CA1085386A - Water-soluble brown l:2-chromium-mixed complex dyestuffs, process for their manufacture and their use for the dyeing of natural or synthetic polyamide fibers - Google Patents
Water-soluble brown l:2-chromium-mixed complex dyestuffs, process for their manufacture and their use for the dyeing of natural or synthetic polyamide fibersInfo
- Publication number
- CA1085386A CA1085386A CA271,082A CA271082A CA1085386A CA 1085386 A CA1085386 A CA 1085386A CA 271082 A CA271082 A CA 271082A CA 1085386 A CA1085386 A CA 1085386A
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- Prior art keywords
- chromium
- mixed complex
- compounds
- formulae
- parts
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Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/046—Material containing basic nitrogen containing amide groups using metallisable or mordant dyes
-
- 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
- C09B45/16—Monoazo compounds containing chromium
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Abstract
Abstract of the disclosure:
Novel, valuable, brown 1:2-chromium-mixed-complex dyestuffs of the two monoazo compounds of the formulae (1) and (2) (1)
Novel, valuable, brown 1:2-chromium-mixed-complex dyestuffs of the two monoazo compounds of the formulae (1) and (2) (1)
Description
1~0 ? 7(~ ' 0 ! ~
Nove~. vall1able brown 1:2~chromi~m-mix~d-complex dyestuffs of monoazo compounds of the general formu]ae ~1) and (2) and mixtures thereof have been folln~
~IO35~ ~ - N = N
. R1 N = N ~ ¦ ~ R4 ~2) ~ ~ CH3 SO3H
.` R2 in which R1 is hydrogen or the nitro group, R2 is lower alkyl, such as methyl or ethyl, especially methyl, chlorine or the nitro group or lower alkoxy, such as methoxy or ethoxy, R3 i.s ~ hydrogen, chlorine or lower alkyl or lower alkoxy, such as methyl, ethyl, methoxy or ethoxy, of these preferably methyl, and R4 is hydrogen or chlorine.
In the novel chromium-mixed complex dyestuffs, the ind-ividual 1:2-chromium complex dyestuffs from (1), from (1) and
Nove~. vall1able brown 1:2~chromi~m-mix~d-complex dyestuffs of monoazo compounds of the general formu]ae ~1) and (2) and mixtures thereof have been folln~
~IO35~ ~ - N = N
. R1 N = N ~ ¦ ~ R4 ~2) ~ ~ CH3 SO3H
.` R2 in which R1 is hydrogen or the nitro group, R2 is lower alkyl, such as methyl or ethyl, especially methyl, chlorine or the nitro group or lower alkoxy, such as methoxy or ethoxy, R3 i.s ~ hydrogen, chlorine or lower alkyl or lower alkoxy, such as methyl, ethyl, methoxy or ethoxy, of these preferably methyl, and R4 is hydrogen or chlorine.
In the novel chromium-mixed complex dyestuffs, the ind-ividual 1:2-chromium complex dyestuffs from (1), from (1) and
(2) as well as from (2) are present in the molar ratio of from about 33:45:22 to about 9:18:73, preferably in the ratio of from about 16:30:54 to 10:20:70, especially from about 13:26:61 to about 11:23:66 molar per cent.
The novel dyestuffs are preferably present i.n the form of their sodium, potassium or ammonium salts.
The novel 1:2-chromium-mixed complex dyestuffs are pre-pared according to the invention by a process which comprises treatin~ a mixture of the known metal-rree starting (ompcunds *
~' ' :' ,~ ' -',:
853~6 :
of ~ormuiae (1) an(~ ~2), for example in a molar ratio of from 1:0.8 to 1:2.7, preferably from 1:1.7 to 1:2.5, especially from 1:1.9 to 1:2.2, with a chroming agent at a temper2ture in the range of from 95 to 145C, preferably of from 105 to 1~5C, and at a pH value between 4.0 and 7.0, preferably between 4.5 and 6.5.
The compounds of formulae (1) and (2) are obtained in kno~n manner by diazotizing and coupling their diazo and coupling i! components. These compounds (1) and (2) may be used for the preparation of the novel mixed-complex dyestuffs directly after their synthesis without an intermediate isolation so that the novel mixed-complex dyestuffs are obtainea in a preferred manner by chroming according to the process conditions ~ecified above the synthesis solutions or suspensions of the compounds (1) and (2) mixed with each other after the synthesis in the respective ratio, i.e. without intermediate separation and isolat:ion of the compounds (1) and (2) from the coupling mixture.
The metallization is effected preferably in an aqueous medium and may be carried out in an open vessel as wel] as in a closed vessel under pressure. As chroming agents theremay be ; mentioned chromic salts of inorganic or organic acids, for example, chromium-(III)-carbonate, potassium-chromium sulfate, chromium-(III)-acetate and chromium-(III)-sulfate. The chroming may be performed in the presence of an acid-binding agent, such as a salt, oxide or hydroxide of an alkali metal, or of an alka-linely reacting salt of an alkali metal; such compounds are, for example,sodium or potassium acetate, sodium or potassium carbonate or -hydrogeno-Farbonate, sodium or potassium hydroxide.
The novel dyestuffs are preferably present i.n the form of their sodium, potassium or ammonium salts.
The novel 1:2-chromium-mixed complex dyestuffs are pre-pared according to the invention by a process which comprises treatin~ a mixture of the known metal-rree starting (ompcunds *
~' ' :' ,~ ' -',:
853~6 :
of ~ormuiae (1) an(~ ~2), for example in a molar ratio of from 1:0.8 to 1:2.7, preferably from 1:1.7 to 1:2.5, especially from 1:1.9 to 1:2.2, with a chroming agent at a temper2ture in the range of from 95 to 145C, preferably of from 105 to 1~5C, and at a pH value between 4.0 and 7.0, preferably between 4.5 and 6.5.
The compounds of formulae (1) and (2) are obtained in kno~n manner by diazotizing and coupling their diazo and coupling i! components. These compounds (1) and (2) may be used for the preparation of the novel mixed-complex dyestuffs directly after their synthesis without an intermediate isolation so that the novel mixed-complex dyestuffs are obtainea in a preferred manner by chroming according to the process conditions ~ecified above the synthesis solutions or suspensions of the compounds (1) and (2) mixed with each other after the synthesis in the respective ratio, i.e. without intermediate separation and isolat:ion of the compounds (1) and (2) from the coupling mixture.
The metallization is effected preferably in an aqueous medium and may be carried out in an open vessel as wel] as in a closed vessel under pressure. As chroming agents theremay be ; mentioned chromic salts of inorganic or organic acids, for example, chromium-(III)-carbonate, potassium-chromium sulfate, chromium-(III)-acetate and chromium-(III)-sulfate. The chroming may be performed in the presence of an acid-binding agent, such as a salt, oxide or hydroxide of an alkali metal, or of an alka-linely reacting salt of an alkali metal; such compounds are, for example,sodium or potassium acetate, sodium or potassium carbonate or -hydrogeno-Farbonate, sodium or potassium hydroxide.
- 3 -. ' ' .
~,. . . ~ - ., ,. : , . .
, ~ , .
-~,' ' , , ` ' ~ - . ~ ' OE '7 6 /F t~ 18 The chromialm-complex dyestuffs thus prepared may be iso-lated from ~heir preparation solutions by salting them out with sodium or potassium chloride or by spray-drying.
The no~e] chromium-mixed complex azo dyestuffs may he used according to the invention for the dyeing of natural and syn-thetic polyamide fibers, for example wool, silk, and polyamides made from -caprolactam, from hexamethylene-diamine and adipic acid or from ~ -amino-undecylic acid. They may be used in a particularly advantageous manner for the dyeing of the above-specified fibers in admixture with other hydrophobic types of fiber, for example, for dyeing of wool in mixtures of wool and polyester fibers, with an excellent resist effect of the hydro-phobic fiber portion.
The dyestuffs are preferably used in the form of their alkali metal salts, such as the sodium, potassium oc ammonium salts. They may also be used for the dyeing, however, in ad-mixture with other 1:2-chromium- or -cohalt complex dyestuffs containing one or two sulfonic acid groups per dyestuff mole-cule. The dyeing is carried out in the manner according to methods known and common for metal complex dyestuffs, preferably from an acid to neutral bath, preferably at a pH range of from
~,. . . ~ - ., ,. : , . .
, ~ , .
-~,' ' , , ` ' ~ - . ~ ' OE '7 6 /F t~ 18 The chromialm-complex dyestuffs thus prepared may be iso-lated from ~heir preparation solutions by salting them out with sodium or potassium chloride or by spray-drying.
The no~e] chromium-mixed complex azo dyestuffs may he used according to the invention for the dyeing of natural and syn-thetic polyamide fibers, for example wool, silk, and polyamides made from -caprolactam, from hexamethylene-diamine and adipic acid or from ~ -amino-undecylic acid. They may be used in a particularly advantageous manner for the dyeing of the above-specified fibers in admixture with other hydrophobic types of fiber, for example, for dyeing of wool in mixtures of wool and polyester fibers, with an excellent resist effect of the hydro-phobic fiber portion.
The dyestuffs are preferably used in the form of their alkali metal salts, such as the sodium, potassium oc ammonium salts. They may also be used for the dyeing, however, in ad-mixture with other 1:2-chromium- or -cohalt complex dyestuffs containing one or two sulfonic acid groups per dyestuff mole-cule. The dyeing is carried out in the manner according to methods known and common for metal complex dyestuffs, preferably from an acid to neutral bath, preferably at a pH range of from
4.0 to 6.5 and at a temperature of fxom 90 to 105C; the common dyeing auxiliary agents may be added to the dyeing liquors, such as, for example, fatty amine- or fatty alcohol-oxethylation products as well as common buffer substances, such as sodium phosphate, sodium acetate, sodium for~ate, optionally in ad-mixture ~m th the corresponding acids, in order to stabilize the pH value of the dye bath.
- HOE 76/F 01~3 Fol- exalllpl~, b~ the addit~on of an acid, such as ~ormic acid or acetic acid, or a mineral acid, to the dye bath which contains an alkali metal salt of the formic acid, acetic acid or an~other organic acid, a pH value of the d~e ba-th rnay be adjusted ~Yhich accords with the optimum dyeing condition in respect of the dyestu~f concentration used and the color depth desired on the fiber.
For the local dyeing by printing, use is made of printing pastes which contain the common thickeners and printing auxi-liary agents as well as a salt of a weak base and of a strong mineral acid or of an organic acid, for example ammonium sulfate or ammonium tartrate. The printed fabrics are dried and then treated for a short time with hot air or steam.
In this way, the novel dyestuffs of the invention yield on natural and synthetic polyamide fibers red-brown ~ dark brown color shades having good to very good properties with regard to the fastness to wet processing for example the fa5tness to washing at a temperature of from 20 to 60C, for example at 40 and 60C according to DIN 54010 and 54014, the fastness to alkaline and acid fulling the fastness to water (under severe conditions), to alkaline and acid perspiration, to pottingr to chlorinated water, to peroxide bleaching, to hot water, steam, formaldehyde and to cross-dyeing, the fastness to acid chlori~
nation of wooL, and good fastness properties with regard to solvents, to carbonizing and decatizing, as well as excel~ent fastness properties with regard to light in the Xenotest and to daylig}lt.
Furthermore, the novel mixed chromium dyestuffs are marked , . . .
- : :
`.' ' ~ ~ , ' ' :.
,. . .
. : ' . :,' ~' HOE 7 ~ / F 0 ? 8 1~85386 by a non-exp~c~ed and surprisingly good and ev~n color build-up and absorption capacity during the dyeing process from the dye bath onto the fiber. Due to their good yield,they produce econo-mical dyein~s on wool and polyamide fibers.
Preference is given to 1:2-chromium-mixed complex dyestuffs of the invention which are based on the starting dyestuff pairs of formulae (1a)/(2d) and (lb)/(2a), especially in the mixing ratios indicated in Examples 4 and 9.
The following Examples serve to illustrate the invention.
The parts are parts by weight, and the percentages stand for per cent by weight.
E X A M P L E
.
29.5 Parts of 6-nitro-1-diazo-2-naphthol-4-~sulfonic acid are stirred into 40 parts by weight of water, and the mixture is adjusted to a pH of from 4 to 5 by mea~s of 9 parts of 33 ~
sodium hydroxide solution. 12 Parts of calcined sodium carbonate and 7.5 parts of calcium hydroxide are added, and swbsequently a solution of 17.5 parts of 2-naphthol in 40 parts of water and 16.3 parts of an aqueous 33 ~ sodium hydroxide so:Lution are irJtro-duced into the mixture. The coupling is completed after 8 hours at room temperature.
The second azo compound is prepared as follows:
15.4 Parts of 4-nitro-2-aminophenol are dissolved with 25 parts of 31 % hydrochloric acid in 150 parts of water and diazotized, after the addition of 50 parts of ice, by introducing 17.3 parts of an aqueous 40 % sodium nitrite solution. Af~er 30 minutes, a small amount of àmidosulfonic acid is added in order to destroy excess nitrous acid~ 32.3 Parts of 3-methyl~ ',5'-., .
.... .. .. . . . . . . .
, .~
., . ., ., . . : ..
- . , . -. :
~:
.
I~OE 76/F_018 `
-- ~L08S3~6 dichloro-~'-sulfo~phenyl)-5-pyrazolon~ are added, and the p~l value is est.ablished at 8 A 5 to 9.0 with calci.ned sodium car-bonate. The coupling is completed after 6 hours at room tempera-ture.
The comb.ined two azo compound suspensions thus obtai.ned are adjusted to a pH value of 5.0 by means of 31 ~ hydrochlori.c acid. After the addition of 15.4 parts of chromium~ acetate and 27.2 parts of crystallized sodium acetate, the mixture is refluxed for 4 hours.
The 1:2--mixed-chromium dyestuff thus prepared is separated by being salted out with sodium chloride or is isolated by spray-dryi.ng. A dark brown dyestuff powder is obtained which contains the mixed chromium products of the azo compounds of formulae (1a) and (2a), indicated as free sulfonic acids, the molar ratio of compounds (1a) and (2a) in the mixed chromium product being about 1~
~il 110 ~ 1 3 ~ N ~ \ 3 ". ' ~ , .
(1 a) ~ (2 .~) .s : yeing Example ' 100 Parts of wool fabric are introduced into a dye bath i~ of 40C which contains 1.0 part of the mixed complex dyestuff of Example 1, 0.15 part of the addition product of 12 moles of ethylene oxide to 1 mole of stearylamine, 2 parts of amm-!.t1ium 3 . 7 ~!
., - . ''' '''~ ' , ., ...... ,,, , ' , ' ' ' ~
-: , , ~' .
. . . : . ., . :: ~ ;
- , 1~0~ 7 6 / I~ n 1 ~
- -acetate and 2 ~arts of an aqueous 60 ~ acetic acid in 3~00 parts of watex. The ~emperature of the dye bath is i.ncreased wi~h-in 30 minut~s to boi.ling point, and the mater.i.al is then dyed for 60 minutes at 100C. Thereafter, the dyei,n~ is afte~--treated and c~ompleted as usual. A brown dyeing is obtained which shows a good evenness, ~ood to very good fastness pro perties with regard to wet processing and a very good fastness to light.
If the wool fabric is replaced by 100 parts of a fabric made of polycaprolactam, a dyeing is obtained which also shows good to very good general fastness properties and an excellent fastness to light.
If in the preparation process of the metal-free azo com-pounds in Exarnple 1 the 6-nitro-1-diazo 2-naphthol-4-sulfonic acid is rep],aced by 25.0 parts of 1-diazo-2-naphthol-4-sulforlic acid and the 4-nitro-2-aminophenol is replaced by 14.4 parts 3 of 4-chloro-2 aminophenol, and if the reactions are carried out in the manrler described, a dark brown dyestuff powder is obtained which contains the mixed chromium compounds of the metal-free compounds of formulae (1b) and (2b), indicated as free sulfonic acids, the mo]ar ratio of the azo compounds (1b) and.(2b) being approximatel.y 1:1. J
OH I1O ~l HO 5- ~ - N.N~ 2l~ 5~3ll 1~ b) ... (2 b~
- ~ . . :: :.
-. .
.
:: : :-::
liOE 7~ 018 1~853~6 D~eing Exa~le __ 100 Parts of polycaprola~tam fabric are introcluced into an aqueous bath having a temperature of 40C which contains 1.5 parts of the mixed comp]ex dyestuff of Example 2, 0.15 part of the addition product of 12 moles of ethylene oxide to 1 mole of stearylamine, 2.0 parts of ammonium acetate and 2.0 parts of 60 % acetic acid in 3000 parts of water. Within 15 minutes, the temperature of thedye bath isincreased to 98 - 100C, and the dyeing is then continued for 60 minutes at 100C. It is then completed (rinsed) as usual. A brown dyeing is obtained whicl~
shows good to very good fastness properties with regard to wet processingas well as a very good fastness to light.
If the polycaprolactam fabric is replaced by 100 parts of wool fabric, a dyeing is obtained which also shows good (3eneral fastness properties and a very good fastness to light.
25.0 Parts of 1-diazo-2-naphthol-4-sulfonic acid are stirre~
into 40 parts of water, and the pH value is adjusted to 4 - 5 by means of 9 parts of an aqueous 33 % sodium hydroxide so]ution.
Subsequently 12 parts of calcined sodium carbonate and 7.5 parts of calcium hydroxide are added, and then a solution of 17.5 parts of 2-naphthol in 40 parts of water and 16.3 parts of an aqueous 33 % sodium hydroxide solution are introduced into the mixture.
The coupling is completed after 8 hours at room temperature.
The second azo compound is prepared as follows:
30.8 Parts of 4--nitro-2-aminophenolare dissolved with 50 parts of 31 % hydrochloric acid in 300 parts of water, and after the addition of 100 parts of ice the solution i~ diazotized by intro-. ~ . .: : ............................... : - .
. . , :.
; - ~
EIOE' 76LF_01,~.
1~85386 ducing 34 0 6 parts of an aqueous 40 % by weight sodium nitr.ite solution. ~fter 30 minutes a small amount of amidosulfonic ~c~d is ~,~dded to destroy the excess n:ltrous acid. Subsequently 50.~s parts of 3-methyl-1-(4'-sulfoph~nyl)-5-pyrazo]one are addcd, and the pH value is established at 8.5 to 9.0 with calcined sodium carbonate. The coupling is completed aft~r 2 hours at room tempexat-~re.
The two azo compound suspensions thus prepared are com-bined, and a pH of 8.0 is at first established with 31 ~ hydro-chloric acicl, and then of 6.0 with acetic acia. After the addition of 41.2 parts of crystallized potassium-chromium s~l-fate and 45 parts of crystallized sodium acetate, the mixture is heated in a closed vessel for 4 hours at a temperature of from 130 to 135C. The mixed chromium dyestuff is separated by being salted out with sodium chloride or is isolated by spxay drying.
A dark brown dyestuff powder is obtained whic~h cont,ains the mixed chromium compounds of the metalfree compounds of formulae (1b~ and (2c), indicated as free sulfonic acids 0~ ~10 , q~ ~0 110 S~ I=N~ N=N~ I ~503~1 7 ,(1 ~) , , , (2 c) ' , - 10 --' ' ~ ,. ' ' ' :' :. ~: ..
HOE 76/}~ 018 the molar ratio oE the compounds (1b) and (2~; in the chromi.uln compound mixture being approximately 1:2.
Dyeing Example Pol~amide caxpet .yarn is treated with an aqueous padding liquor containing 10 parts of the mixed complex dyestuff of Example 3, 5 parts of a carob bean flour preparation, 1 mol~
of isotridecyl alcohol and 10 parts of 60 % acetic aci.d in 1000 parts of the liquor, with a liquor pick-up of 100 % hy weight; subsequently the material is steamed for 6 minutes at 100 - 102C and xinsed with.cold water. The brown carpet dyeing obtained shows very good general fastness properties as well.
as an excellent fastness to day_light.
If in the preparation process of the metal-free monoazo compounds in Example 3 the 1-diazo-2-naphthol-4-sulfonic acid is replaced by 29.5 parts of 6--ni.tro--1-diazo-2-naphthol-~-sul-fonic acid and the 3-methyl-1-(4'-sulfophenyl)-5-pyrazo].one is replaced by 60.6 parts of 3-methyl.-1-(5'-chloro-2'-methyl 4'-sulfophenyl)-5-pyrazolone, and the reactions are carried out analogously in the described manner, a dark brown dyestuff powder is o~tained which contains the mixed chromium compounds of the metalfree compounds of formulae (1a) and (2d~, indicated as free sulfonic acids . ~fl ~ fl }{ 3 IIO~S~ N-N ~ N- N l ~ 5 ., o;~ - .
. (1 a) ~2 d~
:
. -- - - - , . , . : -,, : . : .
~ . ,: . ' ' .
-:' . . .: , : ~ ', ' , HOE 75/F 01~
the molar ratio of the compounds (1a) and (2a) in this mi~ed chromium product b~ing approximately 1:2.
A chromium-mixed complex dyestuff having the same yood qualitjes is obtained when compounds (1a) and (2d) in a molar ratio of 1:2.2 are used.
Dyeing Example 100 Parts of wool flock are introduced into a dye bath having a temperature of 40C and containing 1.0 part of the mixed complex dyestuff of Example 4, 0.15 part of an addition product of 12 moles of ethylene oxide to 1 mole of stearyl-amine, 2 parts of ammonium acetate and 2 parts of 60 % acetic acid in 3000 parts of water. The temperature of the dye bath is increased within 30 minutes to the boiling point, and the dyeing is then continued for 60 minutes at 100C. Thereafter, the dyeing obtained is after-treated and completed in the usual manner; an even red-brown dyeing is obtained wh ch shows good to very good fastness properties with regard to wet processing as well as a very good fastness to light.
` If the 100 parts of wool flock are replaced ~y the same amount of wool hank yarn, an even dyeing is also obtained which shows good to very good fastness properties with regard to wet processing as well as a very good fastness to light.
If the metal--free azo compound pairs specified in the following Table are used in the mixed chrominy process as starting compounds in the molar ratios indicatedJconducting it according to the invention, so~for example, according to one of the Examples 1 through 4, chromium-mixed complex dyestuEfs are obtained which dye wool or fiber material from synthetic ., ' ' .:
~10~ 76/~
~0853~6 polyamides in the colour shades mentioned in the Table with a high e~enness and a constant shade.
Ex .Compound ( 1 ) Compound (2) Colour shade on wool . .
~ ~ H~G. ~ ~ ~
,.~ . ' . . . .
a) 1 mole . 2 m~es . b) 1 mole . 2,2 moles 0~ 0 6 1 ~ ~03H brown ~ N
. .
a) 1 mole 2 moles b) 1 moIe 2.3 Moles I .
'I ' I{ ''~ ~ }~ 1~3R '--~
110 5~ ~ - N-N ~3 ~ N=N 1 ~ ~ 03~1 : ' '' - -. ' - -.. j a) 1 mole -1mole a) dark hr~n ., b) 1 moIe 2moles b) brown ~ 13 - .
,- .
.
.. ~. .. ....... . . . . . . .
.
~ ' ' .' . ~
:: :. . ~
~,: ~: ' . " : : :
~10_76/F n ~, 10853E3~
Ex.Compo~nd (1) Compound (2~ Colour shade on wool H3(`, 1~0 ~ N=N~
3\ / \ ~ 1 - N C, 1 .
al 1 mole 1 mole a) dark bro~m h) 1 mole 2 moles b) hrot,?n Cl t ~ OH HO 0~-1 ITO
?~03~ ~-N=N-~ ~r ~ 03H
a) lmo].e 2~2 moles -b) 1mole . 2.5 moles , ..... . . . . . .
: .:: .... .. : .. ~ . , . - ~ . . . - , : .
- . , : ~, .
: ~ , .
- HOE 76/F 01~3 Fol- exalllpl~, b~ the addit~on of an acid, such as ~ormic acid or acetic acid, or a mineral acid, to the dye bath which contains an alkali metal salt of the formic acid, acetic acid or an~other organic acid, a pH value of the d~e ba-th rnay be adjusted ~Yhich accords with the optimum dyeing condition in respect of the dyestu~f concentration used and the color depth desired on the fiber.
For the local dyeing by printing, use is made of printing pastes which contain the common thickeners and printing auxi-liary agents as well as a salt of a weak base and of a strong mineral acid or of an organic acid, for example ammonium sulfate or ammonium tartrate. The printed fabrics are dried and then treated for a short time with hot air or steam.
In this way, the novel dyestuffs of the invention yield on natural and synthetic polyamide fibers red-brown ~ dark brown color shades having good to very good properties with regard to the fastness to wet processing for example the fa5tness to washing at a temperature of from 20 to 60C, for example at 40 and 60C according to DIN 54010 and 54014, the fastness to alkaline and acid fulling the fastness to water (under severe conditions), to alkaline and acid perspiration, to pottingr to chlorinated water, to peroxide bleaching, to hot water, steam, formaldehyde and to cross-dyeing, the fastness to acid chlori~
nation of wooL, and good fastness properties with regard to solvents, to carbonizing and decatizing, as well as excel~ent fastness properties with regard to light in the Xenotest and to daylig}lt.
Furthermore, the novel mixed chromium dyestuffs are marked , . . .
- : :
`.' ' ~ ~ , ' ' :.
,. . .
. : ' . :,' ~' HOE 7 ~ / F 0 ? 8 1~85386 by a non-exp~c~ed and surprisingly good and ev~n color build-up and absorption capacity during the dyeing process from the dye bath onto the fiber. Due to their good yield,they produce econo-mical dyein~s on wool and polyamide fibers.
Preference is given to 1:2-chromium-mixed complex dyestuffs of the invention which are based on the starting dyestuff pairs of formulae (1a)/(2d) and (lb)/(2a), especially in the mixing ratios indicated in Examples 4 and 9.
The following Examples serve to illustrate the invention.
The parts are parts by weight, and the percentages stand for per cent by weight.
E X A M P L E
.
29.5 Parts of 6-nitro-1-diazo-2-naphthol-4-~sulfonic acid are stirred into 40 parts by weight of water, and the mixture is adjusted to a pH of from 4 to 5 by mea~s of 9 parts of 33 ~
sodium hydroxide solution. 12 Parts of calcined sodium carbonate and 7.5 parts of calcium hydroxide are added, and swbsequently a solution of 17.5 parts of 2-naphthol in 40 parts of water and 16.3 parts of an aqueous 33 ~ sodium hydroxide so:Lution are irJtro-duced into the mixture. The coupling is completed after 8 hours at room temperature.
The second azo compound is prepared as follows:
15.4 Parts of 4-nitro-2-aminophenol are dissolved with 25 parts of 31 % hydrochloric acid in 150 parts of water and diazotized, after the addition of 50 parts of ice, by introducing 17.3 parts of an aqueous 40 % sodium nitrite solution. Af~er 30 minutes, a small amount of àmidosulfonic acid is added in order to destroy excess nitrous acid~ 32.3 Parts of 3-methyl~ ',5'-., .
.... .. .. . . . . . . .
, .~
., . ., ., . . : ..
- . , . -. :
~:
.
I~OE 76/F_018 `
-- ~L08S3~6 dichloro-~'-sulfo~phenyl)-5-pyrazolon~ are added, and the p~l value is est.ablished at 8 A 5 to 9.0 with calci.ned sodium car-bonate. The coupling is completed after 6 hours at room tempera-ture.
The comb.ined two azo compound suspensions thus obtai.ned are adjusted to a pH value of 5.0 by means of 31 ~ hydrochlori.c acid. After the addition of 15.4 parts of chromium~ acetate and 27.2 parts of crystallized sodium acetate, the mixture is refluxed for 4 hours.
The 1:2--mixed-chromium dyestuff thus prepared is separated by being salted out with sodium chloride or is isolated by spray-dryi.ng. A dark brown dyestuff powder is obtained which contains the mixed chromium products of the azo compounds of formulae (1a) and (2a), indicated as free sulfonic acids, the molar ratio of compounds (1a) and (2a) in the mixed chromium product being about 1~
~il 110 ~ 1 3 ~ N ~ \ 3 ". ' ~ , .
(1 a) ~ (2 .~) .s : yeing Example ' 100 Parts of wool fabric are introduced into a dye bath i~ of 40C which contains 1.0 part of the mixed complex dyestuff of Example 1, 0.15 part of the addition product of 12 moles of ethylene oxide to 1 mole of stearylamine, 2 parts of amm-!.t1ium 3 . 7 ~!
., - . ''' '''~ ' , ., ...... ,,, , ' , ' ' ' ~
-: , , ~' .
. . . : . ., . :: ~ ;
- , 1~0~ 7 6 / I~ n 1 ~
- -acetate and 2 ~arts of an aqueous 60 ~ acetic acid in 3~00 parts of watex. The ~emperature of the dye bath is i.ncreased wi~h-in 30 minut~s to boi.ling point, and the mater.i.al is then dyed for 60 minutes at 100C. Thereafter, the dyei,n~ is afte~--treated and c~ompleted as usual. A brown dyeing is obtained which shows a good evenness, ~ood to very good fastness pro perties with regard to wet processing and a very good fastness to light.
If the wool fabric is replaced by 100 parts of a fabric made of polycaprolactam, a dyeing is obtained which also shows good to very good general fastness properties and an excellent fastness to light.
If in the preparation process of the metal-free azo com-pounds in Exarnple 1 the 6-nitro-1-diazo 2-naphthol-4-sulfonic acid is rep],aced by 25.0 parts of 1-diazo-2-naphthol-4-sulforlic acid and the 4-nitro-2-aminophenol is replaced by 14.4 parts 3 of 4-chloro-2 aminophenol, and if the reactions are carried out in the manrler described, a dark brown dyestuff powder is obtained which contains the mixed chromium compounds of the metal-free compounds of formulae (1b) and (2b), indicated as free sulfonic acids, the mo]ar ratio of the azo compounds (1b) and.(2b) being approximatel.y 1:1. J
OH I1O ~l HO 5- ~ - N.N~ 2l~ 5~3ll 1~ b) ... (2 b~
- ~ . . :: :.
-. .
.
:: : :-::
liOE 7~ 018 1~853~6 D~eing Exa~le __ 100 Parts of polycaprola~tam fabric are introcluced into an aqueous bath having a temperature of 40C which contains 1.5 parts of the mixed comp]ex dyestuff of Example 2, 0.15 part of the addition product of 12 moles of ethylene oxide to 1 mole of stearylamine, 2.0 parts of ammonium acetate and 2.0 parts of 60 % acetic acid in 3000 parts of water. Within 15 minutes, the temperature of thedye bath isincreased to 98 - 100C, and the dyeing is then continued for 60 minutes at 100C. It is then completed (rinsed) as usual. A brown dyeing is obtained whicl~
shows good to very good fastness properties with regard to wet processingas well as a very good fastness to light.
If the polycaprolactam fabric is replaced by 100 parts of wool fabric, a dyeing is obtained which also shows good (3eneral fastness properties and a very good fastness to light.
25.0 Parts of 1-diazo-2-naphthol-4-sulfonic acid are stirre~
into 40 parts of water, and the pH value is adjusted to 4 - 5 by means of 9 parts of an aqueous 33 % sodium hydroxide so]ution.
Subsequently 12 parts of calcined sodium carbonate and 7.5 parts of calcium hydroxide are added, and then a solution of 17.5 parts of 2-naphthol in 40 parts of water and 16.3 parts of an aqueous 33 % sodium hydroxide solution are introduced into the mixture.
The coupling is completed after 8 hours at room temperature.
The second azo compound is prepared as follows:
30.8 Parts of 4--nitro-2-aminophenolare dissolved with 50 parts of 31 % hydrochloric acid in 300 parts of water, and after the addition of 100 parts of ice the solution i~ diazotized by intro-. ~ . .: : ............................... : - .
. . , :.
; - ~
EIOE' 76LF_01,~.
1~85386 ducing 34 0 6 parts of an aqueous 40 % by weight sodium nitr.ite solution. ~fter 30 minutes a small amount of amidosulfonic ~c~d is ~,~dded to destroy the excess n:ltrous acid. Subsequently 50.~s parts of 3-methyl-1-(4'-sulfoph~nyl)-5-pyrazo]one are addcd, and the pH value is established at 8.5 to 9.0 with calcined sodium carbonate. The coupling is completed aft~r 2 hours at room tempexat-~re.
The two azo compound suspensions thus prepared are com-bined, and a pH of 8.0 is at first established with 31 ~ hydro-chloric acicl, and then of 6.0 with acetic acia. After the addition of 41.2 parts of crystallized potassium-chromium s~l-fate and 45 parts of crystallized sodium acetate, the mixture is heated in a closed vessel for 4 hours at a temperature of from 130 to 135C. The mixed chromium dyestuff is separated by being salted out with sodium chloride or is isolated by spxay drying.
A dark brown dyestuff powder is obtained whic~h cont,ains the mixed chromium compounds of the metalfree compounds of formulae (1b~ and (2c), indicated as free sulfonic acids 0~ ~10 , q~ ~0 110 S~ I=N~ N=N~ I ~503~1 7 ,(1 ~) , , , (2 c) ' , - 10 --' ' ~ ,. ' ' ' :' :. ~: ..
HOE 76/}~ 018 the molar ratio oE the compounds (1b) and (2~; in the chromi.uln compound mixture being approximately 1:2.
Dyeing Example Pol~amide caxpet .yarn is treated with an aqueous padding liquor containing 10 parts of the mixed complex dyestuff of Example 3, 5 parts of a carob bean flour preparation, 1 mol~
of isotridecyl alcohol and 10 parts of 60 % acetic aci.d in 1000 parts of the liquor, with a liquor pick-up of 100 % hy weight; subsequently the material is steamed for 6 minutes at 100 - 102C and xinsed with.cold water. The brown carpet dyeing obtained shows very good general fastness properties as well.
as an excellent fastness to day_light.
If in the preparation process of the metal-free monoazo compounds in Example 3 the 1-diazo-2-naphthol-4-sulfonic acid is replaced by 29.5 parts of 6--ni.tro--1-diazo-2-naphthol-~-sul-fonic acid and the 3-methyl-1-(4'-sulfophenyl)-5-pyrazo].one is replaced by 60.6 parts of 3-methyl.-1-(5'-chloro-2'-methyl 4'-sulfophenyl)-5-pyrazolone, and the reactions are carried out analogously in the described manner, a dark brown dyestuff powder is o~tained which contains the mixed chromium compounds of the metalfree compounds of formulae (1a) and (2d~, indicated as free sulfonic acids . ~fl ~ fl }{ 3 IIO~S~ N-N ~ N- N l ~ 5 ., o;~ - .
. (1 a) ~2 d~
:
. -- - - - , . , . : -,, : . : .
~ . ,: . ' ' .
-:' . . .: , : ~ ', ' , HOE 75/F 01~
the molar ratio of the compounds (1a) and (2a) in this mi~ed chromium product b~ing approximately 1:2.
A chromium-mixed complex dyestuff having the same yood qualitjes is obtained when compounds (1a) and (2d) in a molar ratio of 1:2.2 are used.
Dyeing Example 100 Parts of wool flock are introduced into a dye bath having a temperature of 40C and containing 1.0 part of the mixed complex dyestuff of Example 4, 0.15 part of an addition product of 12 moles of ethylene oxide to 1 mole of stearyl-amine, 2 parts of ammonium acetate and 2 parts of 60 % acetic acid in 3000 parts of water. The temperature of the dye bath is increased within 30 minutes to the boiling point, and the dyeing is then continued for 60 minutes at 100C. Thereafter, the dyeing obtained is after-treated and completed in the usual manner; an even red-brown dyeing is obtained wh ch shows good to very good fastness properties with regard to wet processing as well as a very good fastness to light.
` If the 100 parts of wool flock are replaced ~y the same amount of wool hank yarn, an even dyeing is also obtained which shows good to very good fastness properties with regard to wet processing as well as a very good fastness to light.
If the metal--free azo compound pairs specified in the following Table are used in the mixed chrominy process as starting compounds in the molar ratios indicatedJconducting it according to the invention, so~for example, according to one of the Examples 1 through 4, chromium-mixed complex dyestuEfs are obtained which dye wool or fiber material from synthetic ., ' ' .:
~10~ 76/~
~0853~6 polyamides in the colour shades mentioned in the Table with a high e~enness and a constant shade.
Ex .Compound ( 1 ) Compound (2) Colour shade on wool . .
~ ~ H~G. ~ ~ ~
,.~ . ' . . . .
a) 1 mole . 2 m~es . b) 1 mole . 2,2 moles 0~ 0 6 1 ~ ~03H brown ~ N
. .
a) 1 mole 2 moles b) 1 moIe 2.3 Moles I .
'I ' I{ ''~ ~ }~ 1~3R '--~
110 5~ ~ - N-N ~3 ~ N=N 1 ~ ~ 03~1 : ' '' - -. ' - -.. j a) 1 mole -1mole a) dark hr~n ., b) 1 moIe 2moles b) brown ~ 13 - .
,- .
.
.. ~. .. ....... . . . . . . .
.
~ ' ' .' . ~
:: :. . ~
~,: ~: ' . " : : :
~10_76/F n ~, 10853E3~
Ex.Compo~nd (1) Compound (2~ Colour shade on wool H3(`, 1~0 ~ N=N~
3\ / \ ~ 1 - N C, 1 .
al 1 mole 1 mole a) dark bro~m h) 1 mole 2 moles b) hrot,?n Cl t ~ OH HO 0~-1 ITO
?~03~ ~-N=N-~ ~r ~ 03H
a) lmo].e 2~2 moles -b) 1mole . 2.5 moles , ..... . . . . . .
: .:: .... .. : .. ~ . , . - ~ . . . - , : .
- . , : ~, .
: ~ , .
Claims (14)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. 1:2-Chromium-mixed complex compounds of monoazo compounds of the general formulae (1) and (2) (1) (2) in which R1 is hydrogen or nitro, R2 is lower alkyl, chlorine, nitro or lower alkoxy, R3 is hydrogen, chlorine, lower alkyl or lower alkoxy, and R4 is hydrogen or chlorine and the molar ratio of the 1:2-chromium complexes of the compound pairs (1)/(1), (1)/(2) and (2)/(2) is between about 33:45:22 and about 9:18:73.
2. A mixed complex compound according to claim 1, wherein the molar ratio of the 1:2-chromium complexes of the compound pairs (1)/(1), (1)/(2) and (2)/(2) is from about 16:30:54 to 10:20:70.
3. A mixed complex compound according to claim 1, wherein the molar ratio of the 1:2-chromium complexes of the compound pairs (1)/(1), (1)/(2) and (2)/(2) is from about 13:26:61 to 11:23:66.
4. A mixed complex compound according to claim 1, 2 or 3, wherein the individual monoazo compounds are present in the form of their sodium, potassium or ammonium salts.
5. A mixed complex compound according to claim 1, 2 or 3, wherein the monoazo compounds are of the formulae:
(1a) and (2d)
(1a) and (2d)
6. A mixed complex compound according to claim 1, wherein the monoazo compounds are of the formulae:
(1a) and (2d) present in a molar ratio of compound (1a) to compound (2d) of 1:2 to 1:2.2.
(1a) and (2d) present in a molar ratio of compound (1a) to compound (2d) of 1:2 to 1:2.2.
7. A mixed complex compound according to claim 6, wherein the monoazo compounds (1a) and (2d) are present in the form of their sodium, potassium or ammonium salts.
8. A mixed complex compound according to claim 1, 2 or 3, wherein the monoazo compounds are of the formulae:
(1b) and (2a)
(1b) and (2a)
9. A mixed complex compound according to claim 1, wherein the monoazo compounds are of the formulae:
(1b) and (2a) present in a molar ratio of compound (1b) to compound (2a) of 1:2.2 to 1:2.5.
(1b) and (2a) present in a molar ratio of compound (1b) to compound (2a) of 1:2.2 to 1:2.5.
10. A mixed complex compound according to claim 9, wherein the monoazo compounds (1b) and (2a) are present in the form of their sodium, potassium or ammonium salts.
11. A process for the preparation of 1:2-chromium-mixed complex compounds as defined in claim 1, which comprises treating a mixture of the metal-free starting compounds of formulae (1) and (2) with a chroming agent at a temperature of from 95 to 145°C and at a pH value of from 4 to 7.
12. A process as claimed in claim 11, which comprises using the starting compounds of formulae (1) and (2) in a molar ratio of 1:0.8 to 1:2.7.
13. A process as claimed in claim 11, which comprises using the starting compounds of formulae (1) and (2) in a molar ratio of from 1:1.9 to 1:2.2.
14. A process for the dyeing and printing of natural and synthetic polyamide fibers, which comprises applying onto this fiber material a 1:2-chromium-mixed complex dyestuff as defined in claim 1, 2 or 3, in a dye bath or by means of a dye liquor or a printing paste in common manner and subsequently fixing the same in common manner on the fiber.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19762604799 DE2604799A1 (en) | 1976-02-07 | 1976-02-07 | WATER-SOLUBLE, BROWN 1 TO 2-CHROME MIXED COMPLEX DYES, THE PROCESS FOR THEIR MANUFACTURING AND THEIR USE FOR COLORING NATURAL AND SYNTHETIC POLYAMIDE FIBERS |
| DEP2604799.4 | 1976-02-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1085386A true CA1085386A (en) | 1980-09-09 |
Family
ID=5969292
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA271,082A Expired CA1085386A (en) | 1976-02-07 | 1977-02-04 | Water-soluble brown l:2-chromium-mixed complex dyestuffs, process for their manufacture and their use for the dyeing of natural or synthetic polyamide fibers |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS5296631A (en) |
| BE (1) | BE851172A (en) |
| CA (1) | CA1085386A (en) |
| CH (1) | CH626112A5 (en) |
| DE (1) | DE2604799A1 (en) |
| FR (1) | FR2340355A1 (en) |
| GB (1) | GB1564749A (en) |
| IT (1) | IT1075928B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2525621A1 (en) * | 1982-04-23 | 1983-10-28 | Ici Francolor | COMPLEX CHROMIFERO 1/2 COLORANTS, THEIR PREPARATION AND THEIR USE |
| US4507125A (en) * | 1982-11-02 | 1985-03-26 | Ciba-Geigy Corporation | Use of 1:2 chrome complex dyes for dyeing leather and furs |
| US4563412A (en) * | 1983-12-21 | 1986-01-07 | Polaroid Corporation | Black image dye-providing materials and photographic products and processes utilizing same |
| DE3478753D1 (en) * | 1983-12-21 | 1989-07-27 | Polaroid Corp | Novel chrome-complexed compounds and photographic system |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR40844E (en) * | 1931-10-05 | 1932-09-07 | Ste Ind Chim Bale | New metalliferous coloring materials and process for their preparation |
| FR770916A (en) * | 1933-04-04 | 1934-09-24 | Ste Ind Chim Bale | New chromium dyes |
| FR1263830A (en) * | 1960-04-05 | 1961-06-19 | Ciba Geigy | Process for dyeing nitrogenous fibers with 1: 2 chromium-containing or cobalt-rich complexes of azo dyes containing aquasolubilizing groups, and preparations suitable for carrying out this process |
-
1976
- 1976-02-07 DE DE19762604799 patent/DE2604799A1/en not_active Withdrawn
-
1977
- 1977-02-02 CH CH125177A patent/CH626112A5/en not_active IP Right Cessation
- 1977-02-04 JP JP1083577A patent/JPS5296631A/en active Pending
- 1977-02-04 CA CA271,082A patent/CA1085386A/en not_active Expired
- 1977-02-04 IT IT1999177A patent/IT1075928B/en active
- 1977-02-07 BE BE174726A patent/BE851172A/en unknown
- 1977-02-07 FR FR7703305A patent/FR2340355A1/en active Granted
- 1977-02-07 GB GB490377A patent/GB1564749A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2340355A1 (en) | 1977-09-02 |
| IT1075928B (en) | 1985-04-22 |
| GB1564749A (en) | 1980-04-10 |
| CH626112A5 (en) | 1981-10-30 |
| JPS5296631A (en) | 1977-08-13 |
| BE851172A (en) | 1977-08-08 |
| FR2340355B1 (en) | 1981-12-11 |
| DE2604799A1 (en) | 1977-08-11 |
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