DE4238231A1 - - Google Patents

Description

It was found that very real, brilliant greenish-yellow colorations on fibers and fiber material made of fully or semi-synthetic, high molecular weight, hydrophobic organic compounds obtained if one this with a mixture of disperse dyes containing 25 to 85 Weight percent of a dye of the general formula I

wherein
R₁ optionally substituted once or twice in the phenyl nucleus by chlorine, bromine, C _1-2 alkyl or C _1-4 alkoxy H₅C₆ - (- O-CH₂-CH₂) _n - or phenyl-C _1-3 alkyl,
R₂C _1-6 -alkyl, C _1-6 -alkoxy-C _2-3 -alkyl, hydroxy-C _2-3 -alkoxy-C _2-3 - alkyl or C _1-4 -alkoxy-C _2-3 - alkoxy-C _2-3 alkyl, and
n is 1, 2 or 3,
5 to 50 percent by weight of a dye of the formula II

wherein

R₃ and R₄ C _1-4 alkyl, preferably ethyl and
R₅ is C _1-4 alkyl or a halogen atom, preferably a chlorine atom and 0 to 35 percent by weight of a dye of the formula III or IV

wherein
R₆ C _1-6 alkyl or phenyl-C _1-2 alkyl,
R₇ optionally substituted by 1 or two halogen atoms, preferably chlorine, phenylaminocarbonyl, benzoyl substituted by C _1-4 -alkoxycarbonyl, para-cyclohexylphenyl or, only in formula III, a group of the formula

mean, or a mixture of two or more dyes of the formula I, in which the group of the formula -CO-O-R₁ is preferably bonded in the ortho position to the azo group, in this mixture of dyes, if R₁ is only optionally substituted benzyl, at least 10 percent by weight of one or more dyes, wherein R₂ is C _1-6 alkoxy- C _2-3 alkyl, are contained, while in admixture with at least 10 percent by weight of a dye, wherein R₁ is optionally substituted phenoxyalkyl, any other dyes of the formula I can be present with the group of the formula -CO-O-R₁ in the ortho position to the azo group, colors, block dyed or printed. These disperse dye mixtures are the subject of the present invention.

Mixtures of disperse dyes which are 45 to 75 are preferred Weight percent of a dye of formula I, 15 to 30 weight percent a dye of the formula II and 0 to 30, in particular 15 to 25 percent by weight contain a dye of formula III.  

The disperse dye mixtures are equally preferred of the formula Ia

wherein
R₁ is a benzyl or phenoxy-ethyl group,
R₂ is C _3-4 alkyl or C _1-6 alkoxy-C _2-3 alkyl, preferably n-butyl or C _2-4 alkoxy-C _2-3 alkyl,
wherein in this mixture of dyes, when R₁ is benzyl, at least 10 percent by weight of one or more dyes, in which R₂ is C _1-6 alkoxy- C _2-3 alkyl, are contained, while in a mixture with at least 10 percent by weight of a dye, wherein R₁ is phenoxyalkyl, any other dyes of the formula Ia may be present.

Unless otherwise stated, the alkyl, alkylene and and alkenyl residues straight-chain.

The majority of the individual dyes of the formulas I to IV are known; insofar as they are not known, they can easily be compared to the Prepare the synthesis of similar dyes.

The new dye mixtures are produced by simple mixing of the individual components, what before dispersing (fine grinding) the Dyes or after that can happen. The dye preparations are preferred a common dispersant is added.

The dye mixtures of the formula I are preferably by coupling a diazotized amine or a mixture of diazotized amines Formula V

with a compound or a mixture of compounds of the formula VI

prepared, in the event that in the amine of formula V R₁ uniform Benzyl is used, a mixture of compounds of formula VI is substituted in the at least 10 weight percent alkoxyalkyl and in the event that at least 10 percent by weight of an amine of formula II are used, wherein R₁ is phenoxyalkyl, any other dye components may be present.

The anthranilic acid benzyl or -phenoxyalkyl esters of the formula V are largely known; as far as you have not yet been described, they can be based on a method known to those skilled in the art Be easily made. The pyridone compounds of the formula VI are known. Diazotization and coupling are carried out in the usual way.

The processing of the new disperse dye mixtures into dyeing preparations takes place in a generally known manner, e.g. B. by grinding in the presence of dispersants and / or fillers. With the possibly in Vacuum or spray-dried preparations can, after addition of more or less water, in so-called short or long Color, pad or print the fleet.

The dye mixtures absorb excellently from an aqueous suspension Textile material made from fully synthetic or semi-synthetic, hydrophobic, high molecular organic substances. They are particularly suitable for Dyeing or printing textile material from linear, aromatic polyesters, as well as from cellulose-2½-acetate and cellulose triacetate. You are suitable are excellent for dyeing so-called microfibers also suitable for thermal transfer printing.

You dye or print according to known, z. B. in the French The method described in Patent Specification No. 14 45 371.  

The dyeings obtained have good to very good general fastness properties; The lightfastness, the heat-setting, sublimation and Fastness to pleating. Another advantage of the dyes according to the invention lies in the high build-up capacity, the high pull-out or fixing speed and the good bathroom pull-out.

It is surprising that the fluorescence of those present in the mixture Coumarin dyes (of formula II) even in combination with blue dyes of all classes (e.g. azo, anthraquinone and methine) not deleted is, that is, the green combinations obtained in this way show an excellent Brilliance.

According to the following examples, the dyes in Tables 1 to 3 used. The dyes in Table 1 correspond to the formula I '

Table 1

The dyes in Table 2 correspond to the formula II '

Table 2

The dyes in Table 3 correspond to the formula III '

Table 3

In the following examples, parts are by weight and Percentages by weight; the temperatures are given in degrees Celsius. A part by volume corresponds to the volume of a part by weight Water.

example 1

16.5 T. of dye No. 3 of the formula

5.8 T. of dye No. 11 of the formula

and
7.7 T. of dye No. 15 of the formula

are mechanically mixed in the form of their press cake (based on 100% dye). The resulting mixture is prepared by aqueous grinding with 70 T. of a dispersant based on lignin sulfonate according to known Method an ultradispere dye mixture with a medium particle size of 1 µm and a coupage ratio of 3.0: 10.

8.0 parts of this dye preparation are worn in 2000 parts demineralized 60 ° water containing 40 parts of ammonium sulfate. With 85% formic acid, the pH of the dyebath is adjusted to 5. In this dyebath of approx. 60 °, 100 parts of cleaned polyester fiber fabric are placed, the apparatus closes and heats up over 40 minutes to 130 ° and dye for a further 60 minutes at this temperature. After this Cooling to 40 °, the polyester fiber fabric is removed from the dyebath, rinsed, soaped and reductive with sodium hydrosulfite in the usual way cleaned up. You get a pure greenish yellow color with very good general fastness.

Example 2

If you replace dye No. 3 in Ex. 1 by 18 parts of the dye No. 7 of the formula

and otherwise proceeds as described in Example 1, one also obtains a pure greenish yellow color with very good general fastness properties.  

Similar favorable results are obtained if one analogously to the preceding examples listed in Table 4 below Dyes of the type (I ′) - (III ′) from Tables 1, 2 and 3 are mixed.

Table 4

Example 37

26.5 parts of anthranilic acid-β-phenoxyethyl ester (97%) are in 70 parts Clear glacial acetic acid at 45 ° and with 31 parts hydrochloric acid (36.5%) and 200 Parts of glacial acetic acid added; the resulting suspension is at 0-5 ° 7.2 parts of sodium nitrite, in the form of a 5n solution, as usual diazotized. After destroying the excess nitrous acid with aminosulfonic acid the clarified diazonium salt solution becomes a solution at 5-10 ° containing 11.0 parts of the coupling component of formula a and 13.9 parts the coupling component of formula b,

10 parts of glacial acetic acid and 400 parts of ice water, with good stirring at pH 4-5 run up. The pH is adjusted by adding sodium hydroxide solution (30%) Range kept constant from 4-5. The resulting yellow suspension is filtered off, washed with 1000 parts of water at 50 ° acid-free and the dye dried in vacuo at 40 °. Can be used for further cleaning the dye mixture z. B. recrystallized from cellosulve as a solvent will.

This gives a dye mixture of the formula c

the PES fibers in a greenish-yellow shade with very good General fastness colors.

The following Table 5 shows further dye mixtures of the formula Ia ′

specified where R₅ is hydrogen in all cases, except in the 1st Dye of Example 51, for which R₅ is methyl in the 5'-position.

These dye mixtures can be analogous to the working instructions of the Manufacture example 1, but can equally well instead of a mixed coupling also produced by subsequently mixing the individual components will.  

Table 5

Example 57

24.8 parts of anthranilic acid benzyl ester (98%) in 100 parts of glacial acetic acid of 45 ° clearly dissolved and with 35 parts of hydrochloric acid (36.5%) and 150 parts Ice water added; the resulting suspension is at 0-5 ° with 7.2 Parts of sodium nitrite, in the form of a 5n solution, diazotized as usual. After destroying the excess nitrous acid with aminosulfonic acid the clarified diazonium salt solution becomes a solution at 5-10 ° containing 22.5 parts of the coupling component of formula d and 2.8 parts the coupling component of formula e,

10 parts of glacial acetic acid and 400 parts of ice water with good stirring at pH 4-5 run up. The pH is adjusted by adding sodium hydroxide solution (30%) Range kept constant from 4-5. The resulting yellow suspension is filtered off, washed with 1000 parts of water at 50 ° acid-free and the dye dried in vacuo at 40 °. Can be used for further cleaning the dye mixture z. B. recrystallized from cellosolve as a solvent will.

This gives a dye mixture of the formula f

the PES fibers in a greenish-yellow shade with very good general fastness properties colors.

In the following Table 6 further dye mixtures are given, they correspond to the formula Ia ′ ′,

for which the variables are listed in Table 6.

These dye mixtures can be analogous to the working instructions of the Manufacture Example 37, but can equally well instead of a mixed coupling can also be obtained by subsequently mixing the individual components.  

Table 6

Application example

The dye mixture obtained according to Example 1 is by means of Sand grinding in the presence of dispersants, e.g. B. commercial Lignin sulfonate, and then atomized into an ultradisperse Dye preparation with an average particle size of 1 µm and a coupage ratio transferred from 3.5: 10.

12 parts of this preparation are antidispersed with 1000 parts of water and of the circulating liquor (13,000 parts containing 30 parts ammonium sulfate and 0.3 parts of formic acid as a buffer and optionally a carrier - / - Leveling agent combination) added at 60 °. The pre-cleaned, pressed Cross-wound bobbin (1000 parts of polyester yarn on a plastic tube) is inserted, the autoclave was sealed and heated to 130 ° in 35 minutes. After 90 minutes, the mixture is cooled to 80 ° and the liquor drawn off is drained off and thoroughly washed the thus colored substrate with cold water and reductively cleaned in the usual way. Then it swings down and dried. A level, pure yellow color is obtained.

Claims (4)

1. Mixture of disperse dyes containing 25 to 85 percent by weight of a dye of the general formula I. wherein
R₁ optionally substituted once or twice in the phenyl nucleus by chlorine, bromine, C _1-2 alkyl or C _1-4 alkoxy H₅C₆ - (- O-CH₂-CH₂) _n - or phenyl-C _1-3 alkyl,
R₂C _1-6 -alkyl, C _1-6 -alkoxy-C _2-3 -alkyl, hydroxy-C _2-3 -alkoxy- C _2-3 -alkyl or C _1-4 -alkoxy-C _2-3 - alkoxy-C _2-3 alkyl, and
n is 1, 2 or 3,
5 to 50 percent by weight of a dye of the formula II wherein R₃ and R₄ C _1-4 alkyl, preferably ethyl and
R₅ C _1-4 alkyl or a halogen atom, preferably a chlorine atom and 0 to 35 percent by weight of a dye of the formula III or IV wherein
R₆ C _1-6 alkyl or phenyl-C _1-2 alkyl,
R₇ optionally substituted by 1 or two halogen atoms, preferably chlorine, phenylaminocarbonyl, benzoyl substituted by C _1-4 -alkoxycarbonyl, para-cyclohexylphenyl or, only in formula III, a group of the formula mean, or a mixture of two or more dyes of the formula I, in which the group of the formula -CO-O-R₁ is preferably bonded in the ortho position to the azo group, in this mixture of dyes, if R₁ is only optionally substituted benzyl, at least 10 percent by weight of one or more dyes, wherein R₂ is C _1-6 alkoxy- C _2-3 alkyl, are contained, while in admixture with at least 10 percent by weight of a dye, wherein R₁ is optionally substituted phenoxyalkyl, any other dyes of the formula I can be present with the group of the formula -CO-O-R₁ in the ortho position to the azo group. 2. Mixtures of disperse dyes according to claim 1, containing 45 to 75 percent by weight of a dye of the general formula I, preferably 15 to 30 percent by weight of a dye of formula II and 0 to 30 preferably 15 to 25 percent by weight of a dye Formula III.   3. Mixtures of disperse dyes according to claim 1, the formula Ia wherein
R₁ is a benzyl or phenoxy-ethyl group,
R₂ is C _3-4 alkyl or C _1-6 alkoxy-C _2-3 alkyl, preferably butyl or C _2-4 alkoxy-C _2-3 alkyl,
wherein in this mixture of dyes, when R₁ is benzyl, at least 10 percent by weight of one or more dyes, in which R₂ is C _1-6 alkoxy- C _2-3 alkyl, are contained, while in a mixture with at least 10 percent by weight of a dye, wherein R₁ is phenoxyalkyl, any other dyes of the formula Ia may be present. 4. Use of the dye mixtures according to claim 1, 2 or 3, for dyeing or printing fibers or threads or from them Material made from fully or semi-synthetic, hydrophobic, high molecular weight organic substances.