CA1239254A - Process for photochemical stabilisation of non-dyed and dyed polyamide fibre material and mixtures thereof - Google Patents
Process for photochemical stabilisation of non-dyed and dyed polyamide fibre material and mixtures thereofInfo
- Publication number
- CA1239254A CA1239254A CA000494753A CA494753A CA1239254A CA 1239254 A CA1239254 A CA 1239254A CA 000494753 A CA000494753 A CA 000494753A CA 494753 A CA494753 A CA 494753A CA 1239254 A CA1239254 A CA 1239254A
- Authority
- CA
- Canada
- Prior art keywords
- hydrogen
- dyed
- formula
- fibre material
- process according
- 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
Links
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic System without C-Metal linkages
-
- 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
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/642—Compounds containing nitrogen
- D06P1/6423—Compounds containing azide or oxime groups
-
- 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
- D06P3/24—Polyamides; Polyurethanes
- D06P3/241—Polyamides; Polyurethanes using acid dyes
-
- 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
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/02—After-treatment
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/92—Synthetic fiber dyeing
- Y10S8/924—Polyamide fiber
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/92—Synthetic fiber dyeing
- Y10S8/926—Polyurethane fiber
Abstract
Process for photochemicaL stabiLisation of non-dyed and dyed poLyamide fibre materiaL
Abstract A process for photochemicaL stabiLisation of non-dyed and dyed poLyamide fibre materiaL and mixtures thereof with other fibres which comprises treating the fibre materiaL
with 3 fibre-reactive copper compLex of bisazomethines pre-pared from, for exampLe, saLicyLaLdehydes and aLiphatic dia-mines is described. Some of these copper compLexes used are noveL compounds. The poLyamide fibre materiaL, for exampLe textiLe materiaL, thus treated LargeLy retains its extensi-biLity and eLasticity even after reLativeLy proLonged exposure to Light. In addition, a cLear improvement in Light-fastness is achieved in dyed materiaL by treatment with the metaL com-pLex.
Abstract A process for photochemicaL stabiLisation of non-dyed and dyed poLyamide fibre materiaL and mixtures thereof with other fibres which comprises treating the fibre materiaL
with 3 fibre-reactive copper compLex of bisazomethines pre-pared from, for exampLe, saLicyLaLdehydes and aLiphatic dia-mines is described. Some of these copper compLexes used are noveL compounds. The poLyamide fibre materiaL, for exampLe textiLe materiaL, thus treated LargeLy retains its extensi-biLity and eLasticity even after reLativeLy proLonged exposure to Light. In addition, a cLear improvement in Light-fastness is achieved in dyed materiaL by treatment with the metaL com-pLex.
Description
~:~3~
CIBA~GEIGY A~
6asle (Switzerland) 1/15341t~
Process for photochemical stabilisation of non-dyed and dyed polyamide fibre material and mixtures thereof The present invention relates to a process for photo-chemical stabilisation of non-dyed and dyed polyamide fibre material and mixtures thereof with other fibres by treating th;s material with water-;nsolubLe copper complexes of bisazo-methines prepared, for example, from subs~ituted or unsub-stituted salicylaldehydes and al;phatic diamines.
The use of copper salts, for example copper sulfate, for improving the light-fastness of dyeings on polyamide fibres with metal complex dyes is generally known; reference is made to the article by I.B. HANES in ADR 3 (1980), pages 19 and 20. However, inorganic or also organic copper salts frequently have the disadvantage that their absorption onto the polyamide fibres is only inadequate and non-uniform and they therefore have to be used in high concentrations in order to achieve the desired effect. Normally they can only be used for aftertreatment and in d;scontinuous processes.
European Patent Applicat;on 51,188 recommends treat-ment of the Polyamide material with copper complexes of bis-azomethines, prepared, for example, from substituted or unsub-stituted salicylaldehydes and aromatic diamines, before, during or after dyeing to improve the light fastness of poly-amide dyeings.
~ Such agents for improving light-fastness have, how-;~ ever, an undesirable intrinsic colour and do not have a sufficiently adequate stability towards hydrolysis or acids, .~
as is appropriately stated in European Patent Application `; 113,856 from the same Appli-cant.
; ~'4~
. ~ .
I~ has now been found that, surprisingly, copper complexes of bisazomethines which are derived, for example, from subst;~uted or unsubstituted salicylaldehydes and ali-phatic diamines do not have the abovementioned disadvantages~
In the concentrations used, these complexes have no undes;-rab(e intrinsic colour, and they also have a better stabi-lity to~ards acids and hydrolysis, than the most closely comparable complexes according to European Patent APpliça-tion 51,188. In addition, they stain the fibre material less than the most closely comparable complexes.
The present invention thus relates to a proces~ for photochemical stabilisation of non~dyed and dyed polyamide fibre materialt or mixtures thereof with other fibres, which comprises treating the polyamide fibre material with a Fibre reactive, organic copper complex compound of the formula R3~ t in ~hich A1 is hydrogen or C1-C3-alkyl, R~, R2, R3 and R4 independently of one another are each hydrogenO halogen, hydroxyl, hydroxyalkyl, alkyl, alkoxy, alkoxyalkoxy, alkoxy-alkoxyalkoxy, carboxymethoxy, alkylamino~ dialkyl-amino~ -S02-NH2, -S02NHR or -S02NR2, in ~h;ch R ;s alkyl or alkoxyalkyl and alkyl or alkoxy is in each case to be understood as a group ~;th 1-4 C atoms, or R1 and RZ or R2 and R3 or R3 ard R~, together with the C atoms to which they are bonded, form a fused-on benzene radical, and X
and y1 independently of one another are each hydrogen, C1-C4-alkyl or an aromatic radical, or X1 and y1~ together wieh the C atoms to which they are bonded, form a cyclo-ali~hatic radical with 5-7 C atoms.
The present in~ention furehermore relates to the polyamide fibre material, or mixtures thereof ~ith o~her fibres, stabilised photochemically by t'ne present process, and the compounds of the formula (1) where these are novel per se.
The copoer complex compounds of the formula (1) are in ~eneral water-insoluble if they contain no carboxymethoxy radicals (-O-CH2-COOH) or salts thereof.
A~ is preferably n-propyl, ethyl or especially methyl or in particular hydrogen. In the radicals R~-R4, halo~en is fluorine, bromine or, in particular, chlorine.
Examples of suitable alkyl radicals are methyl, ethyl, n-propyl, ;sopropyl and tert.-butyl, hydroxyalkyl radicals are, for example, hydroxyethyl, and examples of alkoxy radicals are methoxy, ethoxy and butoxy. An example of an alkoxyalkoxy radical is methoxyethoxy (also called 2-oxabu-toxy) (O-CH2-CH2-0-C~l3), an example of an alkoxyalkoxy-alkoxy radical is ethoxyethoxyethoxy (also called 3,6-t loxY) (-~-CH2-CH2-0-CH2 CH2 0 2 3 example of a dialkylamino radical ;s d;ethylam;no. Parti-cularly suitable sulfonamide radicals are the sulfonamide, N-methylsulfonamide and N,N dimethylsulfonam;de radical~
'Two adjacent radicals R1-R4, together with the C
atoms to which they are bonded, can also form a fused-on benzene radical. Such bisazomethines are derived from
CIBA~GEIGY A~
6asle (Switzerland) 1/15341t~
Process for photochemical stabilisation of non-dyed and dyed polyamide fibre material and mixtures thereof The present invention relates to a process for photo-chemical stabilisation of non-dyed and dyed polyamide fibre material and mixtures thereof with other fibres by treating th;s material with water-;nsolubLe copper complexes of bisazo-methines prepared, for example, from subs~ituted or unsub-stituted salicylaldehydes and al;phatic diamines.
The use of copper salts, for example copper sulfate, for improving the light-fastness of dyeings on polyamide fibres with metal complex dyes is generally known; reference is made to the article by I.B. HANES in ADR 3 (1980), pages 19 and 20. However, inorganic or also organic copper salts frequently have the disadvantage that their absorption onto the polyamide fibres is only inadequate and non-uniform and they therefore have to be used in high concentrations in order to achieve the desired effect. Normally they can only be used for aftertreatment and in d;scontinuous processes.
European Patent Applicat;on 51,188 recommends treat-ment of the Polyamide material with copper complexes of bis-azomethines, prepared, for example, from substituted or unsub-stituted salicylaldehydes and aromatic diamines, before, during or after dyeing to improve the light fastness of poly-amide dyeings.
~ Such agents for improving light-fastness have, how-;~ ever, an undesirable intrinsic colour and do not have a sufficiently adequate stability towards hydrolysis or acids, .~
as is appropriately stated in European Patent Application `; 113,856 from the same Appli-cant.
; ~'4~
. ~ .
I~ has now been found that, surprisingly, copper complexes of bisazomethines which are derived, for example, from subst;~uted or unsubstituted salicylaldehydes and ali-phatic diamines do not have the abovementioned disadvantages~
In the concentrations used, these complexes have no undes;-rab(e intrinsic colour, and they also have a better stabi-lity to~ards acids and hydrolysis, than the most closely comparable complexes according to European Patent APpliça-tion 51,188. In addition, they stain the fibre material less than the most closely comparable complexes.
The present invention thus relates to a proces~ for photochemical stabilisation of non~dyed and dyed polyamide fibre materialt or mixtures thereof with other fibres, which comprises treating the polyamide fibre material with a Fibre reactive, organic copper complex compound of the formula R3~ t in ~hich A1 is hydrogen or C1-C3-alkyl, R~, R2, R3 and R4 independently of one another are each hydrogenO halogen, hydroxyl, hydroxyalkyl, alkyl, alkoxy, alkoxyalkoxy, alkoxy-alkoxyalkoxy, carboxymethoxy, alkylamino~ dialkyl-amino~ -S02-NH2, -S02NHR or -S02NR2, in ~h;ch R ;s alkyl or alkoxyalkyl and alkyl or alkoxy is in each case to be understood as a group ~;th 1-4 C atoms, or R1 and RZ or R2 and R3 or R3 ard R~, together with the C atoms to which they are bonded, form a fused-on benzene radical, and X
and y1 independently of one another are each hydrogen, C1-C4-alkyl or an aromatic radical, or X1 and y1~ together wieh the C atoms to which they are bonded, form a cyclo-ali~hatic radical with 5-7 C atoms.
The present in~ention furehermore relates to the polyamide fibre material, or mixtures thereof ~ith o~her fibres, stabilised photochemically by t'ne present process, and the compounds of the formula (1) where these are novel per se.
The copoer complex compounds of the formula (1) are in ~eneral water-insoluble if they contain no carboxymethoxy radicals (-O-CH2-COOH) or salts thereof.
A~ is preferably n-propyl, ethyl or especially methyl or in particular hydrogen. In the radicals R~-R4, halo~en is fluorine, bromine or, in particular, chlorine.
Examples of suitable alkyl radicals are methyl, ethyl, n-propyl, ;sopropyl and tert.-butyl, hydroxyalkyl radicals are, for example, hydroxyethyl, and examples of alkoxy radicals are methoxy, ethoxy and butoxy. An example of an alkoxyalkoxy radical is methoxyethoxy (also called 2-oxabu-toxy) (O-CH2-CH2-0-C~l3), an example of an alkoxyalkoxy-alkoxy radical is ethoxyethoxyethoxy (also called 3,6-t loxY) (-~-CH2-CH2-0-CH2 CH2 0 2 3 example of a dialkylamino radical ;s d;ethylam;no. Parti-cularly suitable sulfonamide radicals are the sulfonamide, N-methylsulfonamide and N,N dimethylsulfonam;de radical~
'Two adjacent radicals R1-R4, together with the C
atoms to which they are bonded, can also form a fused-on benzene radical. Such bisazomethines are derived from
2-hydroxy-1-naphthaldehyde, 3-hydroxy-2-naphthaldehyde or 1-hydroxy-2-naphthaldehyde.
The radicals X and Y can independently of one ano-ther be C1-C4-alkyl, for example methyl~ ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl and tert.-butyl.
Aromati'c radicals X and Y are, in particular, subst`ituted or unsubstituted naphthyl and, especially, phenyl radicals.
X and Y can also be l~inked to form a cycloaliphatic radi-cal, for example cyclohexylene~ cyclopentylene or cyclo-heptylene.
Preferably, R1-R4 independently of one another are each hydrogen, chlorine, bromine, methyl, ethyl, butyl, methoxy, ethoxy, methoxyethoxy, ethoxyethoxyethoxy or di-ethylamino or R1 and R2 together form a fused-on ben2ene radical.
~3~1;2S~
Of the subs~ituents X1 and y1~ preferably, one is hydrogen and the other is hydrogen, methyL, ethyl or phenyl~
or X1 and y1 together form a cyclohexylene radical.
Copper complexes which are preferably used are the water-insoluble copper complexes of the formula ~ _ ~ R5 (2) 1 It ~cu r 11 R ~ ~/ \0 / ~ Uf ~ / ~7 R8 l8 in which R5-R8 independently of one another are each hydro-gen, hydrox~L, bromine, methyl, tert.-butyl, methoxy, methoxyethoxy, ethoxyethoxyethoxy or diethylamino, x2 is hydrogen, methyl, ethyl or phenyl and y2 is hydrogen~ or R5 and R6 together form a fused-on benzene radical, or x2 and y2 to~ether form a cyclohexylene radical.
Compounds which are of particular ;nterest are those of the formula ~1/ \0~ \0/ \i~
Rll Rll in ~hich R9, R10 and R11 independently of one another are each hydrogen, chlorine, bromine, methyl or methoxy, or in which R9 and R10 together form a fused-on benzene ring, and X3 is hydrogen, methyl, ethyl or phenyl.
Compounds ~hich are of ch;ef interest, however, are those of the formula (3~ in ~hich R9, R10, R11 and X3 are hydrogen.
The compounds of the fornula (1~ are in some cases compounds which are known per se from, for example, Beilstein and Chemical Abstracts, and in so~e cases noYel compounds.
Thus, compounds of the for~ula (1) in which R3 is me~hyl and A1, R1, R~, ~4~ X and x2 are hydrogen; R1 and R4 are th l and A1 R2 R3 X1 and y1 are hydrogen; R and R
are chlorine and A1, R1~ R3, X1 and y1 are hydrogen; R4 is h nd A1 R4 R2 R3, X1 and y1 are hydrogen; R is methoxy~ methoxyethoxy, ethoxyethoxyethoxy or diethylamino and A1, R1, R2, R4, X1 and y1 are hydrogen;. R2 is meth-oxyethoxy or ethoxyethoxyethoxy and A1, R1, R3, R4, X
and y1 are hydrogen; R2 and R3 are methoxyethoxy or ethoxyethoxyethoxy and A1, R1, R4, X1 and y1 are hydrogen, or one of the two substituents R3 is hydroxyl and the other is methoxyethoxy or ethoxyethoxyethoxy and A1, R1, R2, R4, x1 and y1 are hydrogen, are novel per se.
The compounds of the formula (1) are obtained in a manner which is known per se by reaction of 2 equivalents of the corresponding o-hydroxyaldehydes w;th 1 equivalent of the corresponding diamine to give the corresponding Schiff's base and subsequent metallisation with copper salts. However, it is also possible first to form the cop-per complex of the o-hydroxyaldehyde and then to react th;s ~ith a corresponding diamine to give the copper complex of the bisazomethine of the formula (1).
It is also possible, without isolating the inter-mediates, to react the o-hydroxybenzaldehyde, the diamine and the copper salt in a single step in a so called one-pot process directly to give the compoun~ of the formula (1), or subsequently to modify, for example to alkylate, substi-tuents, ;n particular hydroxyl groups, by a further reac-tion ~hen the preparation of the compound of the formula (1) is complete. These 4 preparation methods are described by Pfeiffer in Liebigs Annalen der Chemie, Volume 503, pages 84-130 (1933).
The copper complexes of the formula (1) are advan-tageously applied from an aqueous bath, these advantageously being employed in an amount such that 5 to 200 ~9, in parti-cular 10 to 100 ~9, of copper are present per 9 of poly-amide fibre material.
The compounds of -the formula ~1) are advantageously , em~loyed as finely divided dispersions obtained by grinding in the presence of customary dispersants.
If the copper cornplexes are used for stabilising dyed mater;al, the fibre material can be treated with ehe copper complex before, during or after dyeing. The copper complex is ad~antageously added directly to the dyeing or padding liquor. Dyeirlg is carried out continuously or batchwise. In the continuous procedure, the copper com-plexes can be fixed by steam or heat.
Polyamide material is understood as mean;ng synthe-tic polyamide, for example polyamide-6, polyamide-66 or polyamide-12~ In add;t;on to pure polyamide fibres, f;bre mixtures of polyurethane and polyamide~ thus, for example, tricot material of polyamide/polyurethane in a mixture rat;o of 7~:30, are also particularly suitable. ln prin-ciple, the pure or mixed polyamide material can be in the most diverse processing forms, for example as fibres, yarn, woven fabric or knitted fabric.
In particular polyam;de mater;al which is exposed to light and heat and is in the form of, for example, auto-mobile upholstery or carpets is espec;ally suitable for treatment by the present process.
Dye;ng is carried out in the customary manner, for exam~le with-metal complex dyes or with anthraquinone dyes or azo dyes. The known types of metal complex dyes are used, in particular the 1:2 chromium or 1:2 cobalt com-plexes of mono- or disazo~ or -azomethine dyes, a large number of which are described ;n the l;terature. In addi-tion to these, dyes from other classes of dyes are of course also suitable, for example disperse or vat dyes.
The following preparation instructions and examples serve to illustrate the invention. Parts and percentages are by weight. The percentage data relating to the add;-tions to the 1ndividual treatment baths and dyebaths relate to the fibre material, unless ;ndicated otherwise~ Temper-atures are in degrees Celsius.
5~
~ 7 --Preparation instructions for known comDounds Instructions A: 3 9 of ethylenediamine are added to a solu-tion of 12~2 9 of salicylaldehyde i~ sn ml of ethanol~ The mixture is seirred for a further 15 minutes and the precipi-tate which has separated out is filtered off with suction.
12.7 g (94% of theory) of yellow flakes of melting point 130-131 of the formula CH~ N=CH~ ~^ (101) ~/ bH HO/ ~/
are obtained.
A solution~ prepared ~ith gentle warming, of 1.99 9 of copper-II acetate monohydrate in 50 ml of dimethylfor-mamide ;s added to 2.68 g of th;s compound, dissolved in 20 ml of d;methylformamide. The mixture is stirred for a further 15 minutes and the prec;pitate which has separated out is filtered off with suction and rinsed with a little dimethylformamide and ethanol. 2.8 9 (86% of theory) of the compound of the formul I~ ,J~ /cu~ , ,~ 102) are obtained in the form of dark olive glossy crystals of melting point 324 (decomposition).
Instruct;ons B: O.S g of ethylenediam;ne ;s added to a solu-tion of 4~02 9 of 5-bromo-2-hydroxybenzaldehyde ;n 2û ml of dimethylformamide, the b;funct;onal Schiff's base rapidly separating out as a yello~ prec;pitate. A solution of 2 9 of copper-II acetate monohydrate in 20 ml of dimethylformamide is then added, the m;~ture is stirred for a further 8 hours and the preci~itate is filtered off with suction and washed w;th d;methylformamide and absolute ethanol. After drying~
4.69 9 (96X of theory) of a grey-green solid substance of 1~, . ~, melting ~oint 301-302 (decomposition) and of the formula (103) ~-O
sr\ ~-\ /CH=~ ~;=C~
il `cu~
~ o / --o ~
Instructio s C-I: The procedure described in Example 1 or 2 is repeated, but the aldehydes and diamines listed in the following Table I are used, affording the analogous copper complexes in similar yields.
Table I
nstructionsjAldehyde Di3mine .
C j5-chloro-2-hydroxy- ~ ethylenediamine .
benzaldehyde 2-hydroxy-1-napth- ethylenediamine . aldehyde E 2-hydroxybenzaldehyde 1-phenyl-ethylene-diamine F 3-methyl~2-hydroxy- ethylenediamine benzaldehyde G 5-methyl-2-hydroxy- ethyl.enediamine . benzaldehyde H 5 tert.-butyl-2- ethylenediamine hydroxybenzaldehyde I 2,4-dihydroxybenz- ethylenediamine ` _ _ aldehyde _ _ _ _ Instructions J:_ 48.8 9 of 2-hydroxybenzaldehyde, 12 g of ethylene-diamine and then a solution, warmed to 85~ of ~9.9 g of ~opper~II-sulfatepent~hydrate in 200 ml of water are added in succession to 200 ml of 2 N sodium hydroxide solution at 85, with stirring. The mixture is allowed to cool to room temperature (15-25), with stirr;ng, and is filtered with swctlon and the residue on the filter is washed free from ~ :`
~;~3~
sulfate to give, after drying at 70 uncler reduced pressure (abou~ 100 mm Hg), 6Z.S 9 (94.8X of theory) of the compound of the formu~a (102) as a dark olive-coloured solid substance.
Instructions K-P:
-The procedure described in Instructions B is repeated,but the aldehydes and diamines listed in the follo~ing Table II are used, affording the analogous copper complexes in similar yields:
Table II
_ _ IInstructions Aldehyde Diam;ne , ~
K 5-chloro-2-hydroxy- ; ethylenediamine benzaldehyde L S-bromo-2-hydro~y- i ethylenediamine benzaldehyde M 2-hydroxy-1-naphthyl- , ethylenediamine aldehyde N 2-hydroxybenzaldehyde ¦ methyl~ethylene- ¦
_ I diamine 0 2-hydroxybenzaldehyde 1 1~Z-cyclohexylene-I diamine P 2-hydroxybenzaldehyde 1-phenyl-ethylene-Instructions Q
A warm solution of 3 9 of copper-II acetate mono-hydrate in S0 ml of dimethylformamide is added at 60C to a solution of 4~87 9 of N,N'-bisC1-(2-hydroxyphenyl)-propyli-dene~ethy-lenediamine (prepared from 1 mole of ethylenediamine and 2 moles of 2-hydroxypropiophenone) in 50 ml of dimethylfor-mamide. The mi~ture is allowed to cool and the precipitate is filtered off with s~ction and ~ashed to give, after drying, 4.6 9 (80X of theory) of the compound of the formula (1) in which A1 is ethyl and R1, RZ, R3, R4, X1 and y1 are hydrogen as small violet-red needles (melt;ng point 280-Z 8 1 C ~
Preparation examples for novel compounds Example 1~ 4.2 9 of N,N'-bis(6-hydroxy-Z,5-dimethylbenzyli-dene)ethylenediamine (prepared from 1 mole of ethylenediamine and 2 moles of 3,6-dimeehyl-2-hydroxy-benzaldehyde) are dis-solved in 150 ml of ethanol and 50 ml of dimethylformamide under the influence of heat. A hot solution of 2~58 9 of copper-II acetate monohydrate in 100 ml of ethanol is added, the mixture is allowed to cool, with stirring, and is filtered ~ith suction to give, after dry;ng~ 4.72 9 (91.4X of theory) of the compound of the formula (1~ in which R1 and R4 are methyl andA1, R2, R3, X1 and y1 are hydrogen as p;nk violet-coloured platelets (melting point > 340 ).
Exa~le Z The procedure described in Example 1 is repeated, but 4-methyl-2-hydroxy-benzaldehyde is employed as the s~artin~ component in the preparation of the Schiff's base, affording the compound of the formula (1) in ~hich R3 is ethyl and A1 R1 R2, R4, X1and y1 are hydrogen as an oLive-coloured solid substance in a similar yield.
Example_ : The procedure described in Example 1 is re-peated, but 4-methoxy-2-hydroxy-benzaldehyde is used as the starting component for the preparation of the Schiff's base, affording the compound of the formula t13 in which R3 is methoxy and A1, R1, R2, R4, X1 and r are hydrogen 3S olive-coloured platelets in a similar yield.
Example 4: 1.5 g of ethylenediam;ne are added to a sus-__ . __ pension of 9.66 9 of 4-diethylamino-2-hydroxybenzaldehyde in 20 ml of ethanol. The mixture is refluxed for 1 hour~ allo~ed to cool and filtered with suction to give, after drying, 8.15 9 t77% of theory) of the Schiff's base of the form~la -N ( CH2 ~C1~3 ) 2 as a pale yellow substance wh;ch is novel per se (melting ~1
The radicals X and Y can independently of one ano-ther be C1-C4-alkyl, for example methyl~ ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl and tert.-butyl.
Aromati'c radicals X and Y are, in particular, subst`ituted or unsubstituted naphthyl and, especially, phenyl radicals.
X and Y can also be l~inked to form a cycloaliphatic radi-cal, for example cyclohexylene~ cyclopentylene or cyclo-heptylene.
Preferably, R1-R4 independently of one another are each hydrogen, chlorine, bromine, methyl, ethyl, butyl, methoxy, ethoxy, methoxyethoxy, ethoxyethoxyethoxy or di-ethylamino or R1 and R2 together form a fused-on ben2ene radical.
~3~1;2S~
Of the subs~ituents X1 and y1~ preferably, one is hydrogen and the other is hydrogen, methyL, ethyl or phenyl~
or X1 and y1 together form a cyclohexylene radical.
Copper complexes which are preferably used are the water-insoluble copper complexes of the formula ~ _ ~ R5 (2) 1 It ~cu r 11 R ~ ~/ \0 / ~ Uf ~ / ~7 R8 l8 in which R5-R8 independently of one another are each hydro-gen, hydrox~L, bromine, methyl, tert.-butyl, methoxy, methoxyethoxy, ethoxyethoxyethoxy or diethylamino, x2 is hydrogen, methyl, ethyl or phenyl and y2 is hydrogen~ or R5 and R6 together form a fused-on benzene radical, or x2 and y2 to~ether form a cyclohexylene radical.
Compounds which are of particular ;nterest are those of the formula ~1/ \0~ \0/ \i~
Rll Rll in ~hich R9, R10 and R11 independently of one another are each hydrogen, chlorine, bromine, methyl or methoxy, or in which R9 and R10 together form a fused-on benzene ring, and X3 is hydrogen, methyl, ethyl or phenyl.
Compounds ~hich are of ch;ef interest, however, are those of the formula (3~ in ~hich R9, R10, R11 and X3 are hydrogen.
The compounds of the fornula (1~ are in some cases compounds which are known per se from, for example, Beilstein and Chemical Abstracts, and in so~e cases noYel compounds.
Thus, compounds of the for~ula (1) in which R3 is me~hyl and A1, R1, R~, ~4~ X and x2 are hydrogen; R1 and R4 are th l and A1 R2 R3 X1 and y1 are hydrogen; R and R
are chlorine and A1, R1~ R3, X1 and y1 are hydrogen; R4 is h nd A1 R4 R2 R3, X1 and y1 are hydrogen; R is methoxy~ methoxyethoxy, ethoxyethoxyethoxy or diethylamino and A1, R1, R2, R4, X1 and y1 are hydrogen;. R2 is meth-oxyethoxy or ethoxyethoxyethoxy and A1, R1, R3, R4, X
and y1 are hydrogen; R2 and R3 are methoxyethoxy or ethoxyethoxyethoxy and A1, R1, R4, X1 and y1 are hydrogen, or one of the two substituents R3 is hydroxyl and the other is methoxyethoxy or ethoxyethoxyethoxy and A1, R1, R2, R4, x1 and y1 are hydrogen, are novel per se.
The compounds of the formula (1) are obtained in a manner which is known per se by reaction of 2 equivalents of the corresponding o-hydroxyaldehydes w;th 1 equivalent of the corresponding diamine to give the corresponding Schiff's base and subsequent metallisation with copper salts. However, it is also possible first to form the cop-per complex of the o-hydroxyaldehyde and then to react th;s ~ith a corresponding diamine to give the copper complex of the bisazomethine of the formula (1).
It is also possible, without isolating the inter-mediates, to react the o-hydroxybenzaldehyde, the diamine and the copper salt in a single step in a so called one-pot process directly to give the compoun~ of the formula (1), or subsequently to modify, for example to alkylate, substi-tuents, ;n particular hydroxyl groups, by a further reac-tion ~hen the preparation of the compound of the formula (1) is complete. These 4 preparation methods are described by Pfeiffer in Liebigs Annalen der Chemie, Volume 503, pages 84-130 (1933).
The copper complexes of the formula (1) are advan-tageously applied from an aqueous bath, these advantageously being employed in an amount such that 5 to 200 ~9, in parti-cular 10 to 100 ~9, of copper are present per 9 of poly-amide fibre material.
The compounds of -the formula ~1) are advantageously , em~loyed as finely divided dispersions obtained by grinding in the presence of customary dispersants.
If the copper cornplexes are used for stabilising dyed mater;al, the fibre material can be treated with ehe copper complex before, during or after dyeing. The copper complex is ad~antageously added directly to the dyeing or padding liquor. Dyeirlg is carried out continuously or batchwise. In the continuous procedure, the copper com-plexes can be fixed by steam or heat.
Polyamide material is understood as mean;ng synthe-tic polyamide, for example polyamide-6, polyamide-66 or polyamide-12~ In add;t;on to pure polyamide fibres, f;bre mixtures of polyurethane and polyamide~ thus, for example, tricot material of polyamide/polyurethane in a mixture rat;o of 7~:30, are also particularly suitable. ln prin-ciple, the pure or mixed polyamide material can be in the most diverse processing forms, for example as fibres, yarn, woven fabric or knitted fabric.
In particular polyam;de mater;al which is exposed to light and heat and is in the form of, for example, auto-mobile upholstery or carpets is espec;ally suitable for treatment by the present process.
Dye;ng is carried out in the customary manner, for exam~le with-metal complex dyes or with anthraquinone dyes or azo dyes. The known types of metal complex dyes are used, in particular the 1:2 chromium or 1:2 cobalt com-plexes of mono- or disazo~ or -azomethine dyes, a large number of which are described ;n the l;terature. In addi-tion to these, dyes from other classes of dyes are of course also suitable, for example disperse or vat dyes.
The following preparation instructions and examples serve to illustrate the invention. Parts and percentages are by weight. The percentage data relating to the add;-tions to the 1ndividual treatment baths and dyebaths relate to the fibre material, unless ;ndicated otherwise~ Temper-atures are in degrees Celsius.
5~
~ 7 --Preparation instructions for known comDounds Instructions A: 3 9 of ethylenediamine are added to a solu-tion of 12~2 9 of salicylaldehyde i~ sn ml of ethanol~ The mixture is seirred for a further 15 minutes and the precipi-tate which has separated out is filtered off with suction.
12.7 g (94% of theory) of yellow flakes of melting point 130-131 of the formula CH~ N=CH~ ~^ (101) ~/ bH HO/ ~/
are obtained.
A solution~ prepared ~ith gentle warming, of 1.99 9 of copper-II acetate monohydrate in 50 ml of dimethylfor-mamide ;s added to 2.68 g of th;s compound, dissolved in 20 ml of d;methylformamide. The mixture is stirred for a further 15 minutes and the prec;pitate which has separated out is filtered off with suction and rinsed with a little dimethylformamide and ethanol. 2.8 9 (86% of theory) of the compound of the formul I~ ,J~ /cu~ , ,~ 102) are obtained in the form of dark olive glossy crystals of melting point 324 (decomposition).
Instruct;ons B: O.S g of ethylenediam;ne ;s added to a solu-tion of 4~02 9 of 5-bromo-2-hydroxybenzaldehyde ;n 2û ml of dimethylformamide, the b;funct;onal Schiff's base rapidly separating out as a yello~ prec;pitate. A solution of 2 9 of copper-II acetate monohydrate in 20 ml of dimethylformamide is then added, the m;~ture is stirred for a further 8 hours and the preci~itate is filtered off with suction and washed w;th d;methylformamide and absolute ethanol. After drying~
4.69 9 (96X of theory) of a grey-green solid substance of 1~, . ~, melting ~oint 301-302 (decomposition) and of the formula (103) ~-O
sr\ ~-\ /CH=~ ~;=C~
il `cu~
~ o / --o ~
Instructio s C-I: The procedure described in Example 1 or 2 is repeated, but the aldehydes and diamines listed in the following Table I are used, affording the analogous copper complexes in similar yields.
Table I
nstructionsjAldehyde Di3mine .
C j5-chloro-2-hydroxy- ~ ethylenediamine .
benzaldehyde 2-hydroxy-1-napth- ethylenediamine . aldehyde E 2-hydroxybenzaldehyde 1-phenyl-ethylene-diamine F 3-methyl~2-hydroxy- ethylenediamine benzaldehyde G 5-methyl-2-hydroxy- ethyl.enediamine . benzaldehyde H 5 tert.-butyl-2- ethylenediamine hydroxybenzaldehyde I 2,4-dihydroxybenz- ethylenediamine ` _ _ aldehyde _ _ _ _ Instructions J:_ 48.8 9 of 2-hydroxybenzaldehyde, 12 g of ethylene-diamine and then a solution, warmed to 85~ of ~9.9 g of ~opper~II-sulfatepent~hydrate in 200 ml of water are added in succession to 200 ml of 2 N sodium hydroxide solution at 85, with stirring. The mixture is allowed to cool to room temperature (15-25), with stirr;ng, and is filtered with swctlon and the residue on the filter is washed free from ~ :`
~;~3~
sulfate to give, after drying at 70 uncler reduced pressure (abou~ 100 mm Hg), 6Z.S 9 (94.8X of theory) of the compound of the formu~a (102) as a dark olive-coloured solid substance.
Instructions K-P:
-The procedure described in Instructions B is repeated,but the aldehydes and diamines listed in the follo~ing Table II are used, affording the analogous copper complexes in similar yields:
Table II
_ _ IInstructions Aldehyde Diam;ne , ~
K 5-chloro-2-hydroxy- ; ethylenediamine benzaldehyde L S-bromo-2-hydro~y- i ethylenediamine benzaldehyde M 2-hydroxy-1-naphthyl- , ethylenediamine aldehyde N 2-hydroxybenzaldehyde ¦ methyl~ethylene- ¦
_ I diamine 0 2-hydroxybenzaldehyde 1 1~Z-cyclohexylene-I diamine P 2-hydroxybenzaldehyde 1-phenyl-ethylene-Instructions Q
A warm solution of 3 9 of copper-II acetate mono-hydrate in S0 ml of dimethylformamide is added at 60C to a solution of 4~87 9 of N,N'-bisC1-(2-hydroxyphenyl)-propyli-dene~ethy-lenediamine (prepared from 1 mole of ethylenediamine and 2 moles of 2-hydroxypropiophenone) in 50 ml of dimethylfor-mamide. The mi~ture is allowed to cool and the precipitate is filtered off with s~ction and ~ashed to give, after drying, 4.6 9 (80X of theory) of the compound of the formula (1) in which A1 is ethyl and R1, RZ, R3, R4, X1 and y1 are hydrogen as small violet-red needles (melt;ng point 280-Z 8 1 C ~
Preparation examples for novel compounds Example 1~ 4.2 9 of N,N'-bis(6-hydroxy-Z,5-dimethylbenzyli-dene)ethylenediamine (prepared from 1 mole of ethylenediamine and 2 moles of 3,6-dimeehyl-2-hydroxy-benzaldehyde) are dis-solved in 150 ml of ethanol and 50 ml of dimethylformamide under the influence of heat. A hot solution of 2~58 9 of copper-II acetate monohydrate in 100 ml of ethanol is added, the mixture is allowed to cool, with stirring, and is filtered ~ith suction to give, after dry;ng~ 4.72 9 (91.4X of theory) of the compound of the formula (1~ in which R1 and R4 are methyl andA1, R2, R3, X1 and y1 are hydrogen as p;nk violet-coloured platelets (melting point > 340 ).
Exa~le Z The procedure described in Example 1 is repeated, but 4-methyl-2-hydroxy-benzaldehyde is employed as the s~artin~ component in the preparation of the Schiff's base, affording the compound of the formula (1) in ~hich R3 is ethyl and A1 R1 R2, R4, X1and y1 are hydrogen as an oLive-coloured solid substance in a similar yield.
Example_ : The procedure described in Example 1 is re-peated, but 4-methoxy-2-hydroxy-benzaldehyde is used as the starting component for the preparation of the Schiff's base, affording the compound of the formula t13 in which R3 is methoxy and A1, R1, R2, R4, X1 and r are hydrogen 3S olive-coloured platelets in a similar yield.
Example 4: 1.5 g of ethylenediam;ne are added to a sus-__ . __ pension of 9.66 9 of 4-diethylamino-2-hydroxybenzaldehyde in 20 ml of ethanol. The mixture is refluxed for 1 hour~ allo~ed to cool and filtered with suction to give, after drying, 8.15 9 t77% of theory) of the Schiff's base of the form~la -N ( CH2 ~C1~3 ) 2 as a pale yellow substance wh;ch is novel per se (melting ~1
3~Z~i~
point: 137-138 ).
~ ereafter, a solution of 3 9 of copper-II acetate monohydrate in 100 ml of warm ethanol is added to a solution of 6.15 9 of the Schiff's base of the formula t104~ in 100 ml of warm ethanol. After stirring for 30 minutes, the mixture is filtered with suction. The residue on the fil~er is stirred with 30 ml of 1 N sodium hydroxide solution and 20 ml of ethanol for 3û minutes, filtered off with suct;on, washed neutral with water and dried.
~.9 9 (93% of theory) of the compound of the formula (1) in which R3 is diethylamino and A1, R1, R2, R4, X1 and y1 are hydrogen are obtained as a dark grey finely crystalline substance tmelting point 135-136 (decomposition)). Accor-ding to elemental analysis, the substance contains 1 mole of water of crystallisation.
Example_5: The procedure described in Instructions 8 is re-peated, but 3,5-dichloro~2-hydroxybenzaldehyde is used affording the compound of the formula t1) in which ~2 and R4 are chlorine and A1, R1, R3, X1 and y1 are hydrogen as a violet pink-coloured solid substance in a similar yield.
Example 6: The procedure described in Instructjons B is re-peated, but 3-methoxy-2-hydroxybenzaldehyde is used, afford-ing the compound of the formula (1) in which R4 is methoxy and A1, R1, R2, R3, X1 and y1 are hydrogen as turquoise-coloured platelets in a similar yield.
Example 7: 5.32 9 of 3û% sodium hydroxide solution (dilu-ted with 30 ml of ethanol) are added to a suspens;on of 7.24 9 of the copper complex according to Instructions I in 3ûO ml of ethanol at 8û, w;th st;rring. The m;xture is allowed to cool and the precip;tate is filtered off with suction and washed with ethanol. After drying, 7.4 9 (77~
of theory) of the corresponding sodium salt, which is novel per se, are obtained as a dark violet-coloured finely crystal-line substance which, according to elemental analysis and acidimetric titration, contains 6 moles of water of crystal-lisation. Thereafter~ 25.8 g of 2-methoxyethyltosylate are added to a suspension of 22.4 9 of the disodium salt thus ~3~
obtained in 300 ml of dimethylformamide. The mixture is s~ir-red at 140 for 70 minutesO After cooling, it is poured into 1.5 ~itres of water, with stirrin~, and the precipitate is fil~ered off with suction and washed. The residue on the filter is stirred with 100 ml of 1 N sodiwm hydroxide solu-tion for 1 hour, filtered off with suction, washed neutral and dried. 16.45 9 (58% of theory) of the copper complex which, according to elemental analysis, contains 2 moles of water of crystallisation and corresponds to the formula (1) in which R is methoxyethoxy and A1, R1, ~2, R~, X1 and y1 are hydrogen are obtained as pale turquoise-coloured sub-stance (melting point 132-135 ).
Example 8: The procedure described in Example 7 is repeated, but 2-~2~ethoxy)-ethoxy]-ethyl tosylate is used, affording the compound of the formula (1) in which R is ethoxyethoxy-ethoxy and A1, R1, R2, R4, X1 and y1 are hydrogen as a pale turquoise-coloured solid substance in a similar yield.
Application examples Example 9: 5 9 of the condensation product of naphthalene-sulfonic acid and formaldehyde, as a dispersant, dissolved in 7.5 ml of water, and 20 9 of quartz beads ~diameter about 1 mm) are added to 5 9 of the compounds prepared according to Instructions A and the components are ground with a stirrer at about 10600 revolutions per minute until the particle size is less than 2lum. The dispersion is separated off from the quartz beads by means of a fine mesh sieve and adjusted to 20% of active substance with water.
Stirring in 0.3% of carboxymethylcellulose stabi-lises the dispersion.
Stable dispersions can be prepared from the com-pounds of Instructions 8-Q and 'xamples 1-8 in the same manner.
E~aEpLe 10: Three pieces of a nylon 66 automobile cushion tricot weighing 15 g are treated in a dyeing apparatus with open treatment baths with liquors ~l;quor ratio of 1:25~ con~
taining 2% of ammonium sulfate, û.2% of the dye of the formula (in each case calculated on the fibre weight):
~,Z~
\0 ~, 1 -N=N-~ ~o 2~/ ~u 0 - o SO2NHCH 1:2 Co mi xed co0pi.ex (105) ~H O-C-CH
1l -N=N-C-CO~H- ~ O
/
S02~C~(CH3)2 and 0.35X of the uet-ground dispersion, obta;ned accordi ng to Example 9, of the compounds accord;n~ to Instructions A or C. Dyeing ~ithout the addition of these co~pounds serves as a comparison. Treatment is initially carried out at 50 for 5 minutes, and the temperature ;s then increased to 9S at 2 /m;nute. The goods are treated at this temperature for 30 ~inutes and then cooled to 70 , r;nsed cold~ centr;fuged and dr;ed at 80 ;n a circulat;ng a;r cab;net~ The light-fastnesses of the dyeings are determ;ned ;n accordance ~ith SN-IS0 105-B02 (Xenon) and in accordance ~ith DIN 75,202 tprov.) (Fakra)~ The dye;ngs ~sample si2e about 18 x 10 cm) are furthermore exposed to heat over part of their area tabout 18 x 4.5 cm) w;th covered side parts for 250 hours ;n accordance with DIN 75,202 (prov.). These samples are then tested for their tear strength and elongat;on ;n accordance with SNV 198,461.
The copper content of the f;bre mater;al dyed ;n the presence of the compound according to Instructions A or C ~as de~ermined as 100 ~9 of Cu per g of fibre mater;al.
The light fastness of the dyeings ~h;ch have been produced in the presence of the compounds accord;ng to Instruct;ons A or C is clearly better than the l;ght-fastness - - ~;2 3~
of the comparison dyeing without these compoundsO
Furthermore, hy adding the compounds according to Instructions A or C, the tear strength of the polyamide material after the exposure to lisht is considerably improved and the elongation is greater.
Similar results are achieved if 0.35% of the disPer-sion, obtained according to Example 9~ of the compounds according to Instructions C or D-Q or Examples 1-8 is used.
Example 11~ A 0.2% dyeing with the red dye of the formwla .
HO
~ \-N=N-~ 2 Co complex t106) ~/ / \.
3 ( H2)2NHS 2 is carr;ed out as described ;n Example 10, as well as ;n each case an analogous dye;ng in which 0.35% of a dispersion, obtained according to the statements in Example 9, of the compounds according to Instructions A or C are additionally present. With this dyeing also, the addition of the Cu som-plexes according to Instructions A or C has the effect of a clear i~pro~ement in light-fastness, tear strength and elongation.
The copper content of the fibre material dyed in the presence of the compound according to Instructions A or C was 99 ~9 of Cu per g of fibre material.
Example 12: Dyeing is carried out as described in Example 10 with 0.1% of the dye of the formula OH ~O-C-CH3 2 Co complex tlO7) N=N-c -CO-NH--\ /$
/ C~
, ~3~
The dyed material is investigated as described in Example 10.
With this dyeing also, the addition of the Cu com-plexes according to Instructions A or C has the effect of a clear improvement in the light-fastness, the tear s-trength and the elongationO
Example 13: The compounds of Instructions A, i3 or C or Example 6 formulated according to Example 9 are tested on a nylon-66 filament yarn (7 x 3 tex). For this, beige dyeings are produced, these being obtained as described belo~.
Five yarn strands of 10 9 of the nylon filament yarn are treated on a dyeing apparatus in open dyebaths with a liquor ratio of 1:4û. The dyebaths are charged with 2 g/l of ammonium sulfate (pH 6.8), in each case O or 0.3~ of the formulations, prepared according to Example 10, of the com-pounds according to Instructions A, i3 or C or Example 6 and the dye combination tdissolved in water).
0.04~
dye 1 1:2 Co complex of the formula (107) (yellow) O.OZS% OH ~.-N~
-N=N~
t C~3=N 3 ¦ 1:2 Cr complex (108) N02OH 0~ ~ (brown) c/ ~~-N=N-~ /o \0~ ~/ D
~ N=N J
~3~S~
0.0~3% .
dye 3 ~=4 =~
HO S ~ O/ ~o -N7- ~ ~ ( b l a c k ) o--Cr O
,o/l\o~
OCH3 ~ .-N=N~
/
o~ N=N
Dyeing ; started at 40 ana tne temperature is increased to 95 in the course of about 30 minutes. Dyeing is carried out at this temperature for 60 minutes and the dyed yarn is cooled to 70 , rinsed, centr;fuged and dried.
On the one hand the light-fastness of the dyeings is determined in accordance with SN-ISO 105 ~02 (Xenon~ and DIN
75,202 (prov.~ (Fakra~, and on the other hand the yarn is ~ound onto cards ~30 layers, gauge length about 22 cm) and exposed to heat for 200 hours in accordance with DIN 75,202 (prov.~ Thereafter, the goods are tested for tear strength and elongation in accordance with SNV 97,461~
The addition of the compounds according to Instructions A, ~ or C or Example 6 also has the effect of a clear improvement in light-fastness, tear strength and elongation on the nylon filament yarn dyed with the above dyes. This also applies to the compounds according to Instructions D~Q or Examples 1-5, 7 or 8.
Example 14: Four lU g polyamide 66 filament yarn strands (7 x 3 tex) are prepared for treatment on a yarn-dyeing apparatus. 1% of 80% acetic acid (pH 5.5) is generally added to the treatment baths.
Bath No. 1 contains no further additive, bath No. 2 contains 0.35% of a formulation, obtained according to 'xample 9~ of the compound according to Instructions Ao bath No. 3 con-tains 0~2% of the dye of the formula ~ ~3~5~
~ 17 -O M~-CE~
Il I I
\~/;e/ ~-CH3 O NH- CH-C~ -C~ -6 ~ 0) ca3 and bath NQ. 4 contains 0.2X of this dye and 0.35% of a formu-lation, obtained according to the ;nformat;on of Example 9, of the compound of Instructions A.
Treat~ent is carried ou~ at a liquor ratio of 1:40 initially at 50 , the temperature ;s then increased to 95 in the course of 30 minutes and treatment is carr;ed out for 60 m;nutes. Thereafter, the goods are cooled to 70 ~ rinsed cold, centrifuged and dried at 80 .
The trea~ments are tested as descr;bed ;n Example 13.
The addit;on of a copper compound according ~o Instructions A has the effect of a clear impro~ement ;n the ~ear strength and elongation ;n the samples treated in baths No. Z and 4 in comparison with the samples treated without ~he copper compound~ The l;ght-fastness of the dyeing pro-duced with bath 4 ;s aLso clearly improved ;n comparison with the dye;ng produced with bath 3.
: The procedure ;n Example 10 ;s repeated, but ;n each case 2 pieces of the nylon tr;cot we;ghing 10 9 are dyed w;th a liquor, ;n a l;quor rat;o of 1:30, contain;ng 2% of 80X acetic acid, Q or Q.2X of the d;spers;on, obta;ned-accord ing to Example 9, of the compound accord;ng to Ins~ruct;ons A and 0.1% of the yellow dye of the formula ~;~3~
- 1S ~
f ~ 503Na ( 1 1 1 ) ~ HO~ 3 NH C\ ~--Ci Cl ;~ \ CH
~/
The addition of the compound according to Instructions A to the dye liquor has the effect of substantially improving the light-fastness of the dyeings and the tear strength and elonga-tion of the polyamide material after exposure to light.
This also applies if 1.0% of the dye oF the formula (111) is used in the dye l;quor. Similar results are also achieved if 0.09% of ~he orange-coloured dye of the formul~
._ ,, ._ .
CH -6~ ~q-so2-~ -S03i~1a ~_N Q~ ~-N-CH2--~ /O ~1 12 ~
~=o I ~=.~
~ C2 H5 or O.û9% of the red dye of the formula :: :
~H -~ -SO o ~~ -N=~ N=N-~ - ( 11 3 ) NaS03 ~
i SO ~ .`;a is used in the dye liquor. This also applies if O.~J~ of the dye of the formula (112~ or 0.9% of the dye of ~he formula (113) is used.
If 0.05% of the dye of the formula :
, .
N=CH~ CH (114) 2 k4H9 il-so3Na ~, is used in add;tion to ~he copper complex compound according to Instructions A or C, even more clearly improved tear strength and elon~ation values are obtained on dyeing.
Example 16:
In each case 3 nylon-66 tricot pieces weighing 1~ g are dyed with ;n each case 0.2X of the dyes of the for~ula ~105), (106) or (107), rinsed and dried, as described in Example 10. Whilst ser;es 1 of these dyeings relnains unchanged, the two series 2 and 3 are padded, at a liquor pick-up of 75Xo with a liq~or containing 1/2 g/l of a non-ionic surfactant (adduct of 1 mole of nonylphenol and 9 1/2 moles of ethylene oxide) and 2 g~l of the compound of the formula (102), formulated according to Example 9, and are dried at 1Z0 for 1 minute. The dyeings of series 2 are heat~
treated at 1~0 for 60 seconds, and those of series 3 are treated ~ith saturated steam of about 100 for 5 minutes.
All the dyeings are tes~ed as described in Example 10.
It is found here that the dyeings of ser;es 2 and 3 are sig-nificantly improved in respect of light-fastness ~hen hot~
tear strength and elongat;on in comparison with those of ~series 1.
~i.
point: 137-138 ).
~ ereafter, a solution of 3 9 of copper-II acetate monohydrate in 100 ml of warm ethanol is added to a solution of 6.15 9 of the Schiff's base of the formula t104~ in 100 ml of warm ethanol. After stirring for 30 minutes, the mixture is filtered with suction. The residue on the fil~er is stirred with 30 ml of 1 N sodium hydroxide solution and 20 ml of ethanol for 3û minutes, filtered off with suct;on, washed neutral with water and dried.
~.9 9 (93% of theory) of the compound of the formula (1) in which R3 is diethylamino and A1, R1, R2, R4, X1 and y1 are hydrogen are obtained as a dark grey finely crystalline substance tmelting point 135-136 (decomposition)). Accor-ding to elemental analysis, the substance contains 1 mole of water of crystallisation.
Example_5: The procedure described in Instructions 8 is re-peated, but 3,5-dichloro~2-hydroxybenzaldehyde is used affording the compound of the formula t1) in which ~2 and R4 are chlorine and A1, R1, R3, X1 and y1 are hydrogen as a violet pink-coloured solid substance in a similar yield.
Example 6: The procedure described in Instructjons B is re-peated, but 3-methoxy-2-hydroxybenzaldehyde is used, afford-ing the compound of the formula (1) in which R4 is methoxy and A1, R1, R2, R3, X1 and y1 are hydrogen as turquoise-coloured platelets in a similar yield.
Example 7: 5.32 9 of 3û% sodium hydroxide solution (dilu-ted with 30 ml of ethanol) are added to a suspens;on of 7.24 9 of the copper complex according to Instructions I in 3ûO ml of ethanol at 8û, w;th st;rring. The m;xture is allowed to cool and the precip;tate is filtered off with suction and washed with ethanol. After drying, 7.4 9 (77~
of theory) of the corresponding sodium salt, which is novel per se, are obtained as a dark violet-coloured finely crystal-line substance which, according to elemental analysis and acidimetric titration, contains 6 moles of water of crystal-lisation. Thereafter~ 25.8 g of 2-methoxyethyltosylate are added to a suspension of 22.4 9 of the disodium salt thus ~3~
obtained in 300 ml of dimethylformamide. The mixture is s~ir-red at 140 for 70 minutesO After cooling, it is poured into 1.5 ~itres of water, with stirrin~, and the precipitate is fil~ered off with suction and washed. The residue on the filter is stirred with 100 ml of 1 N sodiwm hydroxide solu-tion for 1 hour, filtered off with suction, washed neutral and dried. 16.45 9 (58% of theory) of the copper complex which, according to elemental analysis, contains 2 moles of water of crystallisation and corresponds to the formula (1) in which R is methoxyethoxy and A1, R1, ~2, R~, X1 and y1 are hydrogen are obtained as pale turquoise-coloured sub-stance (melting point 132-135 ).
Example 8: The procedure described in Example 7 is repeated, but 2-~2~ethoxy)-ethoxy]-ethyl tosylate is used, affording the compound of the formula (1) in which R is ethoxyethoxy-ethoxy and A1, R1, R2, R4, X1 and y1 are hydrogen as a pale turquoise-coloured solid substance in a similar yield.
Application examples Example 9: 5 9 of the condensation product of naphthalene-sulfonic acid and formaldehyde, as a dispersant, dissolved in 7.5 ml of water, and 20 9 of quartz beads ~diameter about 1 mm) are added to 5 9 of the compounds prepared according to Instructions A and the components are ground with a stirrer at about 10600 revolutions per minute until the particle size is less than 2lum. The dispersion is separated off from the quartz beads by means of a fine mesh sieve and adjusted to 20% of active substance with water.
Stirring in 0.3% of carboxymethylcellulose stabi-lises the dispersion.
Stable dispersions can be prepared from the com-pounds of Instructions 8-Q and 'xamples 1-8 in the same manner.
E~aEpLe 10: Three pieces of a nylon 66 automobile cushion tricot weighing 15 g are treated in a dyeing apparatus with open treatment baths with liquors ~l;quor ratio of 1:25~ con~
taining 2% of ammonium sulfate, û.2% of the dye of the formula (in each case calculated on the fibre weight):
~,Z~
\0 ~, 1 -N=N-~ ~o 2~/ ~u 0 - o SO2NHCH 1:2 Co mi xed co0pi.ex (105) ~H O-C-CH
1l -N=N-C-CO~H- ~ O
/
S02~C~(CH3)2 and 0.35X of the uet-ground dispersion, obta;ned accordi ng to Example 9, of the compounds accord;n~ to Instructions A or C. Dyeing ~ithout the addition of these co~pounds serves as a comparison. Treatment is initially carried out at 50 for 5 minutes, and the temperature ;s then increased to 9S at 2 /m;nute. The goods are treated at this temperature for 30 ~inutes and then cooled to 70 , r;nsed cold~ centr;fuged and dr;ed at 80 ;n a circulat;ng a;r cab;net~ The light-fastnesses of the dyeings are determ;ned ;n accordance ~ith SN-IS0 105-B02 (Xenon) and in accordance ~ith DIN 75,202 tprov.) (Fakra)~ The dye;ngs ~sample si2e about 18 x 10 cm) are furthermore exposed to heat over part of their area tabout 18 x 4.5 cm) w;th covered side parts for 250 hours ;n accordance with DIN 75,202 (prov.). These samples are then tested for their tear strength and elongat;on ;n accordance with SNV 198,461.
The copper content of the f;bre mater;al dyed ;n the presence of the compound according to Instructions A or C ~as de~ermined as 100 ~9 of Cu per g of fibre mater;al.
The light fastness of the dyeings ~h;ch have been produced in the presence of the compounds accord;ng to Instruct;ons A or C is clearly better than the l;ght-fastness - - ~;2 3~
of the comparison dyeing without these compoundsO
Furthermore, hy adding the compounds according to Instructions A or C, the tear strength of the polyamide material after the exposure to lisht is considerably improved and the elongation is greater.
Similar results are achieved if 0.35% of the disPer-sion, obtained according to Example 9~ of the compounds according to Instructions C or D-Q or Examples 1-8 is used.
Example 11~ A 0.2% dyeing with the red dye of the formwla .
HO
~ \-N=N-~ 2 Co complex t106) ~/ / \.
3 ( H2)2NHS 2 is carr;ed out as described ;n Example 10, as well as ;n each case an analogous dye;ng in which 0.35% of a dispersion, obtained according to the statements in Example 9, of the compounds according to Instructions A or C are additionally present. With this dyeing also, the addition of the Cu som-plexes according to Instructions A or C has the effect of a clear i~pro~ement in light-fastness, tear strength and elongation.
The copper content of the fibre material dyed in the presence of the compound according to Instructions A or C was 99 ~9 of Cu per g of fibre material.
Example 12: Dyeing is carried out as described in Example 10 with 0.1% of the dye of the formula OH ~O-C-CH3 2 Co complex tlO7) N=N-c -CO-NH--\ /$
/ C~
, ~3~
The dyed material is investigated as described in Example 10.
With this dyeing also, the addition of the Cu com-plexes according to Instructions A or C has the effect of a clear improvement in the light-fastness, the tear s-trength and the elongationO
Example 13: The compounds of Instructions A, i3 or C or Example 6 formulated according to Example 9 are tested on a nylon-66 filament yarn (7 x 3 tex). For this, beige dyeings are produced, these being obtained as described belo~.
Five yarn strands of 10 9 of the nylon filament yarn are treated on a dyeing apparatus in open dyebaths with a liquor ratio of 1:4û. The dyebaths are charged with 2 g/l of ammonium sulfate (pH 6.8), in each case O or 0.3~ of the formulations, prepared according to Example 10, of the com-pounds according to Instructions A, i3 or C or Example 6 and the dye combination tdissolved in water).
0.04~
dye 1 1:2 Co complex of the formula (107) (yellow) O.OZS% OH ~.-N~
-N=N~
t C~3=N 3 ¦ 1:2 Cr complex (108) N02OH 0~ ~ (brown) c/ ~~-N=N-~ /o \0~ ~/ D
~ N=N J
~3~S~
0.0~3% .
dye 3 ~=4 =~
HO S ~ O/ ~o -N7- ~ ~ ( b l a c k ) o--Cr O
,o/l\o~
OCH3 ~ .-N=N~
/
o~ N=N
Dyeing ; started at 40 ana tne temperature is increased to 95 in the course of about 30 minutes. Dyeing is carried out at this temperature for 60 minutes and the dyed yarn is cooled to 70 , rinsed, centr;fuged and dried.
On the one hand the light-fastness of the dyeings is determined in accordance with SN-ISO 105 ~02 (Xenon~ and DIN
75,202 (prov.~ (Fakra~, and on the other hand the yarn is ~ound onto cards ~30 layers, gauge length about 22 cm) and exposed to heat for 200 hours in accordance with DIN 75,202 (prov.~ Thereafter, the goods are tested for tear strength and elongation in accordance with SNV 97,461~
The addition of the compounds according to Instructions A, ~ or C or Example 6 also has the effect of a clear improvement in light-fastness, tear strength and elongation on the nylon filament yarn dyed with the above dyes. This also applies to the compounds according to Instructions D~Q or Examples 1-5, 7 or 8.
Example 14: Four lU g polyamide 66 filament yarn strands (7 x 3 tex) are prepared for treatment on a yarn-dyeing apparatus. 1% of 80% acetic acid (pH 5.5) is generally added to the treatment baths.
Bath No. 1 contains no further additive, bath No. 2 contains 0.35% of a formulation, obtained according to 'xample 9~ of the compound according to Instructions Ao bath No. 3 con-tains 0~2% of the dye of the formula ~ ~3~5~
~ 17 -O M~-CE~
Il I I
\~/;e/ ~-CH3 O NH- CH-C~ -C~ -6 ~ 0) ca3 and bath NQ. 4 contains 0.2X of this dye and 0.35% of a formu-lation, obtained according to the ;nformat;on of Example 9, of the compound of Instructions A.
Treat~ent is carried ou~ at a liquor ratio of 1:40 initially at 50 , the temperature ;s then increased to 95 in the course of 30 minutes and treatment is carr;ed out for 60 m;nutes. Thereafter, the goods are cooled to 70 ~ rinsed cold, centrifuged and dried at 80 .
The trea~ments are tested as descr;bed ;n Example 13.
The addit;on of a copper compound according ~o Instructions A has the effect of a clear impro~ement ;n the ~ear strength and elongation ;n the samples treated in baths No. Z and 4 in comparison with the samples treated without ~he copper compound~ The l;ght-fastness of the dyeing pro-duced with bath 4 ;s aLso clearly improved ;n comparison with the dye;ng produced with bath 3.
: The procedure ;n Example 10 ;s repeated, but ;n each case 2 pieces of the nylon tr;cot we;ghing 10 9 are dyed w;th a liquor, ;n a l;quor rat;o of 1:30, contain;ng 2% of 80X acetic acid, Q or Q.2X of the d;spers;on, obta;ned-accord ing to Example 9, of the compound accord;ng to Ins~ruct;ons A and 0.1% of the yellow dye of the formula ~;~3~
- 1S ~
f ~ 503Na ( 1 1 1 ) ~ HO~ 3 NH C\ ~--Ci Cl ;~ \ CH
~/
The addition of the compound according to Instructions A to the dye liquor has the effect of substantially improving the light-fastness of the dyeings and the tear strength and elonga-tion of the polyamide material after exposure to light.
This also applies if 1.0% of the dye oF the formula (111) is used in the dye l;quor. Similar results are also achieved if 0.09% of ~he orange-coloured dye of the formul~
._ ,, ._ .
CH -6~ ~q-so2-~ -S03i~1a ~_N Q~ ~-N-CH2--~ /O ~1 12 ~
~=o I ~=.~
~ C2 H5 or O.û9% of the red dye of the formula :: :
~H -~ -SO o ~~ -N=~ N=N-~ - ( 11 3 ) NaS03 ~
i SO ~ .`;a is used in the dye liquor. This also applies if O.~J~ of the dye of the formula (112~ or 0.9% of the dye of ~he formula (113) is used.
If 0.05% of the dye of the formula :
, .
N=CH~ CH (114) 2 k4H9 il-so3Na ~, is used in add;tion to ~he copper complex compound according to Instructions A or C, even more clearly improved tear strength and elon~ation values are obtained on dyeing.
Example 16:
In each case 3 nylon-66 tricot pieces weighing 1~ g are dyed with ;n each case 0.2X of the dyes of the for~ula ~105), (106) or (107), rinsed and dried, as described in Example 10. Whilst ser;es 1 of these dyeings relnains unchanged, the two series 2 and 3 are padded, at a liquor pick-up of 75Xo with a liq~or containing 1/2 g/l of a non-ionic surfactant (adduct of 1 mole of nonylphenol and 9 1/2 moles of ethylene oxide) and 2 g~l of the compound of the formula (102), formulated according to Example 9, and are dried at 1Z0 for 1 minute. The dyeings of series 2 are heat~
treated at 1~0 for 60 seconds, and those of series 3 are treated ~ith saturated steam of about 100 for 5 minutes.
All the dyeings are tes~ed as described in Example 10.
It is found here that the dyeings of ser;es 2 and 3 are sig-nificantly improved in respect of light-fastness ~hen hot~
tear strength and elongat;on in comparison with those of ~series 1.
~i.
Claims (8)
1. A process for photochemicaL stabiLisation of poLy-amide fibre materiaL or a mixture thereof with another fibre materiaL, which comprises treating the poLyamide fibre materiaL with a copper compLex of the formuLa (1) in which A1 is hydrogen or C1-C3-aLkyL, R1, R2, R3 and R4 are each hydrogen, haLogen, hydroxyL, hydroxyaLkyL, aLkyL, aLkoxy, aLkoxyaLkoxy, aLkoxyaLkoxyaLkoxy, car-boxymethoxy, aLkyLamino, diaLkyLamino, -SO2NH2, -SO2NHR
or -SO2NK2, in which R is aLkyL or aLkoxyaLkyL and aLkyL or aLkoxy is in each case to be understood as a group with 1-4 C atoms, or R1 and R2 or R2 and R3 or R3 and R4, together with the C atoms to which they are bonded, form a benzene radicaL, and X and Y
are each hydrogen, C1-C4-aLkyL or an aromatic radicaL, or X1 and y1, together with the C atoms to which they are bonded, form a cycLoaLiphatic radicaL with 5-7 C atoms.
or -SO2NK2, in which R is aLkyL or aLkoxyaLkyL and aLkyL or aLkoxy is in each case to be understood as a group with 1-4 C atoms, or R1 and R2 or R2 and R3 or R3 and R4, together with the C atoms to which they are bonded, form a benzene radicaL, and X and Y
are each hydrogen, C1-C4-aLkyL or an aromatic radicaL, or X1 and y1, together with the C atoms to which they are bonded, form a cycLoaLiphatic radicaL with 5-7 C atoms.
2. The process according to cLaim 1, wherein a compound of the formuLa (2) in which R5, R6, R7 and R8 are each hydrogen, hydroxyl, chlorine, bromine, methyl, tert.-butyl, methoxy, methoxyethoxy, ethoxyethoxyethoxy or diethylamino, X2 is hydrogen, methyl, ethyl or phenyl and Y2 is hydrogen, or R5 and R6 together form a benzene radical, or X2 and Y2 together form a cyclo-hexylene radical, is used.
3. The process according to claim 2, wherein a compound of the formula (2) in which R5, R6, R7 and R8 are hydrogen and X2 and Y2 together form a cyclohexylene radical is used.
4. The process according to claim 1, wherein a compound of the formula (3) in which R9, R10 and R11 are each hydrogen, chlorine, bromine methyl or methoxy, or R9 and R10 together form a benzene ring, and X3 is hydrogen, methyl, ethyl or phenyl, is used.
5. The process according to claim 4, wherein a compound of the formula (3) in which R9, R10, R11 and X3 are hydro-gen is used.
6. The process according to claim 1, wherein the copper complex is added directly to the dyebath.
7. The process according to claim 1, wherein the copper complex is employed in an amount such that 5 to 200 µg of copper are present per g of polyamide.
8. The process according to claim 1, wherein fibre mix-tures of polyamide and polyurethane are used.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH197585 | 1985-05-09 | ||
| CH1975/85-2 | 1985-05-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1239254A true CA1239254A (en) | 1988-07-19 |
Family
ID=4222993
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000494753A Expired CA1239254A (en) | 1985-05-09 | 1985-11-07 | Process for photochemical stabilisation of non-dyed and dyed polyamide fibre material and mixtures thereof |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4655783A (en) |
| EP (1) | EP0200843B1 (en) |
| JP (1) | JPS61258082A (en) |
| BR (1) | BR8505623A (en) |
| CA (1) | CA1239254A (en) |
| DE (1) | DE3563462D1 (en) |
Families Citing this family (40)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4874391A (en) * | 1986-07-29 | 1989-10-17 | Ciba-Geigy Corporation | Process for photochemical stabilization of polyamide fiber material and mixtures thereof with other fibers: water-soluble copper complex dye and light-stabilizer |
| ES2059820T3 (en) * | 1988-09-29 | 1994-11-16 | Ciba Geigy Ag | PROCEDURE FOR THE PHOTOCHEMICAL STABILIZATION OF MATERIAL OF DYED AND UNDYED POLYAMIDIC FIBERS, AND OF THEIR MIXTURES. |
| US4902299A (en) * | 1989-02-28 | 1990-02-20 | E. I. Du Pont De Nemours And Company | Nylon fabrics with cupric salt and oxanilide for improved dye-lightfastness |
| US5069681A (en) * | 1990-01-03 | 1991-12-03 | Ciba-Geigy Corporation | Process for the photochemical stabilization of dyed polyamide fibres with foamed aqueous composition of copper organic complexes |
| EP0511166A1 (en) * | 1991-04-26 | 1992-10-28 | Ciba-Geigy Ag | Process for photochemical and thermic stabilization of polyamide fibre material with a fiberaffinitive copper complex and an oxalicacid diarylamide |
| US5700850A (en) | 1993-08-05 | 1997-12-23 | Kimberly-Clark Worldwide | Colorant compositions and colorant stabilizers |
| US6017661A (en) | 1994-11-09 | 2000-01-25 | Kimberly-Clark Corporation | Temporary marking using photoerasable colorants |
| US5721287A (en) | 1993-08-05 | 1998-02-24 | Kimberly-Clark Worldwide, Inc. | Method of mutating a colorant by irradiation |
| US5645964A (en) | 1993-08-05 | 1997-07-08 | Kimberly-Clark Corporation | Digital information recording media and method of using same |
| US5681380A (en) | 1995-06-05 | 1997-10-28 | Kimberly-Clark Worldwide, Inc. | Ink for ink jet printers |
| US5773182A (en) | 1993-08-05 | 1998-06-30 | Kimberly-Clark Worldwide, Inc. | Method of light stabilizing a colorant |
| US6211383B1 (en) | 1993-08-05 | 2001-04-03 | Kimberly-Clark Worldwide, Inc. | Nohr-McDonald elimination reaction |
| US6017471A (en) | 1993-08-05 | 2000-01-25 | Kimberly-Clark Worldwide, Inc. | Colorants and colorant modifiers |
| US5733693A (en) | 1993-08-05 | 1998-03-31 | Kimberly-Clark Worldwide, Inc. | Method for improving the readability of data processing forms |
| US5865471A (en) | 1993-08-05 | 1999-02-02 | Kimberly-Clark Worldwide, Inc. | Photo-erasable data processing forms |
| US5685754A (en) | 1994-06-30 | 1997-11-11 | Kimberly-Clark Corporation | Method of generating a reactive species and polymer coating applications therefor |
| US6071979A (en) | 1994-06-30 | 2000-06-06 | Kimberly-Clark Worldwide, Inc. | Photoreactor composition method of generating a reactive species and applications therefor |
| US6242057B1 (en) | 1994-06-30 | 2001-06-05 | Kimberly-Clark Worldwide, Inc. | Photoreactor composition and applications therefor |
| US6008268A (en) | 1994-10-21 | 1999-12-28 | Kimberly-Clark Worldwide, Inc. | Photoreactor composition, method of generating a reactive species, and applications therefor |
| US5786132A (en) | 1995-06-05 | 1998-07-28 | Kimberly-Clark Corporation | Pre-dyes, mutable dye compositions, and methods of developing a color |
| JP2001515524A (en) | 1995-06-05 | 2001-09-18 | キンバリー クラーク ワールドワイド インコーポレイテッド | New pre-dye |
| ES2161357T3 (en) | 1995-06-28 | 2001-12-01 | Kimberly Clark Co | STABILIZING COLORING COMPOSITION. |
| US6099628A (en) | 1996-03-29 | 2000-08-08 | Kimberly-Clark Worldwide, Inc. | Colorant stabilizers |
| PL321573A1 (en) | 1995-11-28 | 1997-12-08 | Kimberly Clark Co | Improved stabilising agents for dyes |
| US5855655A (en) | 1996-03-29 | 1999-01-05 | Kimberly-Clark Worldwide, Inc. | Colorant stabilizers |
| US5782963A (en) | 1996-03-29 | 1998-07-21 | Kimberly-Clark Worldwide, Inc. | Colorant stabilizers |
| US5891229A (en) | 1996-03-29 | 1999-04-06 | Kimberly-Clark Worldwide, Inc. | Colorant stabilizers |
| US6524379B2 (en) | 1997-08-15 | 2003-02-25 | Kimberly-Clark Worldwide, Inc. | Colorants, colorant stabilizers, ink compositions, and improved methods of making the same |
| BR9906513A (en) | 1998-06-03 | 2001-10-30 | Kimberly Clark Co | New photoinitiators and applications for the same |
| CA2298615C (en) | 1998-06-03 | 2009-03-31 | Kimberly-Clark Worldwide, Inc. | Neonanoplasts produced by microemulsion technology and inks for ink jet printing |
| US6228157B1 (en) | 1998-07-20 | 2001-05-08 | Ronald S. Nohr | Ink jet ink compositions |
| AU1309800A (en) | 1998-09-28 | 2000-04-17 | Kimberly-Clark Worldwide, Inc. | Novel photoinitiators and applications therefor |
| WO2000042110A1 (en) | 1999-01-19 | 2000-07-20 | Kimberly-Clark Worldwide, Inc. | Novel colorants, colorant stabilizers, ink compositions, and improved methods of making the same |
| US6331056B1 (en) | 1999-02-25 | 2001-12-18 | Kimberly-Clark Worldwide, Inc. | Printing apparatus and applications therefor |
| US6294698B1 (en) | 1999-04-16 | 2001-09-25 | Kimberly-Clark Worldwide, Inc. | Photoinitiators and applications therefor |
| US6368395B1 (en) | 1999-05-24 | 2002-04-09 | Kimberly-Clark Worldwide, Inc. | Subphthalocyanine colorants, ink compositions, and method of making the same |
| DE60121588T2 (en) | 2000-06-19 | 2006-11-16 | Kimberly-Clark Worldwide, Inc., Neenah | NEW PHOTOINITIATORS |
| TW200406466A (en) * | 2001-11-13 | 2004-05-01 | Ciba Sc Holding Ag | Compositions comprising at least one oxonol dye and at least one metal complex |
| EP1602779A1 (en) * | 2004-06-04 | 2005-12-07 | Clariant International Ltd. | Copper complexes as light stabilizers for fibre materials |
| DE102011084639A1 (en) | 2011-10-17 | 2013-04-18 | Osram Opto Semiconductors Gmbh | ORGANIC ELECTRONIC COMPONENT WITH DUTY, USE OF A DOPING AGENT AND METHOD FOR PRODUCING THE DUTY |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB799742A (en) * | 1955-09-19 | 1958-08-13 | Ici Ltd | Process for colouring aromatic polyester textile materials |
| NL287100A (en) * | 1961-12-22 | |||
| US3329696A (en) * | 1963-06-17 | 1967-07-04 | Universal Oil Prod Co | N-(2-hydroxyphenylmethylene)-cycloalkyl amines and metal salts thereof |
| US3363969A (en) * | 1964-02-12 | 1968-01-16 | Du Pont | Dyeing and light stabilizing nylon yarns with sulfonated dyes; sterically hindered phenols, and alkylnaphthalene sulfonates with or without other ultraviolet light absorbers |
| GB1321645A (en) * | 1970-07-02 | 1973-06-27 | Ici Ltd | Colouration process |
| GB1392953A (en) * | 1972-07-18 | 1975-05-07 | Ici Ltd | Colouration process |
| US3928328A (en) * | 1972-12-08 | 1975-12-23 | Du Pont | Schiff base and metal bisazomethine metal chelate |
| DE2625386A1 (en) * | 1976-06-05 | 1977-12-15 | Manfred Rembold | Dyestuff mixt. contg. catalytic fading inhibitor - of single oxygen-deactivating type, pref. nickel complex or diazabicyclooctane |
| DE3041153A1 (en) * | 1980-10-31 | 1982-06-16 | Bayer Ag, 5090 Leverkusen | METHOD FOR IMPROVING THE LIGHT FASTNESS OF POLYAMIDE COLORS |
| DE3247051A1 (en) * | 1982-12-20 | 1984-06-20 | Bayer Ag, 5090 Leverkusen | METHOD FOR IMPROVING THE LIGHT FASTNESS OF POLYAMIDE COLORS |
| DE3326640A1 (en) * | 1983-07-23 | 1985-01-31 | Basf Ag, 6700 Ludwigshafen | METHOD FOR IMPROVING THE LIGHT FASTNESS OF COLORING WITH ACID OR METAL COMPLEX DYES ON POLYAMIDE |
| DE3573626D1 (en) * | 1984-05-22 | 1989-11-16 | Ciba Geigy Ag | Process for the photochemical stabilisation of materials containing polyamide fibres |
-
1985
- 1985-11-04 EP EP85810509A patent/EP0200843B1/en not_active Expired
- 1985-11-04 DE DE8585810509T patent/DE3563462D1/en not_active Expired
- 1985-11-07 CA CA000494753A patent/CA1239254A/en not_active Expired
- 1985-11-08 JP JP60250608A patent/JPS61258082A/en active Granted
- 1985-11-08 BR BR8505623A patent/BR8505623A/en unknown
- 1985-11-12 US US06/797,098 patent/US4655783A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| BR8505623A (en) | 1986-12-16 |
| JPS61258082A (en) | 1986-11-15 |
| DE3563462D1 (en) | 1988-07-28 |
| EP0200843B1 (en) | 1988-06-22 |
| US4655783A (en) | 1987-04-07 |
| EP0200843A1 (en) | 1986-11-12 |
| JPH0355590B2 (en) | 1991-08-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1239254A (en) | Process for photochemical stabilisation of non-dyed and dyed polyamide fibre material and mixtures thereof | |
| US4964871A (en) | Process for preventing yellowing of polyamide fibre materials treated with stain-blocking agents by treatment with water-soluble light stabilizer having fibre affinity | |
| US7101408B2 (en) | Disperse dye mixtures | |
| US5076808A (en) | Dyeing of polyamide substrates with an organic n-nitroso-hydroxylamine as light stabilizer | |
| EP0519459B1 (en) | Disperse dye mixture | |
| KR100338371B1 (en) | Dye composition and method for dyeing hydrophobic fiber with the same | |
| DE1619357C3 (en) | Use of highly concentrated, stable, water-miscible, sulfonic acid group-free 1: 2 chromium or cobalt complexes of azo dyes containing stock solutions for the preparation of dye baths or printing pastes | |
| KR920000745B1 (en) | Composition of monoazo dyestaffs | |
| US4118381A (en) | 1:2 Cobalt complex phenol-acetoacetanilide benzene disazo dyestuffs | |
| US4990164A (en) | Process for the photochemical stabilization of undyed and dyed polyamide fibre material and blends thereof with copper complex of hydroxy-salicyl-oyl-hydroxylamine derivative | |
| JP2982988B2 (en) | Anionic dye composition and method for dyeing fiber material using the same | |
| EP0598303A1 (en) | Compositions containing benzodifuranone compounds and methods for coloring hydrophobic materials using the same | |
| US3704086A (en) | Production of highly concentrated,stable stock solutions containing 1:2 metal complex dyes in a single step reaction | |
| US4052157A (en) | Use of water-soluble disazo dyestuffs for dyeing or printing synthetic textile material of polyamide or polyurethane fibers | |
| JPH07258574A (en) | Dye composition and method of dyeing hydrophobic fiber therewith | |
| US5045083A (en) | Light-fast dyeing of synthetic polyamide fibers: anionic dye, oxazolo-anilide and a copper complex | |
| US4518392A (en) | Process for the HT dyeing of polyester materials with ethylene oxide propylene oxide block polymer | |
| JPS6321986A (en) | Method for improving light fastness of polyamide dyed article | |
| US4851012A (en) | Mixtures of blue disperse monoazo dyestuffs | |
| JP3031761B2 (en) | Dye composition and method for dyeing hydrophobic fiber using the same | |
| DE2346504A1 (en) | PROCESS FOR DYING TEXTILE MATERIAL MADE FROM POLYESTER FIBER / CELLULOSE BLENDS | |
| JP3115135B2 (en) | Disperse dye mixture | |
| JPH10120932A (en) | Black-based disperse dye mixture | |
| US4120647A (en) | Process for the dyeing of wool-containing fibre materials | |
| JP2584625B2 (en) | Treatment agent for hydrophobic fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |