JPH04108867A - 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 an alkylnaphthalene sulfonic acid with formaldehyde, and capable of uniformly dyeing a cellulosic fiber into dark color by one bath padding method. CONSTITUTION:The objective composition containing (A) a dye expressed by formula I {A is (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 by condensing an alkylnaphthalene sulfonic acid with formaldehyde, preferably at a weight ratio of 0.25:1 to 9:1.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention is suitable for dyeing textile materials, particularly cellulosic textile materials or textile materials containing seven rho loin fibers, and is extremely resistant to water and aqueous alkaline solutions. Relating to soluble reactive dye compositions.

<Prior art> Buzzing liquid or - such as the one-bath bagging winding method, the bath bagging drying method, and the bath bagging steaming method, which are effective for dyeing natural and regenerated 7μ loin fibers using reactive dyes. The preparation of printing pastes for phase printing requires that the dyes used have sufficient solubility in aqueous alkaline solutions. For example, dyeing by the -bath bagging method involves using a dye bath in which up to about 100 M parts of the dyestuff is dissolved in 1000 parts by weight of an aqueous solution consisting of caustic soda, soda carbonate, or tertiary phosphoric acid and an electrolyte. It is carried out using

Furthermore, when exhaust dyeing cellulose fibers, dyes having sufficient solubility in a solution containing a large amount of electrolyte and alkali are used.

<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> The present inventors have completed the present invention as a result of intensive studies on dye compositions that can satisfy the high market needs for these reactive dyes.

That is, the present invention provides a compound of the general formula (1) [wherein A is a phenylene or naphthylene group that may have a substituent, and R1 and R2 are independently hydrogen or a lower lower group that may have a substituent] Furkyl group, X is -N-
Rs or 10R6 (wherein Re, R4 and Rs are independently hydrogen, alkyl μ which may have a substituent,
Represents a phenyl or naphthyl group. ), either one of Bl and R8 is methiμ, methiμ, methoxy, ethoxy, chloro, bromo, nitro, forceμpokin and nuμ
One is a phenylene group which may be multi-substituted with one or two substituents selected from the group (2), and the other is a naphthylene group which may be substituted with (2). zl and z2
are independently vinyl or -〇HxCHsL (in the formula,
L represents a group that is eliminated by the action of an alkali. ).

] and at least one kind of Al: 11-μ
A reactive dye composition containing a condensate of naphthalene Zμ with toformaldehyde, and a method for dyeing or printing a cellulose fiber material or a fiber material containing cellulose fibers, characterized by using the same.

In the dye composition of the present invention, the weight ratio of the dye represented by the general formula (1) and the condensate of at least one μkylnaftacine sulfonic acid and hopmuanol/dehyde is 0.
A degree of 25:1 to 9:1 is preferable, more preferably 3:1.
The ratio is 2 to 8:2.

In the present invention, examples of the group represented by A include the following general formulas (II) and (ffl).

(II) (II) (where m is 1 or 2, n is 0 or 1, L is 0 or 1, R6 is hydrogen, methoxy, nidoxy, sulfo, methoxy/l/or ethyl, R7 is hydrogen, methoxy , ethoxy, methiρ, methiμ, acetylamino, propioniμamino, or ureido.The bond shown with an asterisk means a bond with the general formula %.) Specific examples of the group represented by A (In the formula, the bond indicated with an asterisk is an asterisk in the general formula (I).
-018-Bl -N=N-K ifa means the same tail bond. ) etc. are exemplified.

In the present invention, the lower alkoxy group represented by R1 and R2 is an alkoxy group having 1 to 4 carbon atoms.
A hydroquine group, a cyano group, an alkoxy group, a halogen, a carboxy group, a carbamoyl group, an apkoxycarbonyl group, an argyl group, a sulfonyloxy group, a sulfo group, a sulfamoyl group, and an optionally substituted group are preferably Groups are preferred.

R1 and R2 are each independently, for example, a hydrogen atom, a methyl group, an ethyl group, an n-propy group, 1so-propy/L'i, a n-butyl group, an iso-butyl group, 5e
C-methyl group, 2-hydroxyethyl group, 2-hydroxypropyρ group, 8-hydroxypropy/l' group, 2-hydroxybutyμ group, 8-hydroxybutyμ group, 4-hydroxyVbutyl group, 2, 8-dihydroxypropyl group, 8
゜4-Dihydroquimbunaμ group, cyanomethyμ group, 2-cyanomethyl group, 8-cyanopropyμ group, methoxymethyl group, methoxymethyl group, 2-methoxye, thi〃 group, 2-
Methoxymethyl group, 8-methoxypropyl group, 8-methoxypropyl group, 2-hydroxy-8-methoxypropyl group, chloromethy/L' group, bromomethyl group, 2-chloromethy/L4.2-promoethyl μ group, 8-chloropropyl group group, 8-bromoproyl group, 4-chlorobutyμ group, 4
-Glomoptyl group, μboxymethyl group, 2-μpoxyethyl/L/ group, 8-carboxypropyμ group, 4-μ
Boxypty p group, 1゜2-cicap poxyethyl p group, carbamoylmethy/L' group, 2-carpamoyμethyl aLs
- p Bamoylpropyμ group, 4-capamoyμbutyμ group, methoxycarbonyμmethy group, ethoxycarbonylmethyl group, 2-methoxycarbonyμethy~ group, 2-ethoxycarbonyμethyl& , 8-' toxycarbonylpropyp group, 8-ethoxycarbonylpropy group, 4-methoxycarbo=μbutyρ group, 4-ethoxycarbonybutyμ group, methyl force! Pony μ Oki V Methi μ group, Echi μ Ka μ
Bonyμoxymethyp group, 2-methylcarbonyloxymethyl group, 2-ethylcarbonyloxyethyl group, 3-ethylcarbonyloxyprobyl group, 4-methy/Vcarbonialeoxybuty/L' group, 4 -ethyμcarponyμoxybutyμ group, sulfomethiμ group, 2-sulfomethy/l/group, 8-sulfopropyμ group, 4-sulfobutyμ group, sulfamoylmethyl group, 2-sulfamoylethyl group, 8-sulfopropyl group, Famoylpropyl μ group and 4-su! A hydrogen atom, a methyl group, and an ethyl group are particularly preferred.

In the present invention, the groups represented by B1 and B2 are:
For example, (in the formula, the nine bonds indicated by 1 are S in the general formula (1)
ong means an open bond. ), etc. B1 and B! One of them is phenylene and the other is naphthylene.

Examples of the group that is eliminated by the action of 1 μ potassium, which is represented by L in m, include a sulfate sulfate μ group, a thiosulfate group, a phosphoric acid ester group, an acetic acid ester group, and a halogen atom. Particularly preferred is NT sulfate group.

In general formula (1), when X is 10Rs and R6 is an alkyl group which may have a substituent, such X is an alkoxy group having 1 to 4 carbon atoms. Preferably, for example, methoxy group, ethoxy group, n-propoxy group, 180-propoxy group, 11-butoxy group,
Examples include β-methoxyethoxy group and 1so-butoxy group. Particularly preferred among these are methoxy and ethoxy groups.

On the other hand, when X is a phenyl/I/l or naphthyl group which may have a substituent, for example, X has 1 to 4 carbon atoms. phenoxy, which may be di-substituted with one or two substituents selected from the group consisting of an alkoxy group having 1 to 4 carbon atoms, a nitro group, a sulfo group, a carboxy group, and a chlorine atom; Naphthoxy group is preferred. Particularly preferred among these are 2-18- or 4-chlorophenoxy groups and 2-18- or 4-methoxyphenoxy groups.

In general formula (1), when X is -N-Rs, the a[mu]kyl group which may have substituents represented by R8 and R4 has, for example, 1 to 4 carbon atoms. A 7μ key having 1 to 4 carbon atoms optionally substituted with 1 or 2 threshold substituents selected from the group of alkoxy groups, sulfo groups, carboxy groups, hydroxy groups, chlorine atoms, phenyl groups, and sulfate groups. Groups are preferred.

Among these, particularly preferred are methy μ group, ethyl/l/ group, n-
propyl group, 1so-propyl group, n-but'tiv&,
Examples include 1so-butyμ group, 5ec-butyμ group, β-hydroxyethyl group, β-sulfatoethyl μ group, β-sulfateμ group, β-methoxyethyl/L/i and β-carboxyethyl group. It will be done.

Further, as the phenyl/I/M which may have a substituent represented by R8 and R4, for example, a 7pkiμ group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, Preferred is a phenyl group which may be di-substituted with one or two substituents selected from the group consisting of a phenyl group, a p-boxy group, and a chlorine atom. Particularly preferred among these are phenyl group, 2-8- or 4-sulfophenyl group, 2-8- or 4-chlorophenyl group, 2-8- or 4-methyphenyl group, 2-18- or 4- Examples include methoxyphenyl group.

Further, the naphthyl group which may have a substituent represented by R8 and R4 is, for example, a hydroxy group, a μboxy group, a sulfo group, an alkyl group having 1 to 4 carbon atoms, a 1 to 4 carbon atom Preferred is a group which may be polysubstituted with 1, 2 or 8 substituents selected from the group consisting of an alkoxy group having carbon atoms and a chlorine atom. Among them, 2-8-14-5-6-17- or 8-
μ group, 1-15-6-17- or 8
-Sulfonaphthyl group, 5.7- 6.8-14.8-1
4,7.8.8-14,6-18,7- or 3,6-disp-2-naphflV group, 4,6.8-2.4.7-
or 8,6.8-1 linulfo-1-naphthyl group, 1,5
．． 7-14, 6.8- or 8, 6.8-) Lis μ Ho 2
- Nafti μ group, etc. Particularly preferred is 6-sho-1-naphthyl group.

The dye of general formula (1) can be prepared by a known method, for example,
It can be produced by the method described in Japanese Patent No. 252671. - For example, it can be produced as follows.

General formula (■) Zl-02S -Bl -NH2(IV) (in the formula, z
l and B1 have the meanings given above. ) is diazotized by a conventional method, and this is converted into a compound represented by the general formula (V) H-A-N-H(V) (wherein A and R1 have the above meanings). Coupling gives the monoazo compound.

The monoazo compound obtained here, general formula 1)% formula%) (wherein R$l, B2 and Zg have the above meanings.

) and the compound represented by the general formula (■) -X (■) (wherein, ) 2,
4.6-Dolyhalogeno is condensed with 1.8.5-triazine in any order. The condensation is carried out in an aqueous medium, firstly at -10-50°C with adjustment to pH 1-10, secondly at 0-70°C with adjustment to pH 2-9, and tertiary. Each reaction is carried out at a temperature of 50 to 100°C while adjusting the pH to 2 to 9. In this way, a dye represented by general formula (1) can be obtained.

The condensate of at least one alky-μ napdacine sulfonic acid and home μ-am μdehyde contained in the composition of the present invention can be produced by a known method.

Among these are μ-kylnaphthacine sulfonic acid, mono- or dimethyl-naphthacine-sulfonic acid, mono- or diethylnaphthalene-sulfuric acid, mono- or dibutyl-naphthacine sulfonic acid, and mono- or dipropylnaphthalene sulfonic acid. At least one kind selected from among them is used, but preferably a mixture of two or more maples is used.

Alkylnaphthalene! Average degree of sulfonation of fonic acid (100% degree of sulfonation for those with 1 moμ substitution of alkylnaphthalene acid groups)
Tosuru. ) is preferably about 50 to 150 Ls-1), more preferably 80 to 120%.

The condensate of γμ naphthalesin sulnic acid and hopamμ dehyde can be used in the form of an alkali metal block, and the average degree of condensation is preferably about 1.1 to 8, and more preferably , 1.5 to 2.5.

The dye composition of the present invention may contain a hydrotrope such as urea or anthofquinone-2-sulfonic acid, or/and dextrin or sucrose. In addition, chlorination is carried out within a small amount that does not adversely affect the solubility of the dye composition.)
Addition of electrolytes such as rum and anhydrous sodium sulfate, anti-scattering agents such as mineral oil emulsion, and pH adjustment of sodium phosphate, IJum, etc.
Stabilizers and water softeners such as polyphosphates may be added.

The dye composition of the present invention can be dyed by various dyeing methods, such as cotton and other vegetable fibers, such as natural cellulose fibers such as linen, hemp, pseudo and ramie fibers, and also regenerated cellulose fibers, such as viscose 1 stable. Filament viscose or blends thereof with other fibers such as polyester can be effectively dyed.

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. using an acid binder, 80-95°C,
Preferably, a method of dyeing at a temperature of 40 to 80°C is exemplified. In the cold pad batch dyeing method, after padding using known inorganic neutral salts such as anhydrous mirabilite and common salt, and known acid binders such as caustic soda and sodium silicate, the dye is left in a sealed packaging material at a constant temperature. A method of staining is exemplified. In the continuous dyeing method, a known acid binder such as sodium hypoacid or sodium bicarbonate is mixed with a dye padding solution, and after padding by a known method, dyeing is carried out by dry heat or steam heat. , a two-bath buzzing method in which known inorganic neutral salts such as anhydrous sodium sulfate and common salt, and known acid binders such as caustic soda and sodium silicate are padded and dyed by dry heat or steam heat using a known method. etc. are exemplified. In the printing method, there is a one-phase printing method in which a printing paste containing a known acid binder such as sodium bicarbonate is printed and then printed using dry heat or steam heat, and a printing method in which a printing paste is printed using an inorganic neutral salt such as common salt after printing. and 90 containing known acid binders such as caustic soda and sodium silicate.
Examples include a two-phase printing method in which printing is carried out by placing the material in a high-temperature solution at a temperature of .degree. C. or higher.

Since the dye composition of the present invention exhibits extremely excellent solubility in various aqueous alkalis, it is possible to obtain a uniform and deep dyed product without spots even when dyed by the -bath buzzing method. Further, even in -phase printing, a thick and stable printing paste can be produced, and a uniform printed product 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. In addition, by dyeing using the exhaust dyeing method, it is possible to obtain a uniform and deep dyed product without spots.

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.

Example 1 Formula (1) 150F is added in the form of free acid, water is further added and the total amount is reduced to M at 25°C.
Immediately after the liquid was made into a liquid, cotton fabric was padded using this liquid as a padding liquid. Roll up the padded cotton fabric, seal it with polyethylene film, and store it in a room at 20℃ for 20 minutes.
After standing for a period of time, the dyed product was washed with cold water, then hot water, soaped in a boiling detergent, washed with cold water and finished by drying. This gave a very deep bright red spotless dyeing.

Example 2 65 parts of a dye represented by the formula (2) in the form of a free acid was mixed with a condensate (sodium salt) of methylnaphthalene sulfonic acid and homamine dehyde having a degree of sulfonation of 110% and an average degree of condensation of 1.5. ) and 1 part of mineral oil emulsilon were added and thoroughly mixed.

The obtained dye composition 100f was dissolved in hot water and cooled to 25°C. To this, 111 parts of an 82.5% aqueous solution of caustic soda and 60 parts of a dye shown in 60° Baume water glass were added with 7 parts of dimethyl chloride having a degree of sulfonation of 110% and an average degree of condensation of 1.8.
Add 20 m of a condensate of V-sulfonic acid and formaldehyde (sodium salt), 19 parts of a condensate of monomethylnaphthalene sulfonic acid and formaldehyde (sodium salt), and 1 part of mineral oil Emma μ Schiff, and mix thoroughly. did.

0.8 t of the obtained dye composition was dissolved in hot water, and water was added to make 200 m. 10 liters of anhydrous sodium sulfate was added to this dye solution, and a 109-grade V)v keratocotton knit was immersed therein, and the temperature was raised to 60° C. while stirring. After raising the temperature, the cotton knit was treated at this temperature for 20 minutes, then 4 f of 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 orange color.

Example 8 To 75 parts of the dye represented by the formula (8) in the form of a free acid, a condensate of dimethylnaphthalene sulfonic acid and formaldehyde (Natriwam 4) having a degree of sulfonation of 110% and an average degree of condensation of 1.86. 5 parts, condensate of naphthalene sulfonic acid toformaldehyde
7.5 parts of IJ Am), 10 parts of sodium sulfate and 1 part of mineral oil emulsion were added and thoroughly mixed.

The resulting dye composition 802 was dissolved in hot water and cooled to 25°C. Immediately after adding 10% of alginic acid, 10% of mep nitrobenzenesulfonic acid sorter, and 209% of sodium bicarbonate, and adding water to bring the total amount to IL at 25°C, this solution was used as a bagging liquid to bag cotton fabric. . The badged cotton fabric was dried at 120°C for 2 minutes and then steamed at 100°C for 5 minutes to fix the dye. Wash the resulting dyed product with cold water, then hot water,
I washed it in boiling detergent, washed it with cold water, and finished it by drying it. This gave a very deep, sharp, spotless red dyeing.

Example 4 To 65 parts of the dye represented by the formula (4) in the form of free acid, 100% of S/l/degree of fonation,
Condensate (sodium salt) of diethyl, TL/naftacine sulfonic acid with a small pmua/l/dehyde with an average degree of condensation of 2.5
10m, 24 parts of a condensate (sodium salt) of monoethyl p-naphthacine sulfonic acid and formaldehyde, 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 aginate 550 parts Boiling water 800 parts Total 1000 parts After printing the obtained printing paste on cotton boblin in the usual manner,
Nuteaming treatment was performed at 100°C for 5 minutes. Then, I finished it by washing with water, washing with hot water, nooping, washing with hot water, washing with water, and drying.

The cotton boblin was uniform and very dark yellow in color.

Example 5 (a) A condensate of dimethylnaphthalene sulfonic acid and formaldehyde (sodium salt) having a degree of sulfonation of 110% and an average degree of condensation of 1.8 was added to 60 parts of the dye represented by formula (5) in the form of a free acid. ), 19 parts of a condensate (sodium salt) of monomethylnaphthalene sulphonic acid and huma-dehyde, and 1 part of mineral oil Emma 7 Resin B were added and thoroughly mixed.

(B), C/L/50% loin fiber and polyester/L
/ 10 parts of a mixed fabric consisting of 5096 fibers was set in a high-pressure circular dyeing machine, bath ratio l: 8, water temperature 80°C.
and the pH was adjusted to 5 using acetic acid.

Using a dispersion containing 0.2 part of a disperse dye of type 9 (6) which had been sufficiently dispersed in advance, the temperature was raised to 180° C. in 40 minutes, and the polyester side was dyed in 40 minutes.

0.81 of the dye composition obtained in sections (c) and (a) was dissolved in hot water, and water was added to make 200 d. Anhydrous sodium sulfate (109) was added to this dye solution, and the dyed product lOf obtained in section (b) was immersed therein, and the temperature was raised to 60° C. while stirring. After raising the temperature, treat the knitted fabric at this temperature for 20 minutes,
42 soda ash was then added and dyeing was carried out at this temperature for 60 minutes.

The knitted fabric was then washed in a conventional manner 2 and dried to finish. cotton-
The polyester blended fabric had a uniform, deep, bright red color.

Examples 6 to 26 Dyeing and printing were performed using the reactive dye compositions shown in Table 1 according to the methods described in Examples 1 to 5, respectively.

The solubility of all the reactive dye compositions shown in Table 1 is good, and it is possible to obtain industrially useful uniform and spotless dyed and printed products with sufficient density. )

Claims (6)

[Claims] (1) The following general formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, A is a phenylene or naphthylene group that may have a substituent, and R_1 and R_2 are independently hydrogen. or a lower alkyl group which may have a substituent; ), and either B_1 or B_2 is methyl, ethyl, methoxy, ethoxy, chloro,
One is a phenylene group which may be substituted with one or two substituents selected from the group of bromo, nitro, carboxy and sulfo, and the other is a naphthylene group which may be substituted with sulfo. Z_1 and _Z2 each independently represent 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 claim 1, claim 2, or claim 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.
, a composition according to claim 2, claim 3 or claim 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.