl group. ) and B
Either one of _1 and B_2 is a phenylene group optionally substituted with one or two substituents selected from the group of methyl, ethyl, methoxy, ethoxy, chloro, bromo, nitro, carboxy, and sulfo, and the other represents a naphthylene group which may be substituted with sulfo. Z_1
and Z_2 are each independently vinyl or -CH_2CH_
2L (in the formula, L represents a group that is eliminated by the action of an alkali). A reactive dye composition comprising a dye represented by the following formula and a condensate of at least one alkylnaphthalene sulfonic acid and formaldehyde. (2) The composition according to claim 1, wherein the weight composition ratio of the dye represented by general formula (I) and the condensate of alkylnaphthalene sulfonic acid and formaldehyde is 0.25:1 to 9:1. (3) C_ with 1 to 3 alkylnaphthalene sulfonic acids
Claim 1 or Claim 2 having a 1 to C_4 alkyl group
The composition described in . (4) The composition according to any one of claims 1 to 3, wherein the degree of sulfonation of the alkylnaphthalene sulfonic acid is 50 to 150%. (5) Claim 1, wherein the average degree of condensation of the condensate of alkylnaphthalene sulfonic acid and formaldehyde is 1.1 to 3.
5. The composition according to any one of 4 to 4. (6) A method for dyeing or printing a cellulose fiber material or a fiber material containing cellulose fiber, which comprises using the reactive dye composition according to claim 1.