JPS6042462A - Disazo dye for cellulose-containing fiber - Google Patents

Abstract

PURPOSE:To produce a disazo dye in high yields, which dyes cellulose-contg. fibers blue with good fastness, by coupling a diazo compd. obtd. from a specified monoazo compd. with a specified aniline. CONSTITUTION:A monoazo compd. of formula I [wherein D is phenyl, pyridyl, (benzo)thiazolyl; X is cyano, alkoxycarbonyl] is diazotized with nitrosylsulfuric acid, etc. The resulting diazo compd. is coupled with an aniline of formula II[wherein Y is H, Cl, methyl, acylamino; R<1> is alkyl, cyclohexyl, alkenyl, aryl; R<2>, R<3> are each -NR<4>R<5>, -OR<6> (wherein R<4>, R<5>, R<6> are each H, alkyl, alkenyl, aryl, etc.); A is a group of formula III, IV or V; Z is -O-, -HN-] to produce a disazo compd. of formula VI.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel disazo dye for cellulose-containing fibers.

Specifically, the present invention relates to a disazo dye for cellulose-containing fibers that has a high coupling yield.

Furthermore, the present invention relates to a disazo dye for cellulose-containing fibers that dyes cellulose-containing fibers, particularly mixed fibers containing cellulose fibers and polyester fibers, in blue color with excellent color fastness including light fastness. It is something.

Dyes having a thionene disazo group in their chemical structure are described, for example, in JP-A-17173-DA as dyes for dyeing polyamide fibers and polyethylene fibers.

However, conventional heterocyclic disazo dyes such as thio7ene disazo dyes have unsatisfactory coupling yields in the dye manufacturing process.

An object of the present invention is to provide a heterocyclic disazo dye exhibiting a high coupling yield.

Furthermore, the present invention provides a disazo dye for cellulose-containing fibers that dyes cellulose-containing fibers, particularly mixed fibers containing cellulose fibers and polyester fibers, in a blue color with excellent color fastness including light fastness. The purpose is to

That is, the dye according to the present invention has the following general formula (formula (1)
(wherein, Diift-substituted or unsubstituted 7-enyl group, pyridyl group, thiazolyl group, or benzothiazolyl group; formula(
It) (In the formula [...], Y represents a hydrogen atom, a chlorine atom, a methyl group, or an acylamino group, R1 represents a substituted or unsubstituted alkyl group, cyclohexyl group, alkenyl group, or aryl group, and R3 and R''ti-1JR'
R' i Taha-OR' ub L, R4, R8 and R6 represent a hydrogen atom, an unsubstituted alkyl group, a cyanoalkyl group, a dialkylaminoalkyl group, an alkenyl group, a cyclohexyl group, an aryl group or an aralkyl group, Or, NR'R' is obtained by coupling with an aniline represented by the S member formed by connecting R4 and RB, or 2 represents an oxygen atom or -NH- group), which is obtained by the following general formula [111 ) (Formula (Ill)
(wherein, D, X, Y, R', R1, R3, A and 2 are the same as defined above) is a cellulose-containing fiber disazo dye.

The forepaw general formulas [1), (II), and (lit) will be explained in detail below.

Substituted or unsubstituted phenyl group, pyridine atom, methyl group, ethyl group, trifluoromethyl group, methoxy group, ethoxy group, phenylaso group, cyano group represented by D in the front leg general formulas (13 and 111) , nitro crystal,
Methylsulfonyl group, ethersulfonyl group, allylsulfonyl group, lower alkoxycarbonyl group, lower alkoxyethoxycarbonyl group, allyloxyethylcarbonyl group, mono-lower alkylaminocarbonyl group, di-lower alkylaminocarbonyl group, diallylaminocarbonyl group, monoallyl Aminocarbonyl group, dimethylaminosulfonyl group, diethylaminosulfonyl group, monomethylaminosulfonyl group, monoethylaminosulfonyl group,
Phenyl group substituted with acetyl group, phenyl group, etc.; Pyridyl group; Pyridyl group substituted with chlorine atom, bromine atom, nitro group, methyl group, methylsulfonyl group, cyano group, etc.; Thiazolyl group; Methyl group, Thiazolyl group disubstituted with chlorine atom, bromine atom, nitro group, lower alkoxycarbonyl group, methoxyethoxycarbonyl group, ethoxyethoxycarbonyl group, trifluoromethyl group, methylsulfonyl group, etc.; benzothiazolyl group; methyl group, chlorine atom , a benzothiazolyl group substituted with a bromine atom, a nitro group, a lower alkoxycarbonyl group, a trifluoromethyl group, a methylsulfonyl group, etc.

In addition, the acylamino group represented by Y in the general formula (II) and [■] is an acetylamino group, a chloroacetylamino group, a benzoylamino group, a methylsulfonylamino group, a chloropropionylamino group, an ethoxycarbonylamino group. , ethylaminocarbonylamino group, etc., and unsubstituted alkyl groups represented by R1, R4, R1 and R6 include methyl group, ethyl group, linear or fractional chain propyl group, butyl group, Examples include pentyl group, hexyl group, heptyl group, octyl group, etc. Substituted alkyl groups represented by R' include lower alkoxyalkyl groups such as methoxyethyl group, ethoxyethyl group, butoxyethyl group; methoxyethoxyethyl group, ethoxy Lower alkoxyalkoxyalkyl groups such as ethoxyethyl groups; phenoxyalkyl groups such as phenoxyethyl groups; optionally substituted aralkyloxy lower alkyl groups such as benzyloxyethyl groups and chlorobenzyloxyethyl groups; hydroxyethyl groups, hydroxypropyl optionally substituted hydroxyalkyl groups such as hydroxybutyl group, hydroxyhexyl group, euhydroxy-3-methoxyglobyl group; cyanogen lower alkyl groups such as cyanomethyl group and cyanethyl group; acetyloxyethyl group, chloro optionally substituted acyloxy lower alkyl groups such as acetyloxyethyl group, chloropropionyloxyethyl group, benzoyloxyethyl group; methoxycarbonyloxyethyl group; alkoxycarbonyloxy lower alkyl group such as methoxyethoxycarbonyloxyethyl group; carbamoyl methyl group,
Carbamoyl lower alkyl groups such as carbamoylethyl group; optionally substituted alkoxycarbonyl lower alkyl groups such as methoxycarbonylmethyl group, ethoxycarbonylmethyl group, methoxyethoxycarbonylmethyl group, benzyloxycarbonylmethyl group; hensyl group, phenethyl group , an optionally substituted aralkyl group such as a clotebenzyl group; an allyloxycarbonyl lower alkyl group such as an allyloxycarbonylethyl group or an allyloxycarbonylmethyl group; a tetrahydronerufuryl phthalic acid imide lower alkyl group; a cyanoethoxyethyl group , cyanoalkoxy lower alkyl groups such as cyanomethoxyethyl group; halogen lower alkyl groups such as chloroethyl group; examples of aryl groups include phenyl group, chlorophenyl group, methylphenyl group, etc.;
Examples of the nitrogen-containing pyrrolidinyl group represented by include l-pyrrolidinyl group, 3-methyl-/-pyrrolidinyl group, cohydroxyethyl-/-pyrrolidinyl group, S,S-dimethyl-7
-pyrrolidinyl a, J-faziridinyl group, /-pyrrolyl group, l-pyrazolyl group, /-imidazolyl group, morpholino group, piperidino group, co, 6-dimethylpiberidino group, /-piperazinyl group, goomethyl-l -piperazinyl group, etc.

As NR'R', a di-substituted amino group having a total of 6 to 1 carbon atoms is particularly desirable.

The monoazo compound represented by the general formula [1] is, for example, an amine represented by the following general formula [IV] D -NH, (IV) (wherein D is the same as defined above). It can be obtained by diazotizing the compound and coupling it with an amine represented by the following formula EV (wherein, X is the same as defined above).

In addition, the anilines represented by the forefoot general formula (II) are represented by the following general formula [■] or a bromine atom, and R2 and R3 are the same as defined above) in a solvent such as N-methylpyrrolidone or acetone in the presence of a deoxidizing agent such as triethylamine or sodium carbonate at 4Io to 10θ°C. It is produced by reacting for ~10 hours.

The amine represented by the general formula (IV) includes benzene-based amines such as aniline, 0-lm- or p-
Fluoroaniline, o-1m- or p-chloroaniline, o-m or p-bromoaniline, s,q-dichloroaniline, λ,3-dichloroanili/,2-chloro-l-bromoaniline, co,cudifluoro Aniline 1
．． 2. Q, A-) dichloroaniline, o-1m-4
fc is p-toluidine, 0-lm- or p-ethylaniline, O% m"'-'J or p-anisidine, m-
Trifluoromethylaniline, dephenylazoaniline, 0- or p-cyanoaniline, 0-lm- or p-nitroaniline, -1chlorol-nitroaniline, 2-promo-nitroaniline, -1cyanoder Nitroaniline, λ-chlorocoumethoxyaniline,
o-lm- or p-methylsulfonylaniline, o-
lm- or p-ethylsulfonylaniline, 0-lm
- or p-methoxycarbonylaniline, o-lm-
or p-ethoxycarbonylaniline, p-butoxycarbonylaniline, p-allyloxycarbonylaniline, p-allyloxyethoxycarbonylaniline,
0-lm- or p-methoxyethoxycarbonylaniline, p'-N, N-diethylaminosulfonylaniline, p-N-ethelaminocarbonylaniline, p-N
-allylaminocarbonylaniline, -monochlorudermethoxycarbonylaniline, p-N,N-dimethylaminosulfonylaniline, m-N,N-diethylaminosulfonylaniline, p-N-ethylaminosulfonylaniline, p-phenylaniline, etc. Examples of pyridine-based amines include 3-aminopyridine, 3-amino-bromopyridine, J-amino-5-bromopyridine, 3-amino-6-chloropyridine, and da,6-dichloro-3-aminopyridine. , 3-amino-, -2-tropyridine, 3-amino-gucyanoviridine, 3-amino-5-methylpyridine, 3-amino-6-methylsulfonylpyridine, 3-ami/-1t-chloro-6-nitrobiridine, 3-Amino-! =Methyl-6-promopyridine US, and the thiazole-based amines include co-aminothiazole, co-amino-coumethyltheazole, co-amino-gumethyl-5-ethoxycarbonylthiazole, copumino-5-nitrothiazole, copumino-S-bromo Examples of benzothiazole-based amines include thiazole, -mono-amino-3-chlorothiazole, co-amino-3-chlorothiazole, co-amino-coumeter-S-methoxyethoxycarbonylthiazole, and co-amino-hiro-methyl-3-bromothiazole. is co-aminopenzothiazole, co-amino-μ, 6-dip4benzothiazole, 2-amino-6-sulfomethylbenzothiazole, -mono-amino&4-dichlorobenzothiazole, -mono-amino-6-nitrobenzothiazole, etc. can be mentioned.

Furthermore, the dyeing method using the dye of the present invention will be explained in detail.

Cellulose-containing fibers dyed with the dye represented by general formula (III) include natural fibers such as wood, cotton, and hemp;
Examples include semi-synthetic fibers such as viscose rayon and cuprammonium rayon, fibers such as partially aminated or partially acylated modified cellulose fibers, and woven or knitted fabrics or nonwoven fabrics thereof. In addition, the above fibers, polyester fibers, cationically dyeable polyester fibers, anionically dyeable polyester fibers, polyamide fibers, wool, acrylic fibers,
Examples include blended products or woven products with other types of fibers such as urethane fibers, diacetate fibers, and triacetate fibers. Among these, cellulose fiber and cellulose t1. ．．
! : Particularly effective for blended products or mixed fiber products with poly-IJ ester fibers.

When dyeing is carried out, it is desirable to finely disperse the dye represented by the general formula [1] in a medium to about O, Sμ to Ωμ. A method in which a water-soluble dispersant such as anionic dispersant such as sodium ligninsulfonate or sodium salt of naphthalenesulfonic acid-formaldehyde condensate is used and finely dispersed in water using a grinder such as a Sandkling or a mill; sulfosuccinic acid Use a poorly water-soluble or water-insoluble dispersant such as a compound with a low mole of ethylene oxide added to ester, nonylphenol, etc., and use a solvent other than the water plate, such as alcohols such as ethyl alcohol, isopropyl alcohol, polyethylene glycol, acetone, methyl ethyl ketone, etc. Ketone M, hydrocarbons such as n-hexano, toluene, xylene, mineral turpentine, chlorogenated hydrocarbons such as tetrachloroethylene, esters such as ethyl acetate, bugle acetate, dioxane, tetraethylene glycol dimethyl ether, etc. Examples include a method of finely dispersing it in an ether or a mixed solvent thereof; a method of finely dispersing it in a mixed system of water and a bath agent which can optionally be mixed with water among the above-mentioned solvents.

Furthermore, in the above-mentioned fine dispersion process, a polymer compound soluble in each dispersion medium or a surfactant having a function other than dispersion may be added.

This dye fine dispersion can be used as a padding bath in padding dyeing methods, even in its trenches, and as a printing dyeing paste in textile printing methods, but when used as a normal padding bath and printing dyeing paste, the dye fine dispersion can be further mixed with water or water. A mixture system of water and a solvent that can be arbitrarily mixed with water, or an O/W emulsion in which the oil layer is a petroleum hydrocarbon such as mineral turpentine or a halogenated hydrocarbon such as tetrachloroethylene, or a 1iW10 emulsion system to achieve the desired dyeing concentration. It is used after diluting it to a proportion according to the situation.

In preparing padding baths and printing dyeing pastes, alkali metal compounds, organic epoxy compounds, organic vinyl compounds, etc. are added to acid for the purpose of promoting the reaction between cellulose fiber swelling agents or dyes and cellulose fibers in order to carry out dyeing advantageously. It can be added as a binder.

Any cellulose fiber swelling agent can be used as long as it has the effect of swelling cellulose fibers with a boiling point of iso°C or higher; for example, N, N, N'
Examples include ureas such as JI'-tetramethylurea, and conductors derived from polyhydric alcohols such as polyethylene glycol and polypropylene glycol. Especially when the average molecular weight is 2
As the cellulose fiber swelling agent, polyhydric alcohol conductors such as polyethylene glycol, polypropylene glycol, etc. of about 00 to SoO, whose hydroxyl groups at both ends are dimethylated or diacetylated and do not react with the reactive groups of the dye, are preferable.

The solution used for the cellulose fiber swelling agent is 5-5% for the padding bath or textile dyeing paste. 2! % weight is appropriate, and preferably about 3 g/3 weight.

In addition to alkali metal carbonates, alkali metal compounds include alkali metal bicarbonates, alkali metal phosphates, alkali metal borates, alkali metal silicates, alkali metal hydroxides, and alkali metal acetates. Alkali precursor compounds that generate alkali when heated in the presence of water, such as fatty acid salts or trichloroacetic acid, sodium acetoacetate, etc., can be used. These usage amounts are usually determined by the padding bath or printing paste p.
H is 7. An amount that satisfies &-za, S is sufficient. As an organic epoxy compound, ethylene glycol diglycidyl ether, average molecular fi/! ;0-1I00 polyethylene glycol diglycidyl ether, etc., and organic vinyl compounds include ethylene glycol diacrylate, average molecular N/! Examples include polyethylene glycol diacrylate or dimethacrylate of TO-da θO. The amount of these components used is about 3 to 6% by weight based on the padding bath or textile dyeing paste.

The preparation of the padding bath or printing dyeing paste is not limited to the above method, and the cellulose fiber swelling agent and acid binder do not necessarily need to be present in the pub ink bath or printing dyeing paste, but are preliminarily present on the fiber side. You can leave it.

In addition, a thickener such as a water-soluble polymer such as sodium alginate may be added to prevent dry migration during padding dyeing or to adjust the viscosity of the color paste to the optimum viscosity for various textile printing methods.

To dye the fibers with the dye represented by the general formula [■], for example, the padding bath or printing dyeing paste prepared by the above method is impregnated or printed on the cellulose fiber-containing material, and after drying, Heat treatment with hot air or superheated steam at 0°C for 30 seconds to 10 minutes, or 7
Treat in high-pressure saturated steam at 20-730°C for 3-30 minutes and wash with hot water containing a surfactant, or use O/W shop where the oil layer is a halogenated hydrocarbon such as tetrachloroethylene or use a W10 type emulsion. This can be completed by cleaning in a cleaning bath or by regular dry cleaning methods.

In this way, the dyes of the invention can be obtained with high coupling yields.

Furthermore, using the dye of the present invention, it is possible to obtain a vivid and uniformly dyed product with good light fastness and wet fastness by the above-described method.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples.

In the examples, "part" indicates "heavy needle part".

Example: A dye dispersion was prepared from a dye composition consisting of 75 parts of a disazo dye represented by the following structural formula, a naphthalene sulfonic acid-formaldehyde condensate/S part, and 70 parts of water using a paint shaker as a fine dispersion machine. . Using this dye dispersion, the following composition: Dye dispersion 6.3 parts 5% sodium alginate aqueous solution 53 parts Average molecular weight t
Ioo polyethylene 9 parts glycol dimethyl ether water 29.5 parts ioo parts CpHg, θ) A printing dyeing paste of vI4 was prepared, and a polyester/cotton (mixing ratio t, z7.ts) blended fabric was printed using a screen printing machine. 1.21 after printing and drying at GO℃ for 3 minutes! r℃
in? It was fixed by dry heat for θ seconds. After washing it with water, it was soaked using a cleaning solution containing 2 g/l of a nonionic surfactant (Scoreol qoo (trademark), manufactured by Kao Soap Co., Ltd.) at a bath ratio of J17 for 20 minutes at GO℃. A blue dyeing with excellent light fastness and wet fastness was obtained.

The dye used in this example was tuamino-3-cyano-3.
-Phenylazothiophene? , / , 1 N to trs%
Add to a mixture of phosphoric acid/40- and 200 mg of glacial acetic acid, cool to below S°C, and add to a mixture of tIo% nitrosyl sulfate of 77.
．． 01 was added gradually. The mixture was stirred at 0-j°C for an hour, and the diazo solution was mixed with urea λg and N-ethyl-N-
[J4-di(N,N-diethylamino)-4-)di-7dinyloxy]ethylaniline/1.01 was dissolved in 300 methanol and added dropwise. The obtained precipitate was separated by F, washed with water, and then dried at room temperature to obtain a blue powder of the dye represented by the above structural formula (pure yield: 90%).

This yield was at a very high level for thiophene disazo dyes. λmax (acetone) of this dye A /
l/, nm.

Example A dye composition consisting of 15 parts of a disazo dye represented by the following structural formula, 10 parts of a Pluronic type surfactant [F] Pluronic LAQ (manufactured by Asahi Denka Kogyo Co., Ltd.), and 75 parts of water was mixed into a sand powder using a fine dispersion machine. A dye dispersion was prepared using a grinder. Using this dye dispersion, make the following composition: Dye dispersion: 7 parts S% Sodium alginate aqueous solution S! Part average molecular weight 3
0θ polypropylene 10 parts Glycol diacetate average molecular weight - 〇〇 polyethylene 3 parts Glycol diglycidyl ether water CoS part ioo part (pH 6, j) (count) using a screen printing machine,
After intermediate drying at 0°C for 3 minutes, it was treated with superheated steam at tgs°C for 7 minutes.

Hereinafter, washing treatment was carried out according to the method described in Examples, and a blue dyed product with excellent light fastness and wet fastness was obtained.

The dye used in this example was synthesized according to the method described in Example 1 (pure yield: tzachi).

λmax (acetone) of this dye is A 41 ? ru
It was n.

Example 3 A dye composition consisting of 2 parts of the following structural formula % Formula % (HLB g, 9.) and gg parts of diethylene glycol-diacetate is finely dispersed and ground using a paint conditioner to prepare a dye ink! Made by l.

After mixing 70 parts of this dye ink and 53 parts of mineral turpentine, this was stirred with a homomixer (s, oθθ~7.
00ORPM) was gradually poured into 35 parts of an aqueous solution having the following composition and stirred until uniform, to prepare a viscous O/W type emulsion color paste.

Water 31 parts Retol G 3.8 parts (trademark, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., special nonionic surfactant) Sodium trichloroacetate 007 parts 3, 9 parts Next, using this color paste, polyester/cotton ( Mixing ratio 6!
r/J3) Print the blended fabric using a screen printing machine, 1
After drying at 00°C for a minute, dry at 73°C using superheated steam.
It was treated for 7 minutes.

Thereafter, it was washed in a hot tetrachloroethylene bath containing sunset water and dried, resulting in a blue dyed product with excellent light fastness and wet fastness and no hot water stains.

The dye used in this example was synthesized according to the method described in Example (purity yield: t?%).

The λmax (acetone) of the crystal was 4 lIs nm.

Example Tei 76 parts of disazo dye represented by the following structural formula, polyoxyethylene glycol nonylphenyl ether (HLB /J, ?
), 3 parts of naphthalene sulfonic acid-formaldehyde condensate, and 747 parts of water were finely dispersed using a sand grinder to prepare a dye dispersion. Using this dye dispersion, a padding bath with the following composition dye dispersion fL 4 parts water 79 parts 700 mts (pHg, 0) was prepared, and the padding bath was impregnated into a polyester/cotton (mixing ratio bs/3g) blended fabric. After narrowing down to qs%, it was dried at 100°C for a minute, and dry heat fixed at 200°C for 1 minute. By washing this product in a hot ethanol bath, a blue dyed product with excellent light fastness and wet fastness was obtained.

The dye used in this example was synthesized according to the method described in Example (pure yield = 90%).

Motoichi's λmax (acetone) was A/II nm.0 Example The old fiber was changed to a nylon/rayon (mixing ratio!; 0/30) blended fabric, and the dry heat fixation temperature was set to tgsr:.

Printing was carried out in exactly the same manner as in Example 1, except that the following was changed, and a blue printed product with good wet fastness and light fastness was obtained.

Example B Printing was carried out according to the method described in Example 1 using the disazo dyes shown in Table 1.

The light fastness and wet fastness of the dyed fabric obtained were both good.

The hue of the dyed fabric and the dye λBax (acetone) are
Shown in the table.

Claims (1)

[Claims] (1) General formula CI) (In formula [I), D is a substituted or unsubstituted 7-enyl group 1
A monoazo compound represented by the following general formula (
n) (In formula (II), Y represents a hydrogen atom, chlorine atom, methyl group or acylamino group, R1 represents a substituted or unsubstituted alkyl group, cyclohexyl group, alkenyl group or aryl group, R2 and R3 represent -NR'R”
or -OR@ represents R4, R6 and R6 hydrogen atom, unsubstituted alkyl group, cyanoalkyl group, hydroxyalkyl group, lower alkoxyalkyl group, dialkylaminoalkyl group, alkenyl group, cyclohexyl group, aryl group or aralkyl group S represents a group or -NR'R' is formed by the linkage of R4 and R5
The following general formula [■] (in formula (III), D,
X, Y, R', R2, R'', A and 2 are the same as defined above) A disazo dye for cellulose-containing fibers.