2,6-Diaminopyridine-based azo dyes for cellulose-containing fibers

FIELD OF THE INVENTION
The present invention relates to diaminopyridine-based azo dyes for cellulose-containing fibers. More particularly, it relates to reactive azo dyes for use in dyeing of cellulose-containing fibers, particularly cellulose fibers and mixed fibers of polyester fibers and cellulose fibers in from orange to blue having excellent fastness to light, etc.
SUMMARY OF THE INVENTION
The present invention is to provide diaminopyridine-based azo dyes for cellulose-containing fibers, represented by the general formula (I): ##STR2## and the other is a hydrogen atom, a phenyl group, a benzyl group, an allyl group, or an alkyl group which may be substituted by a hydroxyl group or a lower alkoxy group
(wherein)
A is a methylene group, an ethylene group, a propylene group, or a 1,3-butylene group;
n is 0 or 1;
Y.sup.1 and Y.sup.2 are each a hydrogen atom, or an alkyl group, an alkenyl group, a cyclohexyl group, an aryl group, or an aralkyl group which may all be substituted by a cyano group, a hydroxy group, a lower alkoxy group, or a dialkylamino group, and they may combine together in combination with nitrogen to form a 5- or 6-membered nitrogen-containing heterocylic ring (NY.sup.1 Y.sup.2), the total number of carbon atoms of Y.sup.1 and Y.sup.2 being 18 or less;
R.sup.1 is a nitro group, a cyano group, a methylsulfonyl group, a phenylsulfonyl group, a mono-lower alkylaminosulfonyl group, a di-lower alkylaminosulfonyl group, an acetyl group, or a benzoyl group;
R.sup.2 and R.sup.3 are each a hydrogen atom, a trifluoromethyl group, a halogen atom, or a cyano group;
R.sup.4 is a hydrogen atom, a lower alkyl group, a mono- or di-lower alkylaminosulfonyl group, a mono- or di-lower alkylcarbamoyl group, or an acetylamino group;
R.sup.5 and R.sup.6 are each a hydrogen atom, a halogen atom, or a lower alkyl group;
R.sup.7 is a lower alkyl group;
R.sup.8 is a trifluoromethyl group, or a halogen atom; and
R.sup.9 is a hydrogen atom, or a halogen atom).
DETAILED DESCRIPTION OF THE INVENTION
The dyes represented by the general formula (I) can be easily prepared, for example, by reacting compounds represented by the general formula (IV): ##STR3## and the other is a hydrogen atom, a phenyl group, a benzyl group, an allyl group, or an alkyl group which may be substituted by a hydroxyl group or a lower alkoxy group, and A and n are the same as described hereinbefore) with compounds represented by the general formula (V): ##STR4## (wherein Y.sup.1 and Y.sup.2 are the same as described hereinbefore) in a solvent, e.g., N-methyl-2-pyrrolidone.
Halogen atoms as indicated by R.sup.2, R.sup.3, R.sup.5, R.sup.6, R.sup.8 and R.sup.9 in the general formulae (I) and (IV) include a fluorine atom, a chlorine atom, and a bromine atom. Lower alkyl groups as indicated by R.sup.4 and R.sup.5 include a methyl group, an ethyl group, and a straight or branched alkyl group containing from 3 to 4 carbon atoms.
Alkyl groups as indicated by X.sup.1, X.sup.2, Z.sup.1 and Z.sup.2 include a methyl group, an ethyl group, and a straight alkyl group containing from 3 to 6 carbon atoms. Examples of alkyl groups substituted by a hydroxyl group include a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, a 2-hydroxybutyl group, a 4-hydroxybutyl group, a 1,1-dimethyl-2-hydroxyethyl group, a 5-hydroxypentyl group, a 6-hydroxyhexyl group, a (.beta.-hydroxy)ethoxyethyl group, a (.gamma.-hydroxy)propoxypropyl group, and a (.beta.-hydroxy)ethoxyethoxyethyl group. Examples of alkyl groups substituted by a lower alkoxy group include a 2-methoxyethyl group, a 2-ethoxyethyl group, a 3-methoxypropyl group, a 3-isopropoxypropyl group, a methoxyethoxyethyl group, an ethoxyethoxypropyl group, a methoxyisopropoxyethyl group, and a methoxyethoxyethoxyethyl group.
Alkyl groups as indicated by Y.sup.1 and Y.sup.2 in the general formulae (I) and (V) include a methyl group, an ethyl group, and a straight or branched alkyl group containing from 3 to 18 carbon atoms. Examples of substituted alkyl groups include cyano group-, hydroxyl group-, lower alkoxy group-, or dialkylamino group-substituted alkyl groups, such as a cyanomethyl group, a 2-cyanoethyl group, a 3-cyanopropyl group, a 2-hydroxyethyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 4-hydroxybutyl group, a 2-(2-hydroxyethoxy)ethyl group, a tris(hydroxymethyl)methyl group, a 2-ethoxyethyl group, a 3-isopropoxypropyl group, a 3-(2-methoxyethoxy)propyl group, a 2,2-diethoxyethyl group, a 2-(N,N-diethylamino)ethyl group, a 2-(N,N-dimethylamino)ethyl group, and a 3-(N,N-dimethylamino)propyl group.
Alkenyl groups include an allyl group, a 2-methylallyl group, a 3-methylallyl group, and a straight or branched alkenyl group containing from 4 to 18 carbon atoms. Substituted alkenyl groups include cyano group-, hydroxy group-, or lower alkoxy group-substituted alkenyl groups, such as a 3-cyanoallyl group, a 2-hydroxyallyl group, a 3-methoxyethoxyallyl group, and a 1-methyl-3-(N,N-diethylamino)allyl group.
Aryl groups include a phenyl group, a naphthyl group, an o-tolyl group, and a p-butylphenyl group. Examples of aryl groups substituted by a cyano group, a hydroxy group, a lower alkoxy group, or a dialkylamino group include an m-cyanophenyl group, a p-hydroxyphenyl group, a p-methoxyphenyl group, a p-(2-methoxyethoxy)phenyl group, a 2,5-dimethoxyphenyl group, and a p-(N,N-dimethylamino)phenyl group.
Aralkyl groups include a benzyl group, a phenetyl group, an m-methylbenzyl group, and a p-methylphenetyl group. Examples of substituted aralkyl groups include an m-cyanobenzyl group, a p-hydroxybenzyl group, a p-hydroxyphenetyl group, and an o-anisyl group.
Nitrogen-containing heterocyclic groups as represented by NY.sup.1 Y.sup.2 include a 1-pyrrolidinyl group, a 3-methyl-1-pyrrolidinyl group, a 2-hydroxyethyl-1-pyrrolidinyl group, a 2,5-dimethyl-1-pyrrolidinyl group, a 3-thiazolidinyl group, a 1-pyrrolyl group, a 1-pyrazolyl group, a 1-imidazolyl group, a morpholino group, a piperidino group, a 2,6-dimethylpiperidino group, a 1-piperadinyl group, and a 4-methyl-1-piperazinyl group.
Of the compounds represented by NY.sup.1 Y.sup.2, di-substituted amino groups having a total number of carbon atoms of from 6 to 12 are particularly preferred.
When n is 0, in particular, light fastness is excellent.
In preparing the disazo dyes of the general formula (I), disazo compounds represented by the general formula (II) are added to from 1 to 1.2 moles of difluorotriazines represented by the general formula (III), per mole of the disazo compound, and they are heated at a temperature of from 40.degree. to 90.degree. C. for a period of from 0.5 to 5 hours in an organic solvent, such as acetone, methyl ethyl ketone, toluene, nitrobenzene, dioxane, N,N-dimethylformaldehyde, N-methyl-2-pyrrolidone, or dimethylsulfoxide, in the presence of from 1 to 2 moles per mole of the disazo compound of an acid coupler, such as tertiary amine, e.g., triethylamine, tributylamine, or N,N-diethylaniline, and inorganic base, e.g., potassium carbonate, or potassium hydrogencarbonate. The reaction solution is then cooled and poured into, for example, water to form a precipitate. By separating the precipitate by techniques such as filtration and centrifugal separation, there can be almost quantitatively obtained the disazo dyes represented by the general formula (I).
Cellulose-containing fibers which are to be dyed with the dyes represented by the general formula (I) include fibers such as natural fibers, e.g., cotton and flax, semi-synthetic fibers, e.g., viscose rayon and copper ammonia rayon, and modified cellulose fibers, e.g., partially aminated or partially acylated cellulose fibers, and their fabrics, unwoven fabrics, and so forth. In addition, mixed fibers of cellulose fibers and other fibers, such as polyester fibers, cation dyeable polyester fibers, anion dyeable polyester fibers, polyamide fibers, wool, acryl fibers, urethane fibers, diacetate fibers, and triacetate fibers, and their fabrics can be used. Of the above-described fibers and fabrics, cellulose fibers, mixed fibers of cellulose fibers and polyester fibers, and their fabrics are particularly suitable for dyeing with the dyes of the general formula (I).
In the practice of dyeing, it is desirable that the dye of the general formula (I) is finely dispersed in a medium so that the grain size is from about 0.5 to 2 microns.
Various techniques can be employed for such fine dispersion, including a method in which a nonionic or Pluronic surface active agent, an anionic dispersant, such as sodium ligninsulfonate, or a water-soluble dispersant, such as a sodium salt of a naphthalene-sulfonic acid-formalin condensate, is employed, and the dye is finely dispersed in water by the use of a grinder such as a sand grinder and a mill; a method in which a water sparingly soluble or water-insoluble dispersant, such as a compound prepared by adding a low molecular amount of ethylene oxide to sulfosuccinic acid ester, nonylphenol, or the like, is employed, and the dye is finely dispersed in a solvent other than water, such as alcohols, e.g., ethyl alcohol, isopropyl alcohol, and polyethylene glycol, ketones, e.g., acetone and methyl ethyl ketone, hydrocarbons, e.g., n-hexane, toluene, xylene, and mineral turpentine, halogenated hydrocarbons, e.g., tetrachloroethylene, esters, e.g., ethyl acetate and butyl acetate, ethers, e.g., dioxane, and tetraethylene glycol dimethyl ether, and their mixed solvents, and a method in which the dye is finely dispersed in a mixture of water and a solvent compatible with water in any proportion, selected from the above-described solvents.
In addition, a polymeric compound soluble in each dispersant, a surface active agent having mainly a function other than the dispersion action, etc., may be added in the course of the fine dispersion.
The finely dispersed dye solution can be used as such as a padding bath for use in a padding dyeing method, or as a printing color paste for use in a printing method. It is usual, however, that the finely dispersed dye solution is diluted with water, a mixture of water and a solvent compatible with water in any proportion, an o/w emulsion in which the oil phase is petroleum hydrocarbon such as mineral turpentine or halogenated hydrocarbon such as tetrachloroethylene, or a w/o emulsion in which the oil phase is the same as above to a level determined depending on the desired dyeing concentration and, thereafter, is used as a padding bath or a printing color paste.
In the preparation of such padding baths and printing color pastes, a cellulose fiber-swelling agent can be added for advantageously effecting dyeing, or alkali metal compounds, organic epoxy compounds, organic vinyl compounds, etc., can be added as acid couplers for the purpose of accelerating the reaction between the dye and cellulose fibers. Alkali metal compounds which can be used include alkali metal carbonic acid salts, alkali metal hydrocarbonic acid salts, alkali metal phosphoric acid salts, alkali metal boric acid salts, alkali metal silicic acid salts, alkali metal hydroxides, alkali metal aliphatic acid salts, e.g., alkali metal acetic acid salts, and alkali metal precursors which generate alkalis when heated in the presence of water, such as sodium trichloroacetate and sodium acetoacetate. The amount of the alkali metal compound being used is usually sufficient to be such that the pH of the padding bath or printing color paste is from 7.5 to 8.5. Organic epoxy compounds which can be used include ethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether having an average molecular weight of from 150 to 400. Organic vinyl compounds include ethylene glycol diacrylate and diacrylate or dimethacrylate of polyethylene glycol having an average molecular weight of from 150 to 400. The amount of the organic epoxy compound or organic vinyl compound being used is from about 3 to 6% by weight based on the padding bath or printing color paste.
In order to prevent dry migration during padding dyeing, or to regulate the color paste viscosity to the optimum level in various printing methods, a tackifier such as a water-soluble polymer, e.g., sodium alginate, may be added.
The preparation of padding bath or printing color paste is not limited to the above-described methods. It is not always necessary for the cellulose swelling agent and acid coupler to be present in the padding bath or printing color paste, and they may be added in advance to cellulose fibers. Any cellulose fiber-swelling agents can be used as long as they have a boiling point of at least 150.degree. C. and have the effect of swelling cellulose fibers. Examples are ureas, such as N,N,N',N'-tetramethylurea, polyhydric alcohols, such as polyethylene glycol and polypropylene glycol, and their derivatives. In particular, polyhydric alcohol derivatives which are prepared by dimethylating or diacetylating both terminal hydroxy groups of polyethylene glycol, polypropylene glycol, or the like having an average molecular weight of from about 200 to 500 and which do not react with the reactive groups of the dye are preferred as cellulose fiber swelling agents.
The amount of the cellulose fiber-swelling agent used is appropriately from 5 to 25% by weight, preferably from 8 to 15% by weight, based on the padding bath or printing color paste.
The above-described cellulose-containing fibers are dyed with the dyes represented by the general formula (I) by the usual method. For example, a cellulose-containing fiber material is impregnated or printed with a padding bath or printing color pastes as prepared by the above-described method, heat-treated with hot air or super heated steam maintained at 160.degree. to 220.degree. C. for 0.5 to 10 minutes, or treated in high pressure saturated steam maintained at 120.degree. to 150.degree. C. for 3 to 30 minutes and, thereafter, washed with heated water containing a surface active agent, an o/w or w/o emulsion cleaning bath in which the oil phase is halogenated hydrocarbon such as tetrachloroethylene, or by the usual dry cleaning method.
In accordance with the above-described method, there can be obtained a dyed product which is sharp and uniformly dyed in a color having good light fastness and moisture fastness.

The following examples are given to illustrate the invention in greater detail although the invention is not limited thereto. All parts are by weight.
EXAMPLE 1
A dye composition consisting of 15 parts of a disazo dye represented by the formula: ##STR5## 15 parts of a naphthalenesulfonic acid-formaldehyde condensate, and 70 parts of water was finely dispersed by the use of a paint shaker as a finely dispersing apparatus to prepare a dye dispersion. The thus-prepared dye dispersion was used to prepare a printing color paste having the following composition:
______________________________________ parts______________________________________Dye dispersion 6.55% Aqueous sodium alginate solution 55Polyethylene glycol dimethyl ethyl 9having an average molecular weightof 400Water 29.5Total 100 (pH: 8.0)______________________________________
A polyester/cotton mixed cloth (mixing ratio: 65/35) was printed with the above-prepared printing color paste by the use of a screen printing machine, which was then subjected to intermediate drying at 80.degree. C. for 3 minutes and fixed by dry heating at 215.degree. C. for 90 seconds. The cloth was washed with water and, thereafter, was subjected to soaping using a cleaning liquid containing 2 g/l of a nonionic surface active agent (Scorerol #900 (trade name) produced by Kao Sekken Co., Ltd.) at 80.degree. C. for 20 minutes at a bath ratio of 1:30. There was thus obtained a product dyed in red having excellent light fastness and wet color fastness.
The dye used in this example was prepared as follows. 3',4'-Dichloro-4-aminoazobenzene was diazotized by the usual method and coupled with 2-(m-hydroxy)anilinio-3-cyano-4-methyl-6-(.gamma.-methoxypropylamino)pyridine to obtain a dye. A mixture of 5.76 g of the above-obtained dye, 2.1 g of 2,4-difluoror-6-(diethyl)aminotriazine, 1.0 g of triethylamine, and 1.0 g of anhydrous potassium carbonate was added to 100 ml of acetone and heated at reflux for 3 hours to achieve a condensation reaction. The reaction solution was then added dropwise to 1,000 ml of water to form a precipitate. The precipitate was separated by filtration, washed with water, and dried at room temperature to obtain 7.1 g of red powder of the dye represented by the above-described formula (yield: 95%). For this dye, .lambda.max (acetone) was 505 nm.
EXAMPLE 2
A dye composition consisting of 15 parts of a disazo dye represented by the formula: ##STR6## 10 parts of a Pluronic surface active agent (Pluronic L64 (trade name) produced by Asahi Denka Kogyo Co., Ltd.), and 75 parts of water was finely dispersed by the use of a sand grinder as a finely dispersing apparatus to prepare a dye dispersion. This dye dispersion was used to prepare a printing color paste having the following composition:
______________________________________ parts______________________________________Dye dispersion 75% Aqueous sodium alginate solution 55Diacetate of polypropylene glycol 10having an average molecular weightof 300Polyethylene glycol diglycidyl ether 3having an average molecular weightof 200Water 25Total 100 (pH: 6.5)______________________________________
A cotton broad (cotton yarn number: 40) which had been subjected to silket processing was printed with the above-prepared printing color paste by the use of a screen printing machine, was subjected to intermediate drying at 80.degree. C. for 3 minutes, and then, was treated with super heated steam at 185.degree. C. for 7 minutes. Thereafter, washing processing was performed in the same manner as in Example 1, and there was thus obtained a product dyed in red having excellent light fastness and wet color fastness.
The dye used in this example was prepared as follows. 2'-Trifluoromethyl-4'-chloro-4-aminoazobenzene was diazotized by the usual method and coupled with 2-(p-hydroxy)anilino-3-cyano-4-methyl-6-(.beta.-hydroxyethylamino)pyridine to prepare a dye. The dye thus obtained was reacted with 2,4-difluoro-6-[di(n-propyl)amino]triazine in N-methyl-2-pyrrolidone by the use of triethylamine as an acid-removing agent to obtain the dye represented by the above-described formula. For this dye, .lambda.max (acetone) was 506 nm.
EXAMPLE 3
A dye composition consisting of 10 parts of a disazo dye represented by the formula: ##STR7## 2 parts of polyoxyethylene glycol nonylphenyl ether (HLB: 8.9), and 88 parts of diethylene glycol diacetate was ground by the use of a paint conditioner as a finely dispersing apparatus to prepare a dye ink.
A mixture of 10 parts of the dye ink as prepared above and 55 parts of mineral turpentine was gradually poured into 35 parts of an aqueous solution having the composition as described hereinafter while stirring by a homomixer at 5,000 to 7,000 rpm, and the resulting mixture was then stirred until it became uniform to prepare a viscous o/w emulsion type color paste.
______________________________________Composition of Aqueous Solution parts______________________________________Water 31Repitol G (trade name, special 3.8nonionic surface active agent,produced by Dai-ichi Kogyo SeiyakuCo., Ltd.)Sodium trichloroacetate 0.1Total 34.9______________________________________
Using the above-prepared color paste, a polyester/cotton mixed cloth (mixing ratio: 65/35) was printed by the use of a screen printing machine, which was then dried at 100.degree. C. for 2 minutes and treated with super heated steam at 175.degree. C. for 7 minutes. Thereafter, when the cloth was washed with a hot tetrachloroethylene bath containing a small amount of water and dried, there was obtained a product dyed in red having excellent light fastness and wet color fastness and free from contamination in the white background.
The dye used in this example was prepared as follows. 3',5'-Dichloro-3-methyl-4-aminoazobenzene was diazotized by the usual method and coupled with 2-ethoxyethylamino-3-cyano-4-methyl-6-(p-hydroxyphenylethylamino)pyridine to prepare a dye. The dye thus prepared was then reacted with 2,4-difluoro-6-piperidinotriazine in the same manner as in Example 1 to obtain the desired dye. For this dye, .lambda.max (acetone) was 506 nm.
EXAMPLE 4
A dye composition consisting of 16 parts of a disazo dye represented by the formula: ##STR8## 7 parts of polyoxyethylene glycol nonylphenyl ether (HLB: 13.3), 3 parts of a naphthalenesulfonic acid-formaldehyde condensate, and 74 parts of water was finely dispersed by the use of a sand grinder to prepare a dye dispersion. This dye dispersion was used to prepare a padding bath having the following composition:
______________________________________ parts______________________________________Dye dispersion 6Tetraethylene glycol dimethyl ether 15Water 79Total 100 (pH: 8.0)______________________________________
A polyester/cotton mixed cloth (mixing ratio: 65/35) was impregnated with the above-prepared padding bath, squeezed at a squeezing ratio of 45%, dried at 100.degree. C. for 2 minutes, and fixed by dry heating at 200.degree. C. for 1 minute. By washing the cloth with a hot ethanol bath, there was obtained a product dyed in red having excellent light fastness and wet color fastness.
The dye used in this example was prepared in the same manner as in Example 1. For this dye, .lambda.max (acetone) was 506 nm.
EXAMPLE 5
Printing was performed in the same manner as in Example 1 except that a nylon/rayon mixed cloth (mixing ratio: 50/50) was used, and the dry heating fixing temperature was 185.degree. C. There was obtained a product dyed in red having good wet color fastness and light fastness.
EXAMPLE 6
Using a series of disazo dyes as shown in Tables 1 to 15, printing was performed in the same manner as in Example 1. All dyed products had good light fastness and wet color fastness. The hue of each dyed cloth and .lambda.max (acetone) of dye are shown in Tables 1 to 15.
TABLE 1__________________________________________________________________________ ##STR9## No. ##STR10## ##STR11## X Z Hue of Dyed .lambda.max (acetone) (nm)__________________________________________________________________________ ##STR12## ##STR13## H N(C.sub.3 H.sub.6 CN).sub.2 red 505 2 ##STR14## " CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3 ##STR15## " 504 3 ##STR16## " " N[C.sub.3 H.sub.7 (n)].sub.2 " 505 4 ##STR17## " " ##STR18## " " 5 " ##STR19## C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5 N(CH.sub.2CHCH.sub.2).sub.2 " 506 6 " ##STR20## " NH.sub.2 deep red 510 7 ##STR21## ##STR22## " ##STR23## red 506 8 ##STR24## ##STR25## ##STR26## ##STR27## " 505 9 " ##STR28## " N(CH.sub.2 CH.sub.2 CH.sub.2 OH).sub.2 " 508 10 ##STR29## ##STR30## " ##STR31## " 504 11 " " ##STR32## N[C.sub.5 H.sub.11 (n)].sub.2 " "12 " ##STR33## " ##STR34## " 506 13 ##STR35## ##STR36## CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 ##STR37## deep red 510 14 " " " ##STR38## " " 15 " ##STR39## C.sub.3 H.sub.7 (i) N[C.sub.3 H.sub.6 N(CH.sub.3).sub.2 "sub.2 512 16 ##STR40## ##STR41## " N[C.sub.9 H.sub.19 (n)].sub.2 " 510 17 " " " NHC.sub.7 H.sub.15 (n) " " 18 " ##STR42## CH.sub.2 CH.sub.2 CH.sub.2 OH ##STR43## " 513__________________________________________________________________________
TABLE 2__________________________________________________________________________ ##STR44## No. ##STR45## ##STR46## X Z Dyed ClothHue (nm)(acetone).lambda.max__________________________________________________________________________19 ##STR47## ##STR48## C.sub.4 H.sub.9 (i) ##STR49## red 506 20 ##STR50## " CH.sub.3 ##STR51## " " 21 " ##STR52## C.sub.2 H.sub.4 OCH.sub.3 ##STR53## deep red 510 22 ##STR54## ##STR55## " ##STR56## red 506 23 ##STR57## " " ##STR58## " " 24 ##STR59## ##STR60## ##STR61## NH.sub.2 " 508 25 " ##STR62## CH.sub.2CHCH.sub.2 N[C.sub.3 H.sub.7 (i)].sub.2 " 506 26 ##STR63## " C.sub.2 H.sub.4 OCH.sub.3 NHC.sub.3 H.sub.7 (i) deep red 509 27 ##STR64## " " N(C.sub.2 H.sub.4 CN).sub.2 red 506 28 ##STR65## " H N(CH.sub.2CHCH.sub.2).sub.2 " " 29 " ##STR66## CH.sub.2 CH.sub.2 OCH.sub.3 ##STR67## deep red 509 30 " ##STR68## ##STR69## N[C.sub.3 H.sub.7 (i)].sub.2 " 508 31 ##STR70## ##STR71## C.sub.5 H.sub.11 (n) ##STR72## red 506 32 " " " N(C.sub.2 H.sub.5).sub.2 " " 33 " ##STR73## CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH N(C.sub.2 H.sub.4 CN).sub.2 red-brown 512 34 ##STR74## ##STR75## " N[C.sub.6 H.sub.13 (sec)].sub.2 deep red 509 35 " ##STR76## CH.sub.2 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 N(C.sub.2 H.sub.4 OH).sub.2 " 510 36 " ##STR77## C.sub.3 H.sub.7 (n) N(C.sub.2 H.sub.5).sub.2 " "__________________________________________________________________________
TABLE 3__________________________________________________________________________ ##STR78## No. ##STR79## ##STR80## X Z Dyed ClothHue (nm)(acetone).la mbda.max__________________________________________________________________________37 ##STR81## ##STR82## (CH.sub.2).sub.3 O(C.sub.2 H.sub.4 O).sub.2 CH.sub.3 ##STR83## red 505 38 ##STR84## ##STR85## C.sub.4 H.sub.9 (i) NHCH.sub.3 " 507 39 ##STR86## ##STR87## ##STR88## ##STR89## deep red 511 40 ##STR90## ##STR91## ##STR92## N[C.sub.3 H.sub.7 (n)].sub.2 red 505 41 ##STR93## " C.sub.3 H.sub.6 OCH.sub.3 NH(CH.sub.2).sub.8 CHCH(CH.sub.2).sub.7 CH.sub.3 " 504__________________________________________________________________________
TABLE 4__________________________________________________________________________ ##STR94## No. ##STR95## ##STR96## X Z Dyed ClothHue of (nm)(acetone).lambda.max__________________________________________________________________________42 ##STR97## ##STR98## C.sub.2 H.sub.4 OC.sub.2 H.sub.5 N[C.sub.9 H.sub.19 (n)].sub.2 red 506 43 ##STR99## " " ##STR100## " " 44 ##STR101## ##STR102## " N[C.sub.3 H.sub.7 (i)].sub.2 deep red 510 45 ##STR103## ##STR104## " N[C.sub.4 H.sub.9 (n)].sub.2 red 507 46 ##STR105## ##STR106## C.sub.6 H.sub.13 (n) N[C.sub.4 H.sub.9 (sec)].sub.2 red 506 47 ##STR107## ##STR108## (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH ##STR109## deep red 512__________________________________________________________________________
TABLE 5__________________________________________________________________________ ##STR110## No. ##STR111## ##STR112## X Z Dyed ClothHue (nm)(acetone).lambda.max__________________________________________________________________________48 ##STR113## ##STR114## ##STR115## ##STR116## red 506 49 ##STR117## ##STR118## " ##STR119## deep red 510 50 ##STR120## ##STR121## CH.sub.2 CH.sub.2 OC.sub.3 H.sub.7 (i) ##STR122## " 511 51 ##STR123## " " ##STR124## red 505__________________________________________________________________________
TABLE 6__________________________________________________________________________ ##STR125## No. ##STR126## ##STR127## X Z Dyed ClothHue of (nm)(acetone).lambda.max__________________________________________________________________________52 ##STR128## ##STR129## (CH.sub.2).sub.5 OH NHC.sub.3 H.sub.6 OH red 50653 ##STR130## " " N(C.sub.2 H.sub.4 OC.sub.2 H.sub.5).sub.2 " " 54 ##STR131## " " ##STR132## deep red 511 55 ##STR133## ##STR134## C.sub.4 H.sub.9 (sec) ##STR135## red 506__________________________________________________________________________
TABLE 7__________________________________________________________________________ ##STR136## No. ##STR137## ##STR138## X Z Dyed ClothHue of (nm)(acetone).lambda.max__________________________________________________________________________56 ##STR139## ##STR140## ##STR141## ##STR142## red 506 57 ##STR143## ##STR144## CH.sub.2CHCH.sub.2 ##STR145## deep red 511 58 ##STR146## ##STR147## C.sub.3 H.sub.6 OCH.sub.3 ##STR148## " 509 59 ##STR149## " " N(C.sub.2 H.sub.4 CN).sub.2 red 504__________________________________________________________________________
TABLE 8__________________________________________________________________________ ##STR150## No. ##STR151## ##STR152## X Z Dyed ClothHue of (nm)(acetone).lambda.max__________________________________________________________________________60 ##STR153## ##STR154## ##STR155## N(C.sub.2 H.sub.5).sub.2 red 505 61 ##STR156## " CH.sub.3 NHC.sub.6 H.sub.13 (sec) " " 62 ##STR157## ##STR158## " N[C.sub.3 H.sub.7 (n)].sub.2 deep red 507 63 ##STR159## ##STR160## C.sub.3 H.sub.7 (i) N(C.sub.2 H.sub.4 OCH.sub.3).sub.2 red 507 64 ##STR161## " C.sub.2 H.sub.4 OH ##STR162## deep red 511__________________________________________________________________________
TABLE 8__________________________________________________________________________ ##STR163## No. ##STR164## ##STR165## X Z Dyed ClothHue of (nm)(acetone).lambda.max__________________________________________________________________________65 ##STR166## ##STR167## C.sub.3 H.sub.6 OCH.sub.3 NHC.sub.3 H.sub.6 OH red 507 66 ##STR168## ##STR169## " N[C.sub.3 H.sub.7 (i)].sub.2 red-brown 514 67 ##STR170## ##STR171## " NHC.sub.2 H.sub.4 OH deep red 511 68 ##STR172## ##STR173## C.sub.3 H.sub.6 OCH.sub.3 N(C.sub.2 H.sub.5).sub.2 red 506 69 ##STR174## " CH.sub.3 ##STR175## deep red 511__________________________________________________________________________
TABLE 10__________________________________________________________________________ ##STR176## No. ##STR177## ##STR178## X Z Dyed ClothHue of (nm)(acetone).lambda.max__________________________________________________________________________70 ##STR179## ##STR180## C.sub.2 H.sub.4 OH N[C.sub.7 H.sub.15 (n)].sub. 2 deep red 513 71 ##STR181## ##STR182## (CH.sub.2).sub.6 OH ##STR183## red 505 72 ##STR184## " " ##STR185## " " 73 ##STR186## " (CH.sub.2).sub.2 OH ##STR187## " 503 74 ##STR188## " C.sub.6 H.sub.13 (n) N(C.sub.2 H.sub.4 OCH.sub.3).sub.2 " 506__________________________________________________________________________
TABLE 11__________________________________________________________________________ ##STR189## No. ##STR190## ##STR191## X Z Dyed ClothHue of (nm)(acetone).lambda.max__________________________________________________________________________75 ##STR192## ##STR193## (CH.sub.2).sub.3 OH ##STR194## red 505 76 " ##STR195## C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OH N(C.sub.3 H.sub.6 CN).sub.2 deep red 509 77 ##STR196## ##STR197## ##STR198## N(C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCH.sub.3).s ub.2 red 504 78 ##STR199## ##STR200## H ##STR201## " 506 79 ##STR202## ##STR203## C.sub.3 H.sub.7 (i) N(CH.sub.3).sub.2 " 504__________________________________________________________________________
TABLE 12__________________________________________________________________________ ##STR204## No. ##STR205## ##STR206## X Z Dyed ClothHue of (nm)(acetone).lambda.max__________________________________________________________________________80 ##STR207## ##STR208## CH.sub.2CHCH.sub.2 ##STR209## red 507 81 " ##STR210## (CH.sub.2).sub.4 OH NHC.sub.7 H.sub.15 (n) " 505 82 ##STR211## " C.sub.3 H.sub.6 OC.sub.3 H.sub.7 (i) NHC.sub.3 H.sub.7 (i) " "83 ##STR212## ##STR213## C.sub.4 H.sub.9 (i) N[C.sub.4 H.sub.9 (i)].sub.2 deep red 513__________________________________________________________________________
TABLE 13__________________________________________________________________________ ##STR214## No. ##STR215## ##STR216## X Z Dyed ClothHue of (nm)(acetone).lambda.max__________________________________________________________________________84 ##STR217## ##STR218## (CH.sub.2).sub.5 OH NHCH.sub.3 deep red 51185 ##STR219## ##STR220## C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3 N[C.sub.4 H.sub.9 (n)].sub.2 " 509 86 ##STR221## ##STR222## " ##STR223## red 507 87 ##STR224## ##STR225## H NH.sub.2 " 506__________________________________________________________________________
TABLE 14__________________________________________________________________________ ##STR226## No. ##STR227## ##STR228## X Z Dyed ClothHue of (nm)(acetone).lambda.max__________________________________________________________________________88 ##STR229## ##STR230## ##STR231## N[C.sub.3 H.sub.7 (n)].sub.2 red 505 89 ##STR232## ##STR233## C.sub.2 H.sub.4 OC.sub.2 H.sub.5 ##STR234## deep red 511 90 ##STR235## ##STR236## C.sub.3 H.sub.6 OH(n) N(C.sub.2 H.sub.5).sub.2 red 505__________________________________________________________________________
TABLE 15__________________________________________________________________________ ##STR237## No. D m Z ##STR238## (T/C mixed cloth)Hue of Dye Cloth (acetone) (nm).lambda.max__________________________________________________________________________91 ##STR239## 2 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5 ##STR240## red-brown 483 92 ##STR241## " OCH.sub.3 ##STR242## red 485 93 " 3 OC.sub.2 H.sub.5 ##STR243## " 487 94 ##STR244## 2 ##STR245## ##STR246## bluish red 512 95 " " OCH.sub.3 ##STR247## " " 96 ##STR248## " OC.sub.3 H.sub.7 (n) ##STR249## orange 470 97 " 3 " ##STR250## " 472 98 ##STR251## 2 OC.sub.2 H.sub.4 OCH.sub.3 ##STR252## gold 469 99 ##STR253## " OC.sub.3 H.sub.6 OC.sub.2 H.sub.5 " " 461 100 ##STR254## " OC.sub.2 H.sub.5 ##STR255## yellowish red 489 101 " 3 OC.sub.4 H.sub.9 (t) ##STR256## " " 102 ##STR257## 2 OCH.sub.3 ##STR258## " 499 103 ##STR259## " " ##STR260## red 501 104 ##STR261## " OC.sub.2 H.sub.5 ##STR262## " 503 105 " 3 ##STR263## " " 505 106 " 2 OCH.sub.3 ##STR264## " 501 107 ##STR265## " OC.sub.3 H.sub.7 (n) ##STR266## " 503 108 " " OC.sub.2 H.sub.4 OCH.sub.3 ##STR267## " 501 109 ##STR268## " OCH.sub.3 ##STR269## deep red 505 110 ##STR270## " ##STR271## " " " 111 " " OC.sub.4 H.sub.9 (sec) ##STR272## " 503 112 ##STR273## " OC.sub.3 H.sub.7 (i) ##STR274## " 507 113 " 3 OCH.sub.3 " " 508 114 ##STR275## 2 OC.sub.2 H.sub.5 " " 505 115 " 3 OC.sub.2 H.sub.4 OCH.sub.3 ##STR276## " 506 116 ##STR277## 2 OC.sub.5 H.sub.11 (n) ##STR278## " 507 117 ##STR279## " OC.sub.4 H.sub.9 (t) ##STR280## " " 118 " " ##STR281## " " " 119 " 3 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5 ##STR282## " 508 120 ##STR283## 2 OC.sub.3 H.sub.6 OCH.sub.3 ##STR284## " 506 121 ##STR285## 3 OCH.sub.3 ##STR286## " 509 122 ##STR287## 2 OC.sub.2 H.sub.5 ##STR288## orange 468 123 ##STR289## " OC.sub.3 H.sub.7 ##STR290## " " 124 ##STR291## " OC.sub.2 H.sub.5 ##STR292## red 494 125 " " " ##STR293## " 492 126 ##STR294## " OC.sub.5 H.sub.11 (sec) ##STR295## reddish blue 594 127 " 3 OC.sub.2 H.sub.5 " " 595 128 " 2 OC.sub.3 H.sub.7 (i) ##STR296## " 592 129 " 3 OC.sub.4 H.sub.9 (sec) ##STR297## " 593__________________________________________________________________________
EXAMPLE 7
A dye composition consisting of 15 parts of a disazo dye represented by the formula: ##STR298## 15 parts of a naphthalenesulfonic acid-formaldehyde condensate, and 70 parts of water was finely dispersed by the use of a paint shaker as a finely dispersing apparatus to prepare a dye dispersion. This dye dispersion was used to prepare a printing color paste having the following composition:
______________________________________ parts______________________________________Dye dispersion 6.55% Aqueous sodium alginate solution 55Polyethylene glycol dimethyl ether 9having an average molecular weightof 400Water 29.5Total 100 (pH 8.0)______________________________________
The thus-prepared printing color paste was printed on a polyester/cotton mixed cloth (mixing ratio: 65/35) by the use of a screen printer, was subjected to intermediate drying at 80.degree. C. for 3 minutes, and was fixed by dry heating at 215.degree. C. for 90 seconds. The cloth was then washed with water and was subjected to soaping using a cleaning liquid containing 2 g/l of a nonionic surface active agent (Scorerol #900 (trade name), produced by Kao Sekken Co., Ltd.) at 80.degree. C. for 20 minutes at a bath ratio of 1:30. There was thus obtained a product dyed in yellowish red having excellent light fastness and wet color fastness.
The dye used in this example was prepared as follows.
In accordance with the usual method, 4-aminoazobenzene was diazotized and coupled with 2(m-hydroxy)anilino-3-cyano-4-methyl-6-(.UPSILON.-methoxypropylamino)pyridine to prepare a dye. A mixture of 5.07 g of the above-prepared dye, 2.1 g of 2,4-difluoro-6-(diethyl)aminotriazine, and 1.0 g of anhydrous potassium carbonate was added to 100 ml of acetone and heated at reflux to achieve a condensation reaction. The resulting reaction solution was added dropwise to 1,000 ml of water. The precipitate thus obtained was separated by filtration, washed with water, and dried at room temperature to obtain 6.5 g of red powder of the dye represented by the above-described formula. For this dye, .lambda.max (acetone was 490 nm.
EXAMPLE 8
A dye composition consisting of 15 parts of a disazo dye represented by the formula: ##STR299## 10 parts of a Pluronic surface active agent, Pluronic L64 (trade name, produced by Asahi Denka Kogyo Co., Ltd.), and 7.5 parts of water was finely dispersed by the use of a sand grinder as a finely dispersing apparatus to prepare a dye. This dye was used to prepare a printing color paste having the following composition:
______________________________________ parts______________________________________Dye dispersion 75% Aqueous sodium alginate solution 55Diacetate of polypropylene glycol 10having an average molecular weightof 300Polyethylene glycol diglycidyl ether 3having an average molecular weightof 200Water 25Total 100 (pH: 6.5)______________________________________
The above-prepared printing color paste was printed on a cotton broad (cotton yarn number: 40) which had been subjected to silket processing, by the use of a screen printing machine, was subjected to intermediate drying at 80.degree. C. for 3 minutes, and was treated with super heated steam at 185.degree. C. for 7 minutes. Thereafter, a cleaning processing was performed in the same manner as in Example 7, and there was thus obtained a product dyed in reddish brown having excellent light fastness and wet color fastness.
The dye used in this example was prepared as follows.
In accordance with the usual method, 1-aminoanthraquinone was diazotized and coupled with 2-(p-hydroxy)anilino-3-cyano-4-methyl-6-(.beta.-hydroxyethylamino)pyridine to prepare a dye. The dye thus formed was then reacted with 2,4-difluoro-6-[di(n-propyl)amino]triazine in N-methyl-2-pyrrolidone by the use of triethylamine as an acid-removing agent to obtain the desired dye. For this dye, .lambda.max (acetone) was 483 nm.
EXAMPLE 9
A dye composition consisting of 10 parts of a monoazo dye represented by the formula: ##STR300## 2 parts of polyoxyethylene glycol nonylphenyl ether (HLB: 8.9), and 88 parts of diethylene glycol diacetate was finely dispersed by the use of a paint conditioner as a finely dispersing apparatus to prepare a dye ink.
A mixture of 10 parts of the above-prepared dye ink and 55 parts of mineral turpentine was gradually poured into 35 parts of an aqueous solution having the composition as described hereinafter while stirring by a homomixer at 5,000 to 7,000 rpm, and the resulting mixture was stirred until it became uniform to prepare a viscous o/w emulsion type color paste.
______________________________________Composition of Aqueous Solution parts______________________________________Water 31Repitol G (trade name, special 3.8nonionic surface active agent,produced by Dai-ichi Kogyo SeiyakuCo., Ltd.)Sodium trichloroacetate 0.1Total 34.9______________________________________
This color paste was printed on a polyester/cotton mixed cloth (mixing ratio: 65/35) by the use of a screen printing machine, dried at 100.degree. C. for 2 minutes, and treated with super heated steam at 175.degree. C. for 7 minutes. Thereafter, the cloth was washed with a hot tetrachloroethylene bath containing a small amount of water and dried, and there was thus obtained a golden dyed product having excellent light fastness and wet color fastness, and free from contamination in the white background.
The dye used in this example was prepared as follows.
In accordance with the usual method, 2-chloro-4-methylsulfonylaniline was diazotized and coupled with 2-(p-hydroxyphenylethylamino)-3-cyano-4-methyl-6-ethoxyethylaminopyridine to form a dye. The dye thus formed was reacted with 2,4-difluoro-6-piperidinotriazine in the same manner as in Example 7 to obtain the desired dye. For this dye, .lambda.max (acetone) was 469 nm.
EXAMPLE 10
A dye composition consisting of 16 parts of a disazo dye represented by the formula: ##STR301## 7 parts of polyoxyethylene glycol nonylphenyl ether (HLB: 13.3), 3 parts of a naphthalenesulfonic acid-formaldehyde condensate, and 74 parts of water was finely dispersed by the use of a sand grinder to prepare a dye dispersion. This dye dispersion was used to prepare a padding bath having the following composition:
______________________________________ parts______________________________________Dye dispersion 6Tetraethylene glycol dimethyl ether 15Water 79Total 100 (pH: 8.0)______________________________________
A polyester/cotton mixed cloth (mixing ratio: 65/35) was impregnated with the above-prepared padding bath, squeezed at a squeezing ratio of 45%, dried at 100.degree. C. for 2 minutes, and fixed by dry heating at 200.degree. C. for 1 minute. By washing the cloth with a hot ethanol bath, there was obtained a product dyed in red having excellent light fastness and wet color fastness.
The dye used in this example was prepared in the same manner as in Example 7. For this dye, .lambda.max (acetone) was 503 nm.
EXAMPLE 11
Printing was performed in the same manner as in Example 1 except that a nylon/rayon mixed cloth (mixing ratio: 50/50) was used and the dry heating fixing temperature was 185.degree. C. There was thus obtained a product dyed in red having good light fastness and wet color fastness.
EXAMPLE 12
Using a series of azo dyes as shown in Tables 16 to 22, printing was performed in the same manner as in Example 7.
All dyed clothes had good light fastness and wet color fastness. The hue of each dyed cloth and .lambda.max (acetone) of each dye are shown in Tables 16 to 22.
TABLE 16__________________________________________________________________________ ##STR302## .lambda.max Hue (acetone)No. D Z W Dyed (nm)h__________________________________________________________________________ ##STR303## C.sub.2 H.sub.4 OC.sub.2 H.sub.5 N[CH.sub.2 CH.sub.2 N(CH.sub.3).su b.2 ].sub.2 red-orange 472 2 " H ##STR304## " 468 3 ##STR305## ##STR306## N(CH.sub.2 CH.sub.2 CH.sub.2 OH).sub.2 deep 513 4 " CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 ##STR307## " " 5 ##STR308## C.sub.5 H.sub.11 (n) ##STR309## red-orange 476 6 ##STR310## (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH ##STR311## reddish yellow 469 7 ##STR312## CH.sub.2 CH.sub.2 CH.sub.2 OC.sub.3 H.sub.7 ##STR313## reddish yellow 470 8 ##STR314## C.sub.4 H.sub. 9 (sec) NH.sub.2 red 503 9 ##STR315## (CH.sub.2).sub.5 OH NHC.sub.3 H.sub.7 (i) " " 10 " CH.sub.2 CH.sub.2 OH N[C.sub.4 H.sub.9 (sec)].sub.2 " 512 11 " (CH.sub.2).sub.3 O(C.sub.2 H.sub.4 O).sub.2 CH.sub.3 ##STR316## " 513 12 ##STR317## ##STR318## ##STR319## orange 469 13 ##STR320## C.sub.4 H.sub.9 (i) ##STR321## " " 14 " C.sub.5 H.sub.11 (sec) ##STR322## red 493 15 " (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH NHC.sub.5 H.sub.11 (i) " " 16 ##STR323## CH.sub.2 CH.sub.2 CH.sub.2 OH ##STR324## reddish blue 593 17 " ##STR325## N(C.sub.2 H.sub.5).sub.2 reddish blue "__________________________________________________________________________
TABLE 17__________________________________________________________________________ ##STR326## .lambda.max Hue (acetone)No. D Z W Dyed (nm)h__________________________________________________________________________18 ##STR327## CH.sub.2 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 ##STR328## reddish yellow 471 19 " C.sub.2 H.sub.5 ##STR329## reddish yellow " 20 ##STR330## (CH.sub.2).sub.3 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5 N(CH.sub.2 CH.sub.2 OCH.sub.3).sub.2 bluish 513 21 " ##STR331## ##STR332## " 514 22 ##STR333## C.sub.3 H.sub.7 (i) N(CH.sub.3).sub.2 yellowish red 487 23 " CH.sub.2 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 NH.sub.2 yellowish 486 red 24 ##STR334## C.sub.5 H.sub.11 (sec) ##STR335## red 492 25 ##STR336## CH.sub.2 CH.sub.2 OH ##STR337## " 501 26 ##STR338## CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH N[C.sub.3 H.sub.7 (i)].sub.2 " 502 27 ##STR339## CH.sub.2 CH.sub.2 CH.sub.2 OH ##STR340## reddish yellow 470 28 ##STR341## H ##STR342## reddish orange 478 29 ##STR343## ##STR344## N(C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCH.sub.3).sub.2 red 502 30 ##STR345## CH.sub.2 CH.sub.2 OCH.sub.3 ##STR346## yellowish red 494 31 ##STR347## (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH ##STR348## red 503 32 ##STR349## ##STR350## N[C.sub.4 H.sub.9 (sec)].sub.2 " 500 33 ##STR351## C.sub.5 H.sub.11 (n) N(CH.sub.2CHCH.sub.2).sub.2 orange 473 34 ##STR352## C.sub.2 H.sub.4 OH N[C.sub.3 H.sub.7 (i)].sub.2 red 492__________________________________________________________________________
TABLE 18__________________________________________________________________________ ##STR353## .lambda.max Hue (acetone)No. D Z W Dyed (nm)h__________________________________________________________________________35 ##STR354## C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCH.sub.3 NHC.sub.2 H.sub.4 OH yellow 461 36 ##STR355## ##STR356## NHC.sub.5 H.sub.11 (n) bluish red 513 37 ##STR357## C.sub.4 H.sub.9 (i) N[C.sub.6 H.sub.13 (n)].sub.2 bluish red 514 38 ##STR358## C.sub.2 H.sub.4 OH NH(CH.sub.2).sub.8 CHCH(CH.sub.2).sub.7 CH.sub.3 bluish red 512 39 ##STR359## CH.sub.3 N[C.sub.9 H.sub.19 (n)].sub.2 orange 469 40 ##STR360## C.sub.2 H.sub.4 OCH.sub.3 N(C.sub.2 H.sub.4 OCH.sub.3).sub.2 red-brown 486 41 ##STR361## C.sub.2 H.sub.4 OC.sub.2 H.sub.5 N[C.sub.3 H.sub.7 (n)].sub.2 reddish blue 592__________________________________________________________________________
TABLE 19__________________________________________________________________________ ##STR362## .lambda.max Hue of (acetone)No. D- Z W Dyed Cloth (nm)__________________________________________________________________________42 ##STR363## CH.sub.2 CH.sub.2 CH.sub.2 OH ##STR364## yellowish red 495 43 ##STR365## " ##STR366## orange 465 44 ##STR367## " N(C.sub.2 H.sub.4 CN).sub.2 bluish red 513 45 ##STR368## CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 N[C.sub.5 H.sub.11 (i)].sub.2 yellowish red 491 46 ##STR369## " ##STR370## red 510 47 ##STR371## CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 NH.sub.2 bluish red 523 48 ##STR372## C.sub.4 H.sub.9 (n) NHC.sub.18 H.sub.37 (n) orange 472__________________________________________________________________________
TABLE 20__________________________________________________________________________ ##STR373## .lambda.max Hue of (acetone)No. D Z W Dyed Cloth (nm)__________________________________________________________________________49 ##STR374## ##STR375## N[C.sub.3 H.sub.7 (i)].sub.2 yellowish red 489 50 ##STR376## " N[C.sub.4 H.sub.9 (n)].sub.2 red-brown 487 51 ##STR377## " NHC.sub.7 H.sub.15 (sec) orange 465 52 ##STR378## CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 ##STR379## red-orange 479 53 ##STR380## " N(C.sub.2 H.sub.4 OCH.sub.3).sub.2 yellowish red 491 54 ##STR381## C.sub.3 H.sub.7 (i) N(C.sub.2 H.sub.4 OH).sub.2 red 505 55 ##STR382## C.sub.2 H.sub.4 OH ##STR383## deep red 511__________________________________________________________________________
TABLE 21__________________________________________________________________________ ##STR384## .lambda.max Hue of (acetone)No. D Z W Dyed Cloth (nm)__________________________________________________________________________56 ##STR385## ##STR386## ##STR387## bluish red 514 57 ##STR388## " NHC.sub.14 H.sub.29 (sec) reddish yellow 469 58 ##STR389## CH.sub.2 CH.sub.2 CH.sub.2 OC.sub.3 H.sub.7 (i) ##STR390## orange 471 59 ##STR391## " ##STR392## red 492 60 ##STR393## CH.sub.2 CH.sub.2 CH.sub.2 OC.sub.3 H.sub.7 (i) N(CH.sub.2CHCH.sub.2).sub.2 " 501 61 ##STR394## C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5 NHC.sub.2 H.sub.5 " " 62 ##STR395## " N[C.sub.3 H.sub.7 (i)].sub.2 " 504__________________________________________________________________________
TABLE 22__________________________________________________________________________ ##STR396## .lambda.max Hue of (acetone)No. D Z W Dyed Cloth (nm)__________________________________________________________________________63 ##STR397## ##STR398## ##STR399## red 505 64 ##STR400## " ##STR401## reddish orange 479 65 ##STR402## C.sub.6 H.sub.13 (i) N[C.sub.3 H.sub.7 (n)].sub.2 yellowish red 491 66 ##STR403## " N[C.sub.7 H.sub.15 (n)].sub.2 bluish red 518 67 ##STR404## CH.sub.2 CH.sub.2 OC.sub.2 H.sub.4 OH ##STR405## orange 466 68 ##STR406## " ##STR407## red 493__________________________________________________________________________
EXAMPLE 13
A dye composition consisting of 15 parts of a disazo dye represented by the formula: ##STR408## 15 parts of a naphthalenesulfonic acid-formaldehyde condensate, and 70 parts of water was finely dispersed by the use of a paint shaker as finely dispersing apparatus to prepare a dye dispersion. This dye dispersion was used to prepare a printing color paste having the following composition:
______________________________________ parts______________________________________Dye dispersion 6.55% Aqueous sodium alginate solution 55Polyethylene glycol dimethyl ether 9having an average molecular weightof 400Water 29.5Total 100 (pH 8.0)______________________________________
The thus prepared printing color paste was printed on a polyester/cotton mixed cloth (mixing ratio: 65/35) by the use of a screen printing machine, was subjected to intermediate drying at 80.degree. C. for 3 minutes, and was fixed by dry heating at 125.degree. C. for 90 seconds. The cloth was then washed with water, and was subjected to soaping using a cleaning liquid containing 2 g/l of a nonionic surface active agent (Scorerol #900 (trade name), produced by Kao Sekken Co., Ltd.) at 80.degree. C. for 20 minutes at a bath ratio of 1:30. There was thus obtained a product dyed in yellowish red having excellent light fastness and wet color fastness.
The dye used in this example was prepared as follows.
In accordance with the usual method, 4-aminoazobenzene was diazotized and coupled with 2-(.gamma.-methoxypropylamino)-3-cyano-4-methyl-6-(m-hydroxyanilino)pyridine to form a dye. A mixture of 5.07 g of the above prepared dye, 2.1 g of 2,4-difluoro-6-(diethyl)aminotriazine, 1.0 g of triethylamine, and 1.0 g of anhydrous potassium carbonate was added to 100 ml of acetone and heated at reflux for 3 hours to achieve a condensation reaction. The reaction solution was then added dropwise to 1,000 ml of water, and the precipitate thus formed was separated by filtration, washed with water, and dried at room temperature to obtain 6.4 g of red powder of the dye represented by the above described formula. For this dye, .lambda.max (acetone) was 490 nm.
EXAMPLE 14
A dye composition consisting of 15 parts of a monoazo dye represented by the formula: ##STR409## 10 parts of a Pluronic surface active agent, Pluronic L64 (trade name, produced by Asahi Denka Kogyo Co., (Ltd.), and 75 parts of water was finely dispersed by the use of a sand grinder as a finely dispersing apparatus to prepare a dye dispersion. This dye dispersion was used to prepare a printing color paste having the following composition:
______________________________________ parts______________________________________Dye dispersion 75% Aqueous sodium alginate solution 55Diacetate of polypropylene glycol 10having an average molecular weightof 300Polyethylene glycol diglycidyl ether 3having an average molecular weightof 200Water 25Total 100 (pH: 6.5)______________________________________
The thus prepared printing color paste was printed on a cotton broad (cotton yarn number: 40) which had been subjected to silket processing, by the use of a screen printing machine, was subjected to intermediate drying at 80.degree. C. for 3 minutes, and was treated using super heated steam at 185.degree. C. for 7 minutes.
Thereafter, a washing processing was performed in the same manner as in Example 13, and there was thus obtained a product dyed in reddish brown having excellent light fastness and wet color fastness.
The dye used in this example was prepared as follows.
In accordance with the usual method, 1-aminoanthraquinone was diazotized and coupled with 2-anilino-3-cyano-4-methyl-6-(4-hydroxybenzylamino)pyridine to form a dye. The dye thus formed was reacted with 2,4-difluoro-6-(N,N-diisopropylamino)triazine in N-methyl-2-pyrrolidone by the use of triethylamine as an acid-removing agent to obtain the desired dye. For this dye, .lambda.max (acetone) was 484 nm.
EXAMPLE 15
A dye composition consisting of 10 parts of a monoazo dye represented by the formula: ##STR410## 2 parts of polyoxyethylene glycol nonylphenyl ether (HLB: 8.9), and 88 parts of diethylene glycol diacetate was ground by the use of a paint conditioner as a finely dispersing apparatus to prepare a dye ink.
A mixture of 10 parts of the above prepared dye ink and 55 parts of mineral turpentine was gradually poured into 35 parts of an aqueous solution having the composition as described hereinafter while stirring by a homomixer at 5,000 to 7,000 rpm, and the resulting mixture was then stirred until it became uniform to obtain a viscous o/w emulsion color paste.
______________________________________Composition of Aqueous Solution parts______________________________________Water 31Repitol G (trade name, special 3.8nonionic surface active agent,produced by Dai-ichi Kogyo SeiyakuCo., Ltd.)Sodium trichloroacetate 0.1Total 34.9______________________________________
The thus prepared color paste was printed on a polyester/cotton mixed cloth (mixing ratio: 65/35) by the use of a screen printing machine, dried at 100.degree. C. for 2 minutes, and treated with super heated steam at 175.degree. C. for 7 minutes. The cloth was washed with a hot tetrachloroethylene bath containing a small amount of water and dried, and there was thus obtained a golden dyed product having excellent light fastness and wet color fastness, and free from contamination in the white background.
The dye used in this example was prepared as follows.
In accordance with the usual method, 2-chloro-4-methylsulfonylaniline was diazotized and coupled with 2-amino-3-cyano-4-methyl-6-(p-hydroxyanilino)pyridine to form a dye. The dye thus formed was reacted at reflux with 2,4-dichloro-6-(n)-hexylaminotriazine in dioxane in the presence of tri-n-butylamine as an acid-removing agent for 3 hours. At the end of the time, the reaction solution was cooled, and crystals separated were collected by filtration to obtain the desired dye. For this dye, .lambda.max (acetone) was 467 nm.
EXAMPLE 16
A dye composition consisting of 16 parts of a disazo dye represented by the formula: ##STR411## 7 parts of polyoxyethylene glycol nonylphenyl ether (HLB: 13.3), 3 parts of a naphthalenesulfonic acid-formaldehyde condensate, and 74 parts of water was finely dispersed by the use of a sand grinder to prepare a dye dispersion. This dye was used to prepare a padding bath having the following composition:
______________________________________ parts______________________________________Dye dispersion 6Tetraethylene glycol dimethyl ether 15Water 79Total 100 (pH: 8.0)______________________________________
A polyester/cotton mixed cloth (mixing ratio: 65/35) was impregnated with the above prepared padding bath, squeezed at a squeezing ratio of 45%, dried at 100.degree. C. for 2 minutes, and fixed by dry heating at 200.degree. C. for 1 minute. The cloth was washed with a hot ethanol bath, and there was thus obtained a product dyed in red having excellent light fastness and wet color fastness.
The dye used in this example was prepared according to the method as described in Example 13. For this dye, .lambda.max (acetone) was 503 nm.
EXAMPLE 17
Printing was performed in the same manner as in Example 13 except that a nylon/rayon mixed cloth (mixing ratio: 50/50) was employed and the dry heating fixing temperature was 185.degree. C. There was obtained a product dyed in red having good light fastness and wet color fastness.
EXAMPLE 18
Using a series of azo dyes as shown in Tables 23 to 30, printing was performed in the same manner as in Example 13.
All dyed clothes had good light fastness and wet color fastness. The hue of each dyed cloth and .lambda.max (acetone) of each dye are shown in Tables 23 to 30.
TABLE 23__________________________________________________________________________ ##STR412## .lambda.max (ace- Hue tone)No. D Z W Dyed (nm)h__________________________________________________________________________ 1 ##STR413## H N(C.sub.2 H.sub.5).sub.2 red 473nge 2 " ##STR414## NHC.sub.2 H.sub.4 OH " 474 3 " C.sub.2 H.sub.4 OCH.sub.3 ##STR415## " " 4 ##STR416## CH.sub.2CHCH.sub.2 ##STR417## deep 514 5 " ##STR418## N[C.sub.3 H.sub.7 (i)].sub.2 " " 6 ##STR419## C.sub.3 H.sub.7 (n) ##STR420## deep 514 7 ##STR421## C.sub.3 H.sub.6 OCH.sub.3 ##STR422## orange 477 8 " C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCH.sub.3 N(C.sub.2 H.sub.4 OCH.sub.3).sub. 2 " " 9 ##STR423## C.sub.3 H.sub.6 OC.sub.2 H.sub.4 ##STR424## reddish yellow 470 10 ##STR425## C.sub.4 H.sub.9 (n) N(CH.sub.2CHCH.sub.2).sub.2 gold 471 11 ##STR426## C.sub.3 H.sub.6 OC.sub.3 H.sub.7 (i) ##STR427## red 504 12 ##STR428## C.sub.2 H.sub.4 OH N(C.sub.2 H.sub.4 CN).sub.2 red 504 13 ##STR429## C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OH ##STR430## " 503 14 ##STR431## " NHC.sub.3 H.sub.7 (i) deep 519 15 ##STR432## C.sub.3 H.sub.6 OH N(n-C.sub.3 H.sub.7).sub.2 orange 471 16 " ##STR433## N(i-C.sub.3 H.sub.7).sub.2 " " 17 ##STR434## C.sub.4 H.sub.9 (i) NHC.sub.6 H.sub.13 (sec) red 495 18 ##STR435## ##STR436## NH.sub.2 reddish blue 595 19 " C.sub.4 H.sub.8 OH N(C.sub.2 H.sub.5).sub.2 " "__________________________________________________________________________
TABLE 24__________________________________________________________________________ ##STR437## .lambda.max Hue of (acetone)No. D Z W Dyed Cloth (nm)__________________________________________________________________________20 ##STR438## C.sub.2 H.sub.4 OH ##STR439## red orange 473 21 ##STR440## C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5 N(C.sub.2 H.sub.4 CN).sub.2 yellowish red 489 22 " H ##STR441## yellowish red " 23 ##STR442## ##STR443## ##STR444## reddish yellow 472 24 ##STR445## C.sub.6 H.sub.13 (n) ##STR446## red-brown 490 25 ##STR447## ##STR448## ##STR449## bluish 517 26 ##STR450## C.sub.5 H.sub.11 (n) ##STR451## red 502 27 ##STR452## C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OH N(CH.sub.3).sub.2 yellow 464 28 ##STR453## ##STR454## ##STR455## red 509 29 ##STR456## C.sub.2 H.sub.4 OC.sub.2 H.sub.5 N[C.sub.4 H.sub.9 (sec)].sub.2 yellowish red 495 30 ##STR457## " ##STR458## yellowish red 494 31 ##STR459## C.sub.2 H.sub.5 " deep red 503 32 " C.sub.3 H.sub.6 OC.sub.3 H.sub.7 ##STR460## deep red " 33 ##STR461## C.sub.3 H.sub.6 OH NHC.sub.7 H.sub.15 (n) deep red 510 34 ##STR462## C.sub.4 H.sub.8 OH N(C.sub.2 H.sub.4 OCH.sub.3).sub.2 deep red 510 35 ##STR463## H N(C.sub.9 H.sub.19).sub.2 orange 475 36 ##STR464## CH.sub.2CHCH.sub.2 N(CH.sub.2CHCH.sub.2).sub.2 red-brown 488__________________________________________________________________________
TABLE 25__________________________________________________________________________ ##STR465## .lambda.max Hue of (acetone)No. D Z W Dyed Cloth (nm)__________________________________________________________________________37 ##STR466## C.sub.2 H.sub.4 OH N[C.sub.3 H.sub.6 N(CH.sub.3).sub.2 ].sub.2 orange 473 38 ##STR467## " ##STR468## yellow 463 39 ##STR469## " ##STR470## red-brown 491 40 ##STR471## C.sub.2 H.sub.4 OC.sub.2 H.sub.5 N(CH.sub.2CHCH.sub.2).sub.2 red 503 41 ##STR472## CH.sub.3 ##STR473## " 506 42 ##STR474## C.sub.3 H.sub.6 OH ##STR475## " 494 43 ##STR476## C.sub.3 H.sub.7 (i) ##STR477## reddish blue 595__________________________________________________________________________
TABLE 26__________________________________________________________________________ ##STR478## .lambda.max Hue of (acetone)No. D Z W Dyed Cloth (nm)__________________________________________________________________________44 ##STR479## C.sub.4 H.sub.9 (i) ##STR480## yellowish red 488 45 ##STR481## H ##STR482## orange 478 46 ##STR483## C.sub.2 H.sub.4 OCH.sub.3 N(C.sub.2 H.sub.5).sub.2 red 504 47 ##STR484## CH.sub.2CHCH.sub.2 N[C.sub.3 H.sub.7 (i)].sub.2 red 508 48 ##STR485## C.sub.3 H.sub.6 OCH.sub.3 N[C.sub.5 H.sub.11 (n)].sub.2 red 510 49 ##STR486## ##STR487## ##STR488## bluish red 524 50 ##STR489## C.sub.2 H.sub.4 OC.sub.3 H.sub.7 (i) ##STR490## orange 471__________________________________________________________________________
TABLE 27__________________________________________________________________________ ##STR491## .lambda.max Hue of (acetone)No. D Z W Dyed (nm)h__________________________________________________________________________51 ##STR492## C.sub.2 H.sub.4 OC.sub.3 H.sub.7 N[C.sub.9 H.sub.19 (n)].sub.2 deep 514 52 ##STR493## ##STR494## N(CH.sub.2 CH.sub.2 CH.sub.2 OH).sub.2 red-brown 488 53 ##STR495## ##STR496## NH(CH.sub.2).sub.8 CHCH(CH.sub.2).sub.7 CH.sub.3 yellow 462 54 ##STR497## C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OH ##STR498## red 507 55 ##STR499## CH.sub.2CHCH.sub.2 N[C.sub.3 H.sub.7 (n)].sub.2 red 508 56 ##STR500## ##STR501## ##STR502## red 493 57 ##STR503## C.sub.3 H.sub.6 OH N[C.sub.4 H.sub.9 (n)].sub.2 red 508 58 ##STR504## C.sub.3 H.sub.6 OH NH.sub.2 deep 510__________________________________________________________________________
TABLE 28__________________________________________________________________________ ##STR505## .lambda.max Hue of (acetone)No. D Z W Dyed Cloth (nm)__________________________________________________________________________59 ##STR506## C.sub.6 H.sub.13 (n) ##STR507## red 502 60 ##STR508## C.sub.2 H.sub. 4 OH N(CH.sub.2CHCH.sub.2).sub.2 " 505 61 ##STR509## ##STR510## N(C.sub.2 H.sub.5).sub.2 reddish yellow 470 62 ##STR511## C.sub.3 H.sub.6 OH ##STR512## orange 472 63 ##STR513## C.sub.4 H.sub.8 OH N(C.sub.2 H.sub.4 OH).sub.2 reddish blue 595__________________________________________________________________________
TABLE 29__________________________________________________________________________ ##STR514## .lambda.max Hue of (acetone)No. D Z W Dyed Cloth (nm)__________________________________________________________________________64 ##STR515## ##STR516## N[C.sub.3 H.sub.7 (n)].sub.2 deep red 514 65 ##STR517## C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCH.sub.3 N[C.sub.6 H.sub. 13 (sec)].sub.2 yellowish red 492 66 ##STR518## C.sub.3 H.sub.7 (i) ##STR519## red-brown 510 67 ##STR520## CH.sub.3 N(C.sub.2 H.sub.4 CN).sub.2 orange 471 68 ##STR521## C.sub.2 H.sub.4 OH N(C.sub.3 H.sub.6 CN).sub.2 red 496__________________________________________________________________________
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Number	Date	Country
56-145943	Sep 1981	JPX
57-208498	Dec 1981	JPX
57-19289	Feb 1982	JPX

Number	Name	Date
4017477	Hegar et al.	Apr 1977
4067864	Obsterlein et al.	Jan 1978
4242259	Harms et al.	Dec 1980
4299764	Jager	Nov 1981

2,6-Diaminopyridine-based azo dyes for cellulose-containing fibers

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