JPS60173062A - Disazo compound and dyeing or printing method using the same - Google Patents

Abstract

NEW MATERIAL:Compounds of formula I , wherein X, X' are each halogen; Y, Y' are each H, sulfo, a group of formula II or III (wherein Z is a group which can be removed by the action of an alkali), etc.; A, A' are each (substd.) phenylene, naphthylene; R1, R2 R'1 R'2 are each H, (substd.) lower alkyl; B, B' are each phenylene which may be substituted with lower alkyl, lower alkoxy, ureido, etc. EXAMPLE:Disazo dye of formula IV. USE:Disazo dyes which dye or print cellulose fiber materials, fibrous polyamides and polyurethanes yellow. PREPARATION:4-Amino-4'-nitrostilbene-2,2'-disulfonic acid is diazotized and then coupled with an aniline derivative. The resulting monoazo compd. of formula Vand a compd. of formula VI are condensed with a trihalogenotriazine in any order. The condensate is reduced with sodium sulfide, diazotized and coupled with an aniline derivative to obtain the disazo compd. of formula VII.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a disazo compound and a method for dyeing or printing using the same.

Reactive dyes having 100 fiber-reactive groups in the molecular structure of the dye are known, but they are insufficient in exhaustion and fixing properties in terms of dyeing performance.

In this regard, the present inventors have made extensive studies and have found that a novel disazo compound can solve the above problems, and have completed the present invention.

That is, the present invention provides the following general formula (1) [wherein X and X each independently represent a halogen atom,
Y and Y are each independently a hydrogen atom, a sulfo group, -8
0zCH=CIi2゜-802(J-IzC■■20H
-8OzCHzCLI2SH-8O2CH2CH2z1
The group that is eliminated by the Z haal force reno action (however, Y,
At least one of Y is -8OzCH-○Rz or -80zCk12c112Z. ), A and A
' represents a phenylene group or a naphthylene group which may have a substituent; Rt, R2, Rt and R2 each independently represent a hydrogen atom or a lower alkyl group which may be substituted.

B and B each independently represent a phenylene group optionally substituted with a lower alkyl group, a lower alkoxy group, a lower alkylcarbonylamino group or a ureido group. The present invention provides a disazo compound or a salt thereof, and a method for dyeing or printing a fiber material using the disazo compound or a salt thereof.

In the general formula (1), examples of the halogen atoms represented by X and X include chlorine, bromine, and fluorine, with chlorine or fluorine being preferred.

Examples of the group represented by 2 which is eliminated by the action of an alkali include a sulfate ester group, a thiosulfate ester group, a phosphate ester group, an acetic acid ester group, and a halogen atom.

A and X are preferably a phenylene group or a sulfo group optionally substituted with one or two substituents selected from the group of methyl group, ethyl group, methoxy group, ethoxy group, chlorine, bromine, and sulfo group. (optionally substituted with one) naphthylene group, for example, most.

1 means a bond that leads to a -N- group. )lt+Jt
In +, 12 and R2, the lower alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, and the optionally substituted group is a hydroxy group,
Cyano group, alkoxy group, halogen group, carboxy group,
A carbamoyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a sulfo group, and a sulfamoyl group are preferred.

Particularly preferred assistant, 几2. Examples of 1 and 2 include hydrogen, methyl group, ethyl group, n-propyl group, 1
so-propyl group, n-butyl group, 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, 3-cyanopropyl group, methoxymethyl group, ethoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 3-methoxypropyl group, 8-ethoxypropyl group 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, 8-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, methylcarbonyloxymethyl group, ethylcarbonyloxymethyl group, 2-methylcarbonyloxyethyl group, 2-ethylcarbonyloxyethyl group, 3- Methylcarbonyloxypropyl group, 8-ethylcarbonyloxypropyl group,
4-methylcarbonyloxybutyl group, 4-ethylcarbonyloxybutyl group, sulfomethyl group, 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group,
Examples include a sulf 7-moylmethyl group, a 2-sulfamoylethyl group, a 3-sulf 1-moylpropyl group, and a 4-sulf 1-moylbutyl group.

The optionally substituted phenylene group represented by B and B' is preferably a phenylene group bonded at the 1.4-position.

The compounds of the invention are present in the form of the free acid or in the form of its salts, in particular the alkali metal and alkaline earth metal salts, especially the soda, potassium and calcium salts.

The compound of the present invention can be produced, for example, in the following manner.

4-amino-4-nitro-stilbene-2,2-disulfonic acid or a salt thereof of the formula T'' (III) in an aqueous medium, B-NR2-(III+ (wherein B and R2 have the above meaning ) or a salt thereof to obtain a monoazo compound of the following general formula (IV) or a salt thereof.

■ (In the formula, B and R2 have the above meanings.) Next, (■
) or a salt thereof, and the following general formula (V) iIN -A -Y (V) (wherein R+, A and Y have the above-mentioned meanings.

) in an aqueous medium in any order, secondly at a temperature of -10°C to 40°C to pH 2 to pH 9, and secondarily at a temperature of 0°C to 70°C.
The compound is condensed with a trihalogenotriazine represented by the following general formula (Vl) (wherein, X has the above-mentioned meaning) while adjusting the pH to 9 to 9 to obtain a compound of the following general formula (■) or a salt thereof.

(In the formula, what are the meanings of A, B, X, Y, R+ and 2 above?) This compound was reduced with sodium sulfide in an aqueous medium and further diazotized by a conventional method to form the following general formula. Coupling with the aniline derivative represented by (■) or a salt thereof (wherein B and 2 have the above-mentioned meanings), the following general formula (■) (in the formula, A
, B, B, X, Y, R+, R2
and 蹉 have the meanings given above. ) Obtain a compound or its salt.

Furthermore, a compound represented by the formula (■) or a salt thereof, and the following general formula (X) 几I.

11iN-A-Y (X) (wherein 几', 1. A' and Y have the meanings given above) in an aqueous medium in any order at a temperature of While adjusting I) H2 to 9 at a temperature of 0°C to 40°C, and secondarily adjusting pH 2 to pH 9 at a temperature of 0°C to 70°C, - the following general formula (X[) X' (in the formula, or By condensation with a trihalogenotriazine having the above-mentioned meaning, a compound of the general formula (R) or a salt thereof can be obtained.

Also, A, X, Y and loss are each A.

When X, Y' and R+ are the same, it can also be produced as follows.

That is, the compound of the general formula QvI or a salt thereof is acylated, the acylated product is reduced with sodium sulfide by a conventional method, and further diazotized by a conventional method, and the compound of the general formula (■) or a salt thereof is combined with the compound of the general formula (■) or a salt thereof. After ringing, it is hydrolyzed at a temperature of 50°C to 100°C in the presence of an acid or an alkali to form the following general formula (Xl). ) or a salt thereof is obtained.

Next, a compound represented by formula (Xl[) or a salt thereof and a compound of general formula (V) (same as the compound of general formula (X)) or a salt thereof are added in an arbitrary order to an aqueous medium. Temperature -
While adjusting the pH to pH 2 to pH 9 at a temperature of 10°C to 40°C, and secondarily adjusting the pH to 2 to pL (9) at a temperature of θ°C to 70°C, The compound of general formula (1) or a salt thereof can be obtained by condensation with the compound (same as the compound).

Furthermore, when A, B, X, Y, 1 and R2 are, it can also be produced as follows.

That is, 4,4-diamino-stilbene 2,2-disulfonic acid or its salt of the following formula (Xlll) is tetrazotized by a conventional method in an aqueous medium to form a compound of the general formula (nl) (general formula (■)). (same as the compound) or a salt thereof to obtain a compound of general formula (XI) or a salt thereof.

Hereinafter, the above-mentioned A, X, Y and R1 are each A'.

The compound of general formula (1) or its salt can be obtained by the process.

The compound of the present invention has fiber reactivity and can be used for dyeing or printing hydroxy group-containing or carbonamide group-containing materials. Preferably, the material is used in the form of a fibrous material or a blend thereof.

Hydroxy group-containing materials are natural or synthetic hydroxy group-containing materials, such as cellulose fiber materials or their regenerated products and polyvinyl alcohol. The cellulosic fiber material is preferably cotton, but also other vegetable fibers such as linen, hemp, jute and ramie fibers. Regenerated cellulose fibers are, for example, viscose staple and filament viscose.

Materials containing carbonamide groups are, for example, synthetic and natural polyamides and polyurethanes, especially in the form of fibers, such as wool and other animal hairs, silk, leather, polyamide-6,
6, polyamide-6, polyamide-11 and polyamide-4.

The compounds of the present invention can be dyed or printed on the above-mentioned materials, in particular on the above-mentioned fiber materials, in a manner depending on their physical and chemical properties.

For example, in the case of exhaust dyeing on cellulose fibers, the presence of an acid binder such as soda carbonate, sodium phosphate or caustic soda, optionally the addition of a neutral salt such as mirabilite or common salt, and, if desired, a solubilizing agent. , use a penetrant or leveling agent together,
It is carried out at relatively low temperatures. The neutral salts which accelerate the exhaustion of the dye can be added only after or before the actual dyeing temperature has been selected, optionally in portions.

When dyeing cellulose fibers according to the padding method, it can be padded at room temperature or at an elevated temperature and, after drying, fixed by steaming or dry heat.

When printing is carried out on cellulose fibers, either in one phase, e.g. by printing with a printing paste containing baking soda or other acid binders and then steaming at 100-160°C, or in two phases, e.g. This can be carried out by printing with a neutral or weakly acidic printing paste, passing it through a hot electrolyte-containing alkaline ectotherm, or by overpadding with an extra-alkaline electrolyte-containing pazinder solution and steaming or dry heat treatment.

Thickening agents or emulsifiers, such as, for example, sodium alginate or starch ethers, are used in the printing pastes, if desired in combination with customary printing auxiliaries and/or dispersants, such as, for example, urea.

Suitable acid binders for fixing the compounds of the invention on cellulose fibers are, for example, water-soluble basic salts of alkali metals or alkaline earth metals with inorganic or organic acids or compounds which liberate alkali under heated conditions. Particular mention may be made of alkali metal hydroxides and alkali metal salts of weak to medium strength inorganic or organic acids, of which soda salts and potassium salts are particularly preferred. Such acid binders include, for example, caustic soda, caustic potash, baking soda, soda carbonate, sodium formate, potassium carbonate, dibasic, dibasic or tertiary sodium phosphate, silica (
ly-da, sodium trichloroacetate, and the like.

The dyeing of synthetic and natural polyamide and polyurethane fibers is carried out first by exhaustion under control of the PA value from an acidic or slightly acidic dye bath, and then by changing to a neutral or even alkaline pH value for fixation. It can be done by Dyeing is usually carried out at a temperature of 60 to 120°C, but in order to achieve level dyeing properties, conventional leveling agents such as a condensation product of cyanuric chloride and 3 times the mole of amine benzenesulfonic acid or aminonaphthalenesulfonic acid or For example, an addition product of stearylamine and ethylene oxide can also be used.

The compound of the present invention is characterized in that it exhibits excellent performance in dyeing and printing textile materials. Especially suitable for dyeing cellulose fiber materials, good light fastness and sweat resistance, good moisture resistance, such as washing resistance, peroxidation washing resistance, chlorine water resistance, chlorine bleaching resistance, sweat resistance , has acid hydrolysis resistance and alkali resistance, as well as good abrasion resistance and ironing resistance. In addition, it has excellent build-up properties, level dyeing properties, and wash-off properties, as well as good solubility and high exhaustion and fixation properties, making it possible to produce dyed products of stable quality that are less affected by fluctuations in dyeing temperature and dye bath ratio. It is characterized by the fact that it is

Next, the present invention will be explained in more detail with reference to Examples. In the text, parts indicate parts by weight.

Example 1 Add 20.0 parts of 4-amino-4-nitro-stilbene-2-2-disulfonic acid to tJ<100 parts and adjust pJ (adjust to 5 to 8 with soda ash).To this solution, add 3 parts of sodium nitrite.
．． 8 parts of 3-ureidoaniline 7, dissolved, and diazotized by injecting 13 parts of concentrated hydrochloric acid at 0 to 5°C.
6 parts and 50 parts of water, pH 5-8.0-20°C.
Add it while adjusting it, and keep the same page until the cup link is finished.
i (, Stir at the same temperature.

Next, 9.2 parts of cyanuric chloride was added at 0 to 10°C, and while adjusting the pH to 5 to 8 with an aqueous sodium carbonate solution, the mixture was heated to 0 to 30°C.
Stir with.

After the condensation, 15.5 parts of aniline-3-β-sulfatoethylsulfone was added, and the mixture was stirred at 10-4°C until the condensation was completed while adjusting the pH to 5-7.

A solution prepared by dissolving 5.9 parts of sodium sulfide in 30 parts of water is added to this solution, and the mixture is stirred at 65° C. for IFJaO minutes. Salt this out with salt to obtain a cake.

Add this cake to 100 parts of water and add soda ash to pH 6-8.
Add 3.8 parts of sodium nitrite to this solution and dissolve it, inject 13 parts of concentrated hydrochloric acid at 0 to 5°C to perform diazotization, and then add 5.4 parts of 3-methylaniline to concentrated hydrochloric acid. 13
Department.

Inject a bath solution of 30 parts of water.

Adjust the pH to 5-7 with soda carbonate to 1i [10-30
Stir at °C until coupling is complete.

Next, it was cooled to 0 to 10°C, 9.2 parts of cyanuric chloride was added, and while adjusting the pki to 5 to 8 with an aqueous sodium carbonate solution,
Stir at 0-30°C until condensation is complete.

After the condensation, 15.5 parts of aniline-4-β-sulfatoethylsulfone was added and condensation was carried out at lo~4°C while adjusting the pH to 5~7 to obtain a disazo compound of the following structural formula in the liberated form. Obtained.

O Example 2 In Example 1, instead of aniline-3-β-sulfatoethylsulfone, the aniline derivative listed in column - In place of methylaniline, equivalent moles of the amines listed in Column (1) and in place of aniline-4-β-sulfatoethylsulfone of the aniline derivatives listed in Column V are used, respectively, in the same manner. A disazo compound was obtained.

Example 3 20.0 parts of 4-amino-4-nitro-stilbene-2-2'-disulfonic acid was added to 100 parts of water and the pH was adjusted with soda ash.
Adjust to 6-8. Add and dissolve 3.8 parts of sodium nitrite into this solution, inject 18 parts of concentrated hydrochloric acid at 0 to 5°C to perform diazotization, and then create a mixture of 7.6 parts of 3-ureidoaniline and 50 parts of water. was added to the solution while adjusting the pH to 5-8.0-20°C, and the mixture was stirred at the same pH and temperature until the coupling was completed.

This was salted out with common salt, taken out, and put into 100 parts of water.
Add 1002 parts of acetic anhydride to this solution, pH 3-7.10-
Add while adjusting the temperature to 40℃. After the acetylation is completed, salt out with common salt and take out.

Add this to 100 parts of water, add 5.9 parts of soda sulfide to 30 parts of water.
Stir at 65°C for about 30 minutes, salt out with common salt, take out, add to 100 parts of water, adjust the pH to 7-12.50-100°C with caustic soda, stir, and add water. Let it break down.

Next, 8.8 parts of sodium nitrite was added and dissolved, and diazotization was carried out by keeping the pH at 0 to 5°C with concentrated hydrochloric acid to 2 or less, and then 3-
Add 5.4 parts of methylaniline.

10-30℃ while adjusting the pH to 5-7 with soda carbonate.
Stir until coupling is complete.

Next, it was cooled to 0 to 10°C, 9.2 parts of cyanuric chloride was added, and while adjusting the pLI to 5 to 8 with an aqueous sodium carbonate solution,
Stir at 0-30°C.

After 1 m, 80.9 parts of aniline-3-β-sulfatoethyl sulfone was added and condensed at 10 to 40°C while adjusting pi (5 to 7) to form a disazo compound of the following structural formula in the form of a free acid. Example 4 In Example 3, instead of 3-ureidoaniline, No.
B ["The amines listed in column (2) can be replaced with the amines listed in column (2) in place of 3-methylaniline, and the aniline derivatives listed in column (2) can be used in place of aniline-3-β-sulfatoethylsulfone." , the corresponding disazo compounds were obtained in the same manner using equimolar amounts of each.

Example 5 18.5 parts of disulfonic acid was added to 100 parts of water and the pH was adjusted to 6.
8. Add and dissolve 7.6 parts of sodium nitrite. Cool to 0-5°C, inject 26 parts of concentrated hydrochloric acid to perform tetrazotization, and then add 15.2 parts of 8-ureidoaniline.
Add 1 part to 10 parts of water to a mixed solution, and add B to the mixture while adjusting the pH to 5 to 8.0 to 20°C.

Next, 18.4 parts of cyanuric chloride was added at 0 to 10°C, and while adjusting the pH to 5 to 8 with an aqueous sodium carbonate solution, the mixture was heated to 0 to 30°C.
The mixture was stirred until the condensation was completed.

After condensation, 82.7 parts of aniline-3-β-sulfatoethyl sulfone was added and the pki was adjusted to 5-7 at 10-30C.
The disazo compound having the following structural formula was obtained in the form of a free acid.

Example 6 A corresponding monoazo compound was obtained in the same manner as in Example 5, except that equimolar amounts of the following aniline derivatives were used in place of aniline-3-β-sulfatoethylsulfone.

\\\\\, Example 7 18.4 parts of cyanuric chloride was added to a solution in which 4,4'-diaminostilbene-2,2-disulfonic acid and 3-ureidoaniline were coupled in the same manner as in Example 5. water i
Aniline was added to the oo part at 0-10℃ and dispersed.
82.7 parts of 4-β-sulfatoethyl sulfone was added, and the solution was stirred for 5 hours while maintaining the temperature at 0 to 10°C and p'' to 2 to 5.

This solution was stirred at 10-40°C and pH 5-7 for about 5 hours to obtain a monoazo compound having the following structural formula in the form of a free acid.

Example 8 In Example 7, equivalent moles of the following amines were used in place of 3-ureidoaniline, and the corresponding disazo compound was obtained in the same manner as in Example 7.

Example 9 A bath solution in which 4,4'-diaminostilbene-2,2-disulfone and 3-ureidoaniline were coupled in the same manner as in Example 5 was cooled to 0°C, and 2,4.6 -1
- 13.5 parts of refluoro-1,8,5-triazine was added dropwise, and at the same time the pH was maintained at 5 to 6 with an aqueous solution of sodium carbonate. After 16 minutes, 32.7 parts of aniline-3-β-sulfatoethyl sulfone was added. , with carbonated soda water faH (5-7 pl)
The disazo compound having the following structural formula was obtained in the form of a free acid by heating the mixture to 80-40°C and stirring for 5 hours at the same temperature while adjusting the pH to 5-7 with an aqueous solution of sodium carbonate. Ta.

λmax 4050m Example 10 In the same manner as in Example 9, using equimolar moles of the amine in column ① instead of 3-ureidoaniline, and replacing aniline-3-β-sulfa-toethylsulfone with aniline in column ①. Equimolar amounts of the derivatives were used to obtain the corresponding disazo compounds.

Example 11 4-Amino-4-nitro-stilbene-2,2-disulfonic acid was diazotized in the same manner as in Example 1, coupled with 3-ureidoaniline, condensed with cyanuric chloride, and further aniline-3 - Condensation with β-sulfatoethylsulfone.

Similarly, after reduction with sodium sulfide, diazotization and coupling with 3-methylaniline are performed to obtain a diazotide solution.

This bath liquid was cooled to 0°C, and 2, 4. Add dropwise 6.8 parts of rhotrifluoro-1,8,5-)riazine, and simultaneously maintain pL at 5 to 6 with an aqueous solution of sodium carbonate.After condensation, aniline-3-β-sulfa-toethylsulfone t 5.5
By stirring for 5 hours while adjusting the pH to 5 to 7 with an aqueous sodium carbonate solution, a disazo compound having the following structural formula was obtained in the form of a free acid.

Example 12 0.1, 0.8 and 0.6 parts of the disazo compound described in Example 1 were each dissolved in 200 parts of water, 10 parts of Glauber's salt and 10 parts of cotton were added, and the temperature was raised to 60°C. Add 4 parts of carbonated soda,
Stain for 1 hour.

By washing with water, soaping, washing with water and drying, a yellow dyed product was obtained which was excellent in various fastnesses, especially fastness to sunlight, sweat, sunlight and chlorine, and had extremely good build-up properties and good dischargeability.

This compound also has excellent solubility, and has good level dyeing and dyeing reproducibility.

Example 18 The same performance is exhibited by using the dis-azo compounds described in Examples 2 to 8 and 11 and dyeing according to the method described in the examples.

Example 14 For each of the disazo compounds described in Examples 9 and 10, 0.8 and 0.6 parts of 0.1% thereof were each added to 2 parts of water.
00 parts, add 10 parts of Glauber's salt and 10 parts of cotton, and mix at 50°C.
Add 4 parts of soda carbonate and dye at the same temperature for 1 hour. Next, by washing with water, soaping, rinsing with water and drying, a yellow dyed product with excellent build-up and fastness is obtained, which has excellent discharge properties, and is less affected by dyeing temperature fluctuations and has stable quality. He is also great at giving things away.

Continuation of page 1 0 shots Takashi Omura, Haru company, Konohana-ku, Osaka city

Claims (1)

[Claims] l) In the following general formula, X and or each independently a halogen atom,
Y and Y are each independently a hydrogen atom, a sulfo group, -8
t)zCH=(Jz. -80z(JzChzOIi, -8O2CHzCR
z8H. -802Cout0H2Z, Z is a group that is eliminated by the action of an alkali (however, at least one of Y and Y' is -8020fi=(Jz or -802C1i2C
H2Z Teal. ), A oyohi A ha represents a phenylene group or a naphthylene group which may have a fil substituent. R+, R2, it'1 and 2 each independently represent a hydrogen atom or an optionally substituted lower alkyl group. B and B each independently represent a phenylene group optionally substituted with a lower alkyl group, a lower alkoxy group, a lower alkylcarbonylamino group or a ureido group. ] A disazo compound or a salt thereof. 2) The following general formula [wherein X and X each independently represent a halogen atom,
Y and Y are each independently a hydrogen atom, a sulfo group, -8
020ki=CH2°-80zOHzCu20H, -8
O2CH2 (JH2SH. -802CkI2CH2Z, Z Hyl A group that is eliminated by lucarino action (provided that at least one of Y and Y' is -802CIi=CH2 or 802CH2
CM 2 Z Theal. ), A Oyohi A represents a phenylene group or a naphthylene group which may have a substituent. Rt, R2, Rt and R2 each independently represent a hydrogen atom or an optionally substituted lower alkyl group. B and B each independently represent a phenylene group optionally substituted with a lower alkyl group, a lower alkoxy group, a lower alkylcarbonylamino group or a ureido group. ] A method of dyeing or printing textile materials using the disazo compound or its salt shown in the following.