CA1169052A - 1:2 chromium and cobalt complex dyes - Google Patents
1:2 chromium and cobalt complex dyesInfo
- Publication number
- CA1169052A CA1169052A CA000381720A CA381720A CA1169052A CA 1169052 A CA1169052 A CA 1169052A CA 000381720 A CA000381720 A CA 000381720A CA 381720 A CA381720 A CA 381720A CA 1169052 A CA1169052 A CA 1169052A
- Authority
- CA
- Canada
- Prior art keywords
- chromium
- dye
- mixture
- formula
- complex
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B45/00—Complex metal compounds of azo dyes
- C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
- C09B45/14—Monoazo compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
Abstract of the Disclosure The novel asymmetrical 1:2 metal complex dyes of the formula I as defined in claim 1, and mixtures thereof with the metal complex dyes of the formula II and III, are suitable for dyeing and printing natural or synthetic polyamide material.
Printing pastes or padding liquors prepared from these dyes or mixtures have no tendency to gel.
Printing pastes or padding liquors prepared from these dyes or mixtures have no tendency to gel.
Description
3 a s 2 Case 1-12963/=
1: 2 Chromium and cobal t compl ex dyes The present invention relates to 1: 2 metal complex dyes o~ the formula I
i i~
\ i/ ¦ Q (I) ~e ~3 wherein Me is chromilLm or cobalt and Q~33 is a ca~ion, and mixtures thereof with the me~al complex dyes of the . formulae II and III
.
.
, ., 0 5 ~
~ ~OC~3 O ~ COC';~3 ~ (~) 7~ ~ i, ~1' b ~ ,i1 Q~) ~1' b = ~ ! Q~3 Me (II) ~1@ (III) whereinMeand Q~ have the above mèanings. Q0 is the cation of an alkali metalg in particular a sodium or lithium cation, or is also an ammonium ion or the cation of an organic amine, e.g. of triethanolamine.
The symmetrical chromium complexes of the above form~e II and III are known. The 1:2 chromium or cobalt complexes of the formula II gel in conventional padding liquors or prin~ing pastes, so that these are normal-ly unfit for use. ~he wetastness properties of the 1:2 chromium complex dye of the :formula III are not satisfactory in all respects.
Accordingly, it is the objezt of the present in~ention to provide similar dyes which do not have these drawbacks. This objeck is accomplished by means of the dyes 6~ûS2 and/or dyestuff mixtures of this inventionO Surprisingly9 ~ padding liquors or printing pastes containing the 1:2 i chromium complex dye of the formula I, or mixtures of the 1:2 chromium or cobalt complex dyes of the formulae I, II
and II~ do not gel,and ~he wetfastness properties are better than those of the 1:2 chromium complex dye of the formula - III.
Preferred metal complex dyes of the formula I, and mixtu~es thereof with the metal complex dyes of the j formulaeII and III,are the chromium complex dyes.
The mixtures of the metal complexes of the formulae I, II and III are obtained e.g. by reacting a mixture of the azo dyes of the ~ormulae IV and V
!
. ~X
(IV) ~ / ( ~2~2 2 ~
Ca3 with a cobalt or, preferably~ a chromium donor. The reaction is carried out by suspending the azo dyes of the ~ormulae IV and V in water, an organic solvent or a mixture of water and an organic solvent, adding a chromium or cobalt donor, stirring the mixture preferably in the temperature ra~ge from 80 to 100C, and adjusting the pH to a value between 6 and 9.
The composition of the mixture can be varied by appropriate choice of the ra~io of the dyes of the formulae IV and V employed for the metallisa~ion. It is .~, . .
' ' - ~ .
' preferred to use both dyes in the molar ratio of 35:65 to 65:35, in particular 45:55 to 55:45.
The purP asymmetrical chromium complex dye of the fo~mula VI
_ oac~3 ~ ~) S02NP,2 .~ ~.
~ ~ !, \ // Q (3 (Vl) Cr jC/~ q\il I
,1~ i go2N~2L~.~
ca3 wherein ~ is a c~tion3 is obtained by firs~ preparing the 1:1 chromium co~plex of the dye of the formula IV
~ ~o ~
.~ 2 C~OC~3 '' . ' ' .
, s ~
- s -or the l:l chromium complex of the dye of the formula V
(v) ::1 c~3 11 and then reacting this complex with the d~re of the form~la V
.,~ or IV ~o give the 1:~ chromium complex dye of the formula VI, which constitutes a preferred embodiment of the dyes of the ;~ present invention. This reaction is carried out by suspending the 1:1 chromium complex of the dye of the ormula IV or V in water, an organic solvent or a mixture : of water and an organic solven~, adding the dye of the formula V or IV, stirring the mixtura in the temperature range from 80 to 100C, adjusting the pH to a value . between 6 and 9, and, finally, isolating the 1:2 chromium complex dye of ~he.formula VI from the reaction solutionu , . The me~allisation is carried out by conventional methods~ e.g. with cobalt ~lfate or cobal~ aeetate or wi~h sodium chromwsalicylate, in neutral or we~kly alkaline :! solution. To obtain the dyes of the formula VI it is ~ :
` preferred to prepare irst, in acid solution, the 1:1 j chromium complex of the azo compound of the formula IV or V
1 and then to react this 1:1 complex, in neutral to weakly alkaline medium, wi~h the azo compound of the formula V or Exampl~s of suitabLe organic solvents are ketones, e.g. me~hyl isobutyl ketone~ or alcohols, e.g. glycol or -- butanol.
., .~
..
. ,' . .: ~-. ' ~ ' :. . . . .
.. ; ~ . . -:
I I B~ 0 5 2 The metal complex dyes obtainable by the above process are isolated in the form of their salts, preferably th~ alkali me~al salts, most preerably sodium or lithium salts, or also ammonium salts or salts of organic amines having a positively charged nitrogen atom, and they are suitable for dyeing and printing a variety of ~abrics, especially for dyeing ni~rogen-containing fabrics such as silk, leather and, in psr~icular, wool, as well as synthetic fibres made rom polyamides or polyurethanes. They are suitable, in particul~r, for dyeing from a weakly alkaline , neutral or weakly acid bath, e.g. from a bath containing acetic acid. The dyeings obtained are level and have good fastness to light, washing, water, hot w2ter, fulling, decatising and carbonising.
The 1:2 chromium complex dyes o the formula I, and the mixtures of the 1:2 rhromium or cobalt compLex dyes of the formulae I7 II and III, are of particular advantage when used in aqueous padding liquors or printing pastes, as no problems du~ to gelling occur.
The padding liquors or printing pastes usually contain further ingredients, e g. ~etting agents, antifoamsa or agents which affect the properties of the fabric, e.g~ softeners, flame retardants, or dirt, water and oil repellents, especially, hawever, natural or synthetic thickeners.
Examples of suitable neutral thickeners are caxob seed gum ether; starch ether, alginates, starch, tragacanth, carboxy~ethyl celiulose and cellulo.se ethers.
Examples of suitable synthetîc thickeners are high molecular mono- or copolymers of acrylic acid, methacrylic acid or maleic a~id, with ethylenically unsaturated - ~ .
9~ 2 comonomers such as ethylene, butadiene, hydxoxyalkyl-acrylates, divinyldioxane and divinylbenzne, in the form of water-soluble alkali metal, ammonium or amine salts.
The pad dyeing or printing is carried out by conventional methods.
The invention is illustrated by the following Examples, in which parts and percentages are by weight, unless otherwise stated.
, ~ .
.
' ' :
"'~" . ' ' . .
.
:. .
9~52 . -- 8 --20 . 8 parts of the dye of the formula IV
N - 7~ ~.
1: 2 Chromium and cobal t compl ex dyes The present invention relates to 1: 2 metal complex dyes o~ the formula I
i i~
\ i/ ¦ Q (I) ~e ~3 wherein Me is chromilLm or cobalt and Q~33 is a ca~ion, and mixtures thereof with the me~al complex dyes of the . formulae II and III
.
.
, ., 0 5 ~
~ ~OC~3 O ~ COC';~3 ~ (~) 7~ ~ i, ~1' b ~ ,i1 Q~) ~1' b = ~ ! Q~3 Me (II) ~1@ (III) whereinMeand Q~ have the above mèanings. Q0 is the cation of an alkali metalg in particular a sodium or lithium cation, or is also an ammonium ion or the cation of an organic amine, e.g. of triethanolamine.
The symmetrical chromium complexes of the above form~e II and III are known. The 1:2 chromium or cobalt complexes of the formula II gel in conventional padding liquors or prin~ing pastes, so that these are normal-ly unfit for use. ~he wetastness properties of the 1:2 chromium complex dye of the :formula III are not satisfactory in all respects.
Accordingly, it is the objezt of the present in~ention to provide similar dyes which do not have these drawbacks. This objeck is accomplished by means of the dyes 6~ûS2 and/or dyestuff mixtures of this inventionO Surprisingly9 ~ padding liquors or printing pastes containing the 1:2 i chromium complex dye of the formula I, or mixtures of the 1:2 chromium or cobalt complex dyes of the formulae I, II
and II~ do not gel,and ~he wetfastness properties are better than those of the 1:2 chromium complex dye of the formula - III.
Preferred metal complex dyes of the formula I, and mixtu~es thereof with the metal complex dyes of the j formulaeII and III,are the chromium complex dyes.
The mixtures of the metal complexes of the formulae I, II and III are obtained e.g. by reacting a mixture of the azo dyes of the ~ormulae IV and V
!
. ~X
(IV) ~ / ( ~2~2 2 ~
Ca3 with a cobalt or, preferably~ a chromium donor. The reaction is carried out by suspending the azo dyes of the ~ormulae IV and V in water, an organic solvent or a mixture of water and an organic solvent, adding a chromium or cobalt donor, stirring the mixture preferably in the temperature ra~ge from 80 to 100C, and adjusting the pH to a value between 6 and 9.
The composition of the mixture can be varied by appropriate choice of the ra~io of the dyes of the formulae IV and V employed for the metallisa~ion. It is .~, . .
' ' - ~ .
' preferred to use both dyes in the molar ratio of 35:65 to 65:35, in particular 45:55 to 55:45.
The purP asymmetrical chromium complex dye of the fo~mula VI
_ oac~3 ~ ~) S02NP,2 .~ ~.
~ ~ !, \ // Q (3 (Vl) Cr jC/~ q\il I
,1~ i go2N~2L~.~
ca3 wherein ~ is a c~tion3 is obtained by firs~ preparing the 1:1 chromium co~plex of the dye of the formula IV
~ ~o ~
.~ 2 C~OC~3 '' . ' ' .
, s ~
- s -or the l:l chromium complex of the dye of the formula V
(v) ::1 c~3 11 and then reacting this complex with the d~re of the form~la V
.,~ or IV ~o give the 1:~ chromium complex dye of the formula VI, which constitutes a preferred embodiment of the dyes of the ;~ present invention. This reaction is carried out by suspending the 1:1 chromium complex of the dye of the ormula IV or V in water, an organic solvent or a mixture : of water and an organic solven~, adding the dye of the formula V or IV, stirring the mixtura in the temperature range from 80 to 100C, adjusting the pH to a value . between 6 and 9, and, finally, isolating the 1:2 chromium complex dye of ~he.formula VI from the reaction solutionu , . The me~allisation is carried out by conventional methods~ e.g. with cobalt ~lfate or cobal~ aeetate or wi~h sodium chromwsalicylate, in neutral or we~kly alkaline :! solution. To obtain the dyes of the formula VI it is ~ :
` preferred to prepare irst, in acid solution, the 1:1 j chromium complex of the azo compound of the formula IV or V
1 and then to react this 1:1 complex, in neutral to weakly alkaline medium, wi~h the azo compound of the formula V or Exampl~s of suitabLe organic solvents are ketones, e.g. me~hyl isobutyl ketone~ or alcohols, e.g. glycol or -- butanol.
., .~
..
. ,' . .: ~-. ' ~ ' :. . . . .
.. ; ~ . . -:
I I B~ 0 5 2 The metal complex dyes obtainable by the above process are isolated in the form of their salts, preferably th~ alkali me~al salts, most preerably sodium or lithium salts, or also ammonium salts or salts of organic amines having a positively charged nitrogen atom, and they are suitable for dyeing and printing a variety of ~abrics, especially for dyeing ni~rogen-containing fabrics such as silk, leather and, in psr~icular, wool, as well as synthetic fibres made rom polyamides or polyurethanes. They are suitable, in particul~r, for dyeing from a weakly alkaline , neutral or weakly acid bath, e.g. from a bath containing acetic acid. The dyeings obtained are level and have good fastness to light, washing, water, hot w2ter, fulling, decatising and carbonising.
The 1:2 chromium complex dyes o the formula I, and the mixtures of the 1:2 rhromium or cobalt compLex dyes of the formulae I7 II and III, are of particular advantage when used in aqueous padding liquors or printing pastes, as no problems du~ to gelling occur.
The padding liquors or printing pastes usually contain further ingredients, e g. ~etting agents, antifoamsa or agents which affect the properties of the fabric, e.g~ softeners, flame retardants, or dirt, water and oil repellents, especially, hawever, natural or synthetic thickeners.
Examples of suitable neutral thickeners are caxob seed gum ether; starch ether, alginates, starch, tragacanth, carboxy~ethyl celiulose and cellulo.se ethers.
Examples of suitable synthetîc thickeners are high molecular mono- or copolymers of acrylic acid, methacrylic acid or maleic a~id, with ethylenically unsaturated - ~ .
9~ 2 comonomers such as ethylene, butadiene, hydxoxyalkyl-acrylates, divinyldioxane and divinylbenzne, in the form of water-soluble alkali metal, ammonium or amine salts.
The pad dyeing or printing is carried out by conventional methods.
The invention is illustrated by the following Examples, in which parts and percentages are by weight, unless otherwise stated.
, ~ .
.
' ' :
"'~" . ' ' . .
.
:. .
9~52 . -- 8 --20 . 8 parts of the dye of the formula IV
N - 7~ ~.
2~2 1 and 20 parts of the dye of the formNla V
= N ~ ~;
i !~ ,i! ~ , ~f ~2~2 C~l are heated in a reflux condenser, in 800 partQ by volume ~:~ of water, with 156 parts by volume of a solu~ion of sodium chromosalicylate (-3.25 parts of chromium)~ until the starting dyes can no longer be detected. The mix~ure of
= N ~ ~;
i !~ ,i! ~ , ~f ~2~2 C~l are heated in a reflux condenser, in 800 partQ by volume ~:~ of water, with 156 parts by volume of a solu~ion of sodium chromosalicylate (-3.25 parts of chromium)~ until the starting dyes can no longer be detected. The mix~ure of
3 chromium-containing dyes is salted out of ~he resultant : dark bluish-grey solu~ion with sodium chloride. The j : precipitate is isvlated by filtration and dried, affording :~ : a bluish-black powder which is soluble in hot water and :' dyes wo~l from a neutral to weakly acid dye bath in grey ~, shade~ o~ good fastness propertiesO
~ ~;9U52 Grey dyestuff mixtures having similar properties are obtained by replacing, in this Example~ 20.8 parts of the dye of formula IV and 20 parts of the dye of formula V by the amounts indicated in the follo~ing table:
No. Dye of the formula IV Dye of the formuLa V
1 16.6 parts 24 parts 2 18~7 parts 22 parts 3 22.9 parts 18 parts
~ ~;9U52 Grey dyestuff mixtures having similar properties are obtained by replacing, in this Example~ 20.8 parts of the dye of formula IV and 20 parts of the dye of formula V by the amounts indicated in the follo~ing table:
No. Dye of the formula IV Dye of the formuLa V
1 16.6 parts 24 parts 2 18~7 parts 22 parts 3 22.9 parts 18 parts
4 24.9 parts 16 parts 20.8 parts of the dye of formula IV and 20 parts of the dye of formMla V are stirred in 800 par~s by volume of water with 14.8 parts of cobalt sulfahep~ahydrate ~-3.1 par~s of cobalt) at 90 95C until no more starti~g dye can be detec~ed~ while keeping the pH of the reaction mixture at abou~ 7 by addition of approx. 5N sodium hydroxide, The mixture of cobalt-containing dyes is then precipitated with sodium chloxide solution. The precipitate is isolat d by iltration and dried) affording a dark powder which dyes wool from a neutral to weakly acid bath in very fast corinth shades.
A dyes~uff mixture having s~milar ~inctorial properties is obtained by replacing, in this Example, the 20~8 parts of the dye of formula IV by 22,9 parts of the same dye and the 20 parts of the dye of onmu1a V by 18 parts of the same dye, ., ~: `
~i ~
`~ .
~ . , ~ 52 ~e~
~ coca3 ~ ~) ~ D\ ssI~
\ 1/ Na~
.~q~
cooca 3 _ 23.3 part.s o the 1:1 chromium complex compound correspondlng to 2.6 parts of chromium and 20.8 parts of the monoazo dye of the formula IV (obt~ined by methods known per sel e.g, by chromi~g the monoazo dye in butanol with chromium chloride he~ahydride) and 20 parts of the noazo dye of the formula V, are suspended in 250 parts by volume of ethylene gylcol. The mixture is heated to 80-85C, while simultaneously raising the pH o~ the suspensio~ to 7~7.5 with 5N NaOH, and is kep~ at t~is temperature and constant pH (with further addition of 5N
NaOH) until the starting materials can no longer be detected. The chromium-containing dye of the above fonmula is then precipitated with sodium chloride solution, The precipi~ate is isolated by filtration and dried9 afford-ing a dark powder which forms a grey solution in water and dy~s wool in faqt grey shades~
~ ~ 8~ 052 i Example 4:
A printing paste of the follow~ng composition is prepared:
30 g of the dyestuff mixture of Example 1 50 g of thiodiglycol 1 260 g of boiling water 100 g of urea 500 g of thickener solution based on carob bean gum 60 g of ammonium tartrate ~15 Be) __ . 1000 g I
Th~s pas~e is mos~ suitable for prin~ing on account o its consistency and keeps its good properties even aPer standing for several days. It does not gel.
A wool or polyamide fabric is printed with this paste and steamed for 20-30 minutes at 0.2 bar (102-104 C).
The grey printed abric has good fastness properties.
espeeially wetfastness.
Replacing the dyestuff mixture of Example 1 by the sam~ amount o~ the symmetrical L:2 chromium complex of ~he dye of formula VI gives a printing paste which g ls : strongly and is ther fore no longer fit or printing.
' ' 2 parts of the dyestuff mixture of Example 1 are : dissolved in 4000 parts of water. Into this bath are put 100 parts of wool at 50C and ~hen 3 parts of ammonium acetate are added. The bath is then heated over 45 mînutes : to the boil and kept at this temperature for 1 1/2 hours, while turning the w901 well in the bath. The wool is , . . -. ... ...
.
A
' ~' ' '~
~ :~ 690 subsequen~ly rinsed and dried. It is dyed in a grey shade of good fastness proper~ies.
' .
.; :
.
A dyes~uff mixture having s~milar ~inctorial properties is obtained by replacing, in this Example, the 20~8 parts of the dye of formula IV by 22,9 parts of the same dye and the 20 parts of the dye of onmu1a V by 18 parts of the same dye, ., ~: `
~i ~
`~ .
~ . , ~ 52 ~e~
~ coca3 ~ ~) ~ D\ ssI~
\ 1/ Na~
.~q~
cooca 3 _ 23.3 part.s o the 1:1 chromium complex compound correspondlng to 2.6 parts of chromium and 20.8 parts of the monoazo dye of the formula IV (obt~ined by methods known per sel e.g, by chromi~g the monoazo dye in butanol with chromium chloride he~ahydride) and 20 parts of the noazo dye of the formula V, are suspended in 250 parts by volume of ethylene gylcol. The mixture is heated to 80-85C, while simultaneously raising the pH o~ the suspensio~ to 7~7.5 with 5N NaOH, and is kep~ at t~is temperature and constant pH (with further addition of 5N
NaOH) until the starting materials can no longer be detected. The chromium-containing dye of the above fonmula is then precipitated with sodium chloride solution, The precipi~ate is isolated by filtration and dried9 afford-ing a dark powder which forms a grey solution in water and dy~s wool in faqt grey shades~
~ ~ 8~ 052 i Example 4:
A printing paste of the follow~ng composition is prepared:
30 g of the dyestuff mixture of Example 1 50 g of thiodiglycol 1 260 g of boiling water 100 g of urea 500 g of thickener solution based on carob bean gum 60 g of ammonium tartrate ~15 Be) __ . 1000 g I
Th~s pas~e is mos~ suitable for prin~ing on account o its consistency and keeps its good properties even aPer standing for several days. It does not gel.
A wool or polyamide fabric is printed with this paste and steamed for 20-30 minutes at 0.2 bar (102-104 C).
The grey printed abric has good fastness properties.
espeeially wetfastness.
Replacing the dyestuff mixture of Example 1 by the sam~ amount o~ the symmetrical L:2 chromium complex of ~he dye of formula VI gives a printing paste which g ls : strongly and is ther fore no longer fit or printing.
' ' 2 parts of the dyestuff mixture of Example 1 are : dissolved in 4000 parts of water. Into this bath are put 100 parts of wool at 50C and ~hen 3 parts of ammonium acetate are added. The bath is then heated over 45 mînutes : to the boil and kept at this temperature for 1 1/2 hours, while turning the w901 well in the bath. The wool is , . . -. ... ...
.
A
' ~' ' '~
~ :~ 690 subsequen~ly rinsed and dried. It is dyed in a grey shade of good fastness proper~ies.
' .
.; :
.
Claims (13)
1. A 1:2 metal complex dye of the formula I
(I) wherein Me is chromium or cobalt and Q? is a cation, or a mixture thereof with the metal complex dyes of the formulae II and III
(II) (III) wherein Me and Q? have the above meanings.
(I) wherein Me is chromium or cobalt and Q? is a cation, or a mixture thereof with the metal complex dyes of the formulae II and III
(II) (III) wherein Me and Q? have the above meanings.
2. A metal complex dye of the formula I, or a mixture thereof with the metal complex dyes of the formulae II and III, wherein Me is chromium.
3. A 1:2 chromium complex dye of the formula VI
(VI) wherein Q? is a cation.
(VI) wherein Q? is a cation.
4. A process for the production of a mixture of the 1:2 metal complex dyes of the formulae I, II and III
(I) (II) (III) wherein Me is chromium or cobalt and Q? is a cation, which process comprises reacting a mixture of the azo dyes of the formulae IV and V
(IV) (V) with a chromium or cobalt donor.
(I) (II) (III) wherein Me is chromium or cobalt and Q? is a cation, which process comprises reacting a mixture of the azo dyes of the formulae IV and V
(IV) (V) with a chromium or cobalt donor.
5. A process according to claim 4, which comprises reacting a mixture of the azo dyes of the formula IV and V, in the molar ratio of 35:65 to 65:35, preferably 45:55 to 55:45, with a chromium or cobalt donor.
6. A process for the production of a 1:2 chromium complex dye of the formula VI
(VI) wherein Q? is a cation, which process comprises preparing first the 1:1 chromium complex of the dye of the formula IV
(IV) or the 1:1 chromium complex of the dye of the formula V
(V) and subsequently reacting said complex with the dye of the formula V or IV to give the 1:2 chromium complex dye of the formula VI.
(VI) wherein Q? is a cation, which process comprises preparing first the 1:1 chromium complex of the dye of the formula IV
(IV) or the 1:1 chromium complex of the dye of the formula V
(V) and subsequently reacting said complex with the dye of the formula V or IV to give the 1:2 chromium complex dye of the formula VI.
7. A mixture of the 1:2 metal complex dyes of the formulae I, II and III
(I) (II) (III) wherein Me is chromium or cobalt and Q? is a cation, said mixture being obtained by reacting a mixture of the azo dyes of the formulae IV and V
(IV) (V) with a chromium or cobalt donor.
(I) (II) (III) wherein Me is chromium or cobalt and Q? is a cation, said mixture being obtained by reacting a mixture of the azo dyes of the formulae IV and V
(IV) (V) with a chromium or cobalt donor.
8. A mixture according to claim 7, said mixture being obtained by preparing a suspension of the azo dyes of the formulae IV and V
(IV) (v) in water, an organic solvent or a mixture of water and an organic solvent, adding a chromium or cobalt donor, stirring the mixture in the temperature range from 80° to 100°C, adjusting the pH to a value between 6 and 9, and, finally, isolating the mixture of the chromium or cobalt-containing dyes from the reaction solution.
(IV) (v) in water, an organic solvent or a mixture of water and an organic solvent, adding a chromium or cobalt donor, stirring the mixture in the temperature range from 80° to 100°C, adjusting the pH to a value between 6 and 9, and, finally, isolating the mixture of the chromium or cobalt-containing dyes from the reaction solution.
9. A dyestuff mixture according to either of claims 7 or 8, said mixture being obtained by reacting a mixture of the azo dyes of the formulae IV and V in the molar ratio of 35:65 to 65:35, preferably 45:55 to 55:45, with a chromium or cobalt donor.
10 . A 1:2 chromium complex dye of the formula VI
(VI) wherein Q? is a cation,said complex dye being obtained by preparing the 1:1 chromium complex of the dye of the formula IV
(IV) or the 1:1 chromium complex of the dye of the formula V
(V) and then suspending said complex in water, an organic solvent or a mixture of water and an organic solvent, adding the dye of the formula V or IV, stirring the mixture in the temperature range from 80° to 100°C, adjusting the pH to a value between 6 and 9, and, finally, isolating the dye of the formula VI from the reaction solution.
(VI) wherein Q? is a cation,said complex dye being obtained by preparing the 1:1 chromium complex of the dye of the formula IV
(IV) or the 1:1 chromium complex of the dye of the formula V
(V) and then suspending said complex in water, an organic solvent or a mixture of water and an organic solvent, adding the dye of the formula V or IV, stirring the mixture in the temperature range from 80° to 100°C, adjusting the pH to a value between 6 and 9, and, finally, isolating the dye of the formula VI from the reaction solution.
11. A process for the preparation of non-gelling dye baths, padding liquors or printing pastes, which includes the use of a dye according to either of claims 1 or 2.
12. A method of dyeing or printing natural or synthetic polyamide material, which comprises the use of a dye according to any one of claims 1 to 3.
13. A dyed or printed natural or synthetic polyamide material having applied thereto a dye according to claims 1, 2, or 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH545680 | 1980-07-16 | ||
| CH5456/80-7 | 1980-07-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1169052A true CA1169052A (en) | 1984-06-12 |
Family
ID=4293898
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000381720A Expired CA1169052A (en) | 1980-07-16 | 1981-07-14 | 1:2 chromium and cobalt complex dyes |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0045276B1 (en) |
| JP (2) | JPS5912695B2 (en) |
| BR (1) | BR8104525A (en) |
| CA (1) | CA1169052A (en) |
| DE (1) | DE3160489D1 (en) |
| ES (1) | ES503976A0 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4452602A (en) * | 1981-03-23 | 1984-06-05 | Puentener Alois | Process for dyeing leather with mixtures of dyes |
| US4611890A (en) * | 1984-01-24 | 1986-09-16 | Research Corporation | Redox chromophore compounds and electrodes of metal containing substituted bipyridines |
| JPS60138788U (en) * | 1984-02-28 | 1985-09-13 | 株式会社 きもと | A writing sheet that can be written on and erased on the design. |
| JPS6183986U (en) * | 1984-11-08 | 1986-06-03 | ||
| JPS6247416U (en) * | 1985-09-12 | 1987-03-24 | ||
| JPS63173826U (en) * | 1987-05-06 | 1988-11-11 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2499133A (en) * | 1945-12-18 | 1950-02-28 | Allied Chem & Dye Corp | Monazo dyestuff |
| US2610175A (en) * | 1949-11-18 | 1952-09-09 | Ciba Ltd | Complex chromium compounds of monoazo-dyestuffs |
| US2813853A (en) * | 1954-06-29 | 1957-11-19 | Saul & Co | Monoazo dyestuffs and metal complex compounds thereof |
| BE633094A (en) * | 1962-02-09 |
-
1981
- 1981-07-10 EP EP19810810278 patent/EP0045276B1/en not_active Expired
- 1981-07-10 DE DE8181810278T patent/DE3160489D1/en not_active Expired
- 1981-07-14 CA CA000381720A patent/CA1169052A/en not_active Expired
- 1981-07-15 ES ES503976A patent/ES503976A0/en active Granted
- 1981-07-15 BR BR8104525A patent/BR8104525A/en unknown
- 1981-07-16 JP JP11011181A patent/JPS5912695B2/en not_active Expired
-
1983
- 1983-07-01 JP JP11835183A patent/JPS6052175B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5912695B2 (en) | 1984-03-24 |
| JPS6052175B2 (en) | 1985-11-18 |
| JPS59172552A (en) | 1984-09-29 |
| BR8104525A (en) | 1982-03-30 |
| ES8203939A1 (en) | 1982-04-16 |
| DE3160489D1 (en) | 1983-07-28 |
| ES503976A0 (en) | 1982-04-16 |
| EP0045276A3 (en) | 1982-02-17 |
| JPS5749662A (en) | 1982-03-23 |
| EP0045276A2 (en) | 1982-02-03 |
| EP0045276B1 (en) | 1983-06-22 |
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| Date | Code | Title | Description |
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| MKEX | Expiry |