EP0432597B1 - Process for dyeing polyamide substrates - Google Patents
Process for dyeing polyamide substrates Download PDFInfo
- Publication number
- EP0432597B1 EP0432597B1 EP90123037A EP90123037A EP0432597B1 EP 0432597 B1 EP0432597 B1 EP 0432597B1 EP 90123037 A EP90123037 A EP 90123037A EP 90123037 A EP90123037 A EP 90123037A EP 0432597 B1 EP0432597 B1 EP 0432597B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- dyes
- groups
- dyeing
- polyamide
- azo
- 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 - Lifetime
Links
- 239000004952 Polyamide Substances 0.000 title claims description 22
- 229920002647 polyamide Polymers 0.000 title claims description 22
- 238000004043 dyeing Methods 0.000 title claims description 17
- 238000000034 method Methods 0.000 title claims description 11
- 239000000758 substrate Substances 0.000 title claims description 9
- 150000004699 copper complex Chemical class 0.000 claims description 9
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- NFMHSPWHNQRFNR-UHFFFAOYSA-N hyponitrous acid Chemical compound ON=NO NFMHSPWHNQRFNR-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000004611 light stabiliser Substances 0.000 claims description 5
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims description 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 2
- 125000004648 C2-C8 alkenyl group Chemical group 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 238000009472 formulation Methods 0.000 claims description 2
- 239000002657 fibrous material Substances 0.000 claims 1
- 239000000975 dye Substances 0.000 description 22
- -1 2-Ethylhexyl Chemical group 0.000 description 20
- 239000010949 copper Substances 0.000 description 8
- 150000001879 copper Chemical class 0.000 description 8
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- 239000000987 azo dye Substances 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 239000001000 anthraquinone dye Substances 0.000 description 4
- LXCJGJYAOVCKLO-UHFFFAOYSA-N n-cyclohexyl-n-hydroxynitrous amide Chemical compound O=NN(O)C1CCCCC1 LXCJGJYAOVCKLO-UHFFFAOYSA-N 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000004753 textile Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 239000000986 disperse dye Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000000434 metal complex dye Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000449 nitro group Chemical class [O-][N+](*)=O 0.000 description 2
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 2
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 2
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZYECOAILUNWEAL-NUDFZHEQSA-N (4z)-4-[[2-methoxy-5-(phenylcarbamoyl)phenyl]hydrazinylidene]-n-(3-nitrophenyl)-3-oxonaphthalene-2-carboxamide Chemical compound COC1=CC=C(C(=O)NC=2C=CC=CC=2)C=C1N\N=C(C1=CC=CC=C1C=1)/C(=O)C=1C(=O)NC1=CC=CC([N+]([O-])=O)=C1 ZYECOAILUNWEAL-NUDFZHEQSA-N 0.000 description 1
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 125000006276 2-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C(*)C([H])=C1[H] 0.000 description 1
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 1
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 description 1
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical class C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 description 1
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 description 1
- 125000006275 3-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C([H])C(*)=C1[H] 0.000 description 1
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 1
- 125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 description 1
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 1
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000004861 4-isopropyl phenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 1
- SOYBJIUDKRLQTA-UHFFFAOYSA-N benzene;dinaphthalen-1-yldiazene Chemical compound C1=CC=CC=C1.C1=CC=C2C(N=NC=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 SOYBJIUDKRLQTA-UHFFFAOYSA-N 0.000 description 1
- 235000012745 brilliant blue FCF Nutrition 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000004700 cobalt complex Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- WSEFXLKPOBQART-UHFFFAOYSA-N dinaphthalen-1-yldiazene;naphthalene Chemical compound C1=CC=CC2=CC=CC=C21.C1=CC=C2C(N=NC=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 WSEFXLKPOBQART-UHFFFAOYSA-N 0.000 description 1
- UWZDBZPEHOCLPU-UHFFFAOYSA-N diphenyldiazene stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1.C1=CC=CC=C1N=NC1=CC=CC=C1 UWZDBZPEHOCLPU-UHFFFAOYSA-N 0.000 description 1
- CDRJVFHKXDHCCI-UHFFFAOYSA-N diphenyldiazene;naphthalene Chemical compound C1=CC=CC2=CC=CC=C21.C1=CC=CC=C1N=NC1=CC=CC=C1 CDRJVFHKXDHCCI-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- JIQNWFBLYKVZFY-UHFFFAOYSA-N methoxycyclohexatriene Chemical compound COC1=C[C]=CC=C1 JIQNWFBLYKVZFY-UHFFFAOYSA-N 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- DAHPIMYBWVSMKQ-UHFFFAOYSA-N n-hydroxy-n-phenylnitrous amide Chemical compound O=NN(O)C1=CC=CC=C1 DAHPIMYBWVSMKQ-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000000979 synthetic dye Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
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
- 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
- D06P1/6422—Compounds containing nitro or nitroso 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
-
- 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
- Y10S8/916—Natural fiber dyeing
- Y10S8/917—Wool or silk
-
- 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
Definitions
- the present invention relates to an improved process for dyeing polyamide substrates from aqueous baths with suitable dyes and with copper complexes as light stabilizers for the colored polyamide.
- the invention further relates to dye formulations which contain a copper complex of an organic N-nitrosohydroxylamine as a light stabilizer for the colored polyamide.
- colored polyamide loses lightfastness due to the catalytic influence of the dye, i.e. it is subject to chemical changes under the influence of light and especially light and heat, which deteriorate the mechanical and thermal properties and also cause undesirable discoloration.
- lightfastness stabilizers have therefore been used in the coloring, which are primarily copper complexes, e.g. of salicylaldehydes (EP-A 252 368), salicyloximes (EP-A 113 856 and EP-A 162 811) and water-soluble azo dyes (EP-A 255 481) and of hydroxamic acids (DE-A 3 326 640).
- copper complexes e.g. of salicylaldehydes (EP-A 252 368), salicyloximes (EP-A 113 856 and EP-A 162 811) and water-soluble azo dyes (EP-A 255 481) and of hydroxamic acids (DE-A 3 326 640).
- the concentration in the dye bath must be chosen higher than the amount required, and moreover they have too strong their own color, so that they shift the color tone and brilliantly tarnish the dyeing, particularly in the case of brilliant dyeings.
- the object of the invention was therefore to remedy these disadvantages.
- the copper complexes to be used according to the invention which have the general structure I correspond and in which the radicals R are aliphatic, cycloaliphatic, araliphatic or aromatic organic groups, can in principle be derived from any organic N-nitrosohydroxylamines.
- the cycloalkyl and aryl groups can in turn carry one to three substituents.
- N-nitrosohydroxylamines on which the complexes are based are known or can be obtained in a known manner, e.g. by the action of nitrosating agents such as alkali metal nitrites on N-monosubstituted hydroxylamines (DE-A 10 19 657). The same applies to the production of the complexes.
- Suitable dyes are azo and anthraquinone dyes, their metal complexes and also other metal complex dyes.
- azo dyes mono- and bisazo dyes of benzene-azo-naphthalene, benzene-azo-1-phenylpyrazol-5-one, benzene-azo-benzene, naphthalene-azo-benzene, benzene-azo-aminonaphthalene are particularly suitable.
- Particularly suitable disperse dyes are metal complex dyes, for example 1: 1 or preferably 1: 2 complexes of metallized azo, azomethine and phthalocyanine dyes.
- Azo and azomethine dyes preferentially complex chromium or cobalt, phthalocyanines especially copper and nickel. Examples of the latter class of dyes are described in F.H. Moser, D.L. Thomas: The Phthalocyanines ", Vol. II, CRC Press, Boca Raton, Florida 1983.
- the process according to the invention is suitable for dyeing any polyamides, e.g. also natural polyamides such as wool and silk, but is of particular practical importance for dyeing synthetic polyamides such as nylon 6, nylon 6.6 and nylon 12 or materials containing these polyamides.
- the substrates can be of any shape - for example injection molded articles, foils, tapes and fibers, but primarily fiber structures such as yarns, nonwovens and mainly textiles come into consideration.
- the dyeing process is carried out under the conditions recommended for the respective dyes, as usual, from an aqueous bath, so that detailed explanations for this are unnecessary.
- the amount of copper complexes to be used according to the invention in the case of polyamide textile goods, is generally between 0.01 and 2% by weight of copper, depending on the type of fabric and the amount of dye applied, based on the amount of the polyamide content in the textile goods.
- the concentration of the complex in the dyebath depends on this amount, which is expediently dimensioned in such a way that the used dyebath contains only 0.001 to 1% by weight of copper in the form of the complexes because of the excellent absorption capacity.
- the effective amounts of dyes and complexes can be determined by means of a few preliminary tests.
- the copper complexes are normally finished at the same time as the dyeing process, but it is also possible to apply the complexes to the substrate from a separate bath before or after the dyeing.
- the process according to the invention is of great importance for the dyeing of textiles made of polyamides, which are not only exposed to light to a special degree but also to heat, which are primarily fabrics for the seats and interior linings of cars.
- the lower intrinsic color of the complexes enables the fabrics to be colored in clearer shades than before.
- the yarn dyed in this way is characterized by high light fastness and brilliant coloring.
- the orange-brown dyeing obtained in this way showed a significantly improved light fastness in accordance with the fakrotest DIN 75 202 compared to a dyeing which had not been post-treated.
- the gray color produced in this way showed, according to the facotest DIN 75 202, a significantly improved light fastness compared to a corresponding color without the addition of the copper complex.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Coloring (AREA)
Description
Die vorliegende Erfindung betrifft ein verbessertes Verfahren zum Färben von Polyamidsubstraten aus wäßrigen Bädern mit hierfür geeigneten Farbstoffen sowie mit Kupferkomplexen als Lichtschutzstabilisatoren für das gefärbte Polyamid.The present invention relates to an improved process for dyeing polyamide substrates from aqueous baths with suitable dyes and with copper complexes as light stabilizers for the colored polyamide.
Weiterhin betrifft die Erfindung Farbstoffzubereitungen, welche als Lichtschutzstabilisator für das gefärbte Polyamid einen Kupferkomplex eines organischen N-Nitrosohydroxylamins enthalten.The invention further relates to dye formulations which contain a copper complex of an organic N-nitrosohydroxylamine as a light stabilizer for the colored polyamide.
Es ist allgemein bekannt, daß gefärbtes Polyamid infolge des katalytischen Einflusses des Farbstoffes an Lichtechtheit verliert, d.h. es unterliegt unter der Einwirkung von Licht und besonders von Licht und Wärme chemischen Veränderungen, welche die mechanischen und thermischen Eigenschaften verschlechtern und außerdem unerwünschte Verfärbungen bedingen.It is well known that colored polyamide loses lightfastness due to the catalytic influence of the dye, i.e. it is subject to chemical changes under the influence of light and especially light and heat, which deteriorate the mechanical and thermal properties and also cause undesirable discoloration.
Zur Behebung dieses Nachteils hat man daher Lichtechtheitsstabilisatoren bei der Färbung mitverwendet, wobei es sich vornehmlich um Kupferkomplexe handelt, z.B. von Salicylaldehyden (EP-A 252 368), Salicyloximen (EP-A 113 856 und EP-A 162 811) und wasserlöslichen Azofarbstoffen (EP-A 255 481) sowie von Hydroxamsäuren (DE-A 3 326 640).To remedy this disadvantage, lightfastness stabilizers have therefore been used in the coloring, which are primarily copper complexes, e.g. of salicylaldehydes (EP-A 252 368), salicyloximes (EP-A 113 856 and EP-A 162 811) and water-soluble azo dyes (EP-A 255 481) and of hydroxamic acids (DE-A 3 326 640).
Das Aufziehvermögen dieser Komplexe läßt jedoch zu wünschen übrig, d.h. für eine zügige Färbung muß die Konzentration im Färbebad höher gewählt werden als es der benötigten Menge entspricht, und außerdem haben sie eine zu starke Eigenfarbe, so daß sie insbesondere bei brillanten Färbungen den Farbton verschieben und die Färbung mehr oder weniger stark abtrüben.However, the uptake of these complexes leaves something to be desired, i.e. for rapid dyeing, the concentration in the dye bath must be chosen higher than the amount required, and moreover they have too strong their own color, so that they shift the color tone and brilliantly tarnish the dyeing, particularly in the case of brilliant dyeings.
Der Erfindung lag daher die Aufgabe zugrunde, diesen Nachteilen abzuhelfen.The object of the invention was therefore to remedy these disadvantages.
Demgemäß wurde ein Verfahren zum Färben von Polyamidsubstraten aus wäßrigen Bädern mit hierfür geeigneten Farbstoffen sowie mit Kupferkomplexen als Lichtschutzstabilisatoren für das gefärbte Polyamid gefunden, welches dadurch gekennzeichnet ist, daß man hierbei als Kupferkomplexe solche von organischen N-Nitrosohydroxylaminen verwendet.Accordingly, a process for dyeing polyamide substrates from aqueous baths with suitable dyes and with copper complexes as light stabilizers for the colored polyamide has been found, which is characterized in that the copper complexes used are those of organic N-nitrosohydroxylamines.
Die erfindungsgemäß zu verwendenden Kupferkomplexe, welche der allgemeinen Struktur I
entsprechen und in denen die Reste R aliphatische, cycloaliphatische, araliphatische oder aromatische organische Gruppen bedeuten, können sich prinzipiell von beliebigen organischen N-Nitrosohydroxylaminen ableiten.The copper complexes to be used according to the invention, which have the general structure I
correspond and in which the radicals R are aliphatic, cycloaliphatic, araliphatic or aromatic organic groups, can in principle be derived from any organic N-nitrosohydroxylamines.
Aus wirtschaftlichen Gründen werden jedoch solche Komplexe I bevorzugt, in denen die Reste R folgende Bedeutung haben:
- C₁-C₂₀-Alkylgruppen, vorzugsweise C₁-C₁₀-Alkylgruppen, darunter vorzugsweise 2-Ethylhexyl sowie C₁-C₄-Alkylgruppen wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl und iso-Butyl;
- C₃-C₂₀-Alkenylgruppen, vorzugsweise C₃-C₆-Alkenylgruppen wie Propenyl, Butenyl, Pentenyl, Hexenyl, sowie vor allem Oleyl;
- C₇-C₁₂-Arylalkylgruppen, vorzugsweise Benzyl und Phenylethyl;
- C₅-C₁₂-Cycloalkylgruppen, vorzugsweise C₅-C₇-Cycloalkylgruppen wie Cyclopentyl, Cycloheptyl und besonders Cyclohexyl;
- Arylgruppen wie vorzugsweise Phenyl.
- C₁-C₂₀ alkyl groups, preferably C₁-C₁₀ alkyl groups, including preferably 2-ethylhexyl and C₁-C₄ alkyl groups such as methyl, ethyl, n-propyl, iso-propyl, n-butyl and iso-butyl;
- C₃-C₂₀ alkenyl groups, preferably C₃-C₆ alkenyl groups such as propenyl, butenyl, pentenyl, hexenyl, and especially oleyl;
- C₇-C₁₂ arylalkyl groups, preferably benzyl and phenylethyl;
- C₅-C₁₂ cycloalkyl groups, preferably C₅-C₇ cycloalkyl groups such as cyclopentyl, cycloheptyl and especially cyclohexyl;
- Aryl groups such as preferably phenyl.
Hierbei können die Cycloalkyl- und die Arylgruppen ihrerseits ein bis drei Substituenten tragen.The cycloalkyl and aryl groups can in turn carry one to three substituents.
Als Substituenten an den Cycloalkylresten kommen C₁-C₄-Alkylgruppen in Betracht. Bevorzugte Alkylcycloalkylgruppen sind 4-Methyl- und 4-tert.-Butylcyclohexyl. Für die Arylgruppen seien folgende Substituenten hervorgehoben:
- Vorzugsweise C₁-C₁₂-Alkylgruppen, C₁-C₁₂-Alkoxygruppen, C₂-C₈-Alkenylgruppen, Aminogruppen und Chlor;
- Weiterhin Fluor, Brom, die Sulfonsäuregruppe und Reste der Formeln -CO-O-R¹ und -SO₂-R¹, und
- außerdem Hydroxy, Nitro, Nitroso und Reste der Formeln -N(R¹)R² und -NH-CO-R¹,
wobei R¹ und R² C₁-C₁₂-Alkylgruppen, Phenylgruppen oder C₇-C₁₂-Phenylalkylgruppen bezeichnen.As substituents on the cycloalkyl radicals come C₁-C₄ alkyl groups. Preferred alkylcycloalkyl groups are 4-methyl and 4-tert-butylcyclohexyl. The following substituents should be emphasized for the aryl groups:
- Preferably C₁-C₁₂ alkyl groups, C₁-C₁₂ alkoxy groups, C₂-C₈ alkenyl groups, amino groups and chlorine;
- Furthermore, fluorine, bromine, the sulfonic acid group and radicals of the formulas -CO-O-R¹ and -SO₂-R¹, and
- also hydroxy, nitro, nitroso and radicals of the formulas -N (R¹) R² and -NH-CO-R¹,
wherein R¹ and R² denote C₁-C₁₂ alkyl groups, phenyl groups or C₇-C₁₂ phenylalkyl groups.
Als Verbindungen I mit substituierten Phenylgruppen als Reste sind hervorzuheben:
Tolyl, 2,3- oder 4-Chlorphenyl, 2,3- oder 4-Bromphenyl, 2,3- oder 4-Fluorphenyl, 2,3- oder 4-Ethylphenyl, 2,3- oder 4-Propylphenyl, 2,3- oder 4-iso-Propylphenyl, 2,3- oder 4-Dodecylphenyl, 2,3- oder 4-Methoxyphenyl, 2,3- oder 4-Ethoxyphenyl, 2,3- oder 4-Propoxyphenyl, 2,3- oder 4-Butoxyphenyl, 4-Nitrosophenyl, 4-Hydroxyphenyl, 4-Dimethylaminophenyl, 4-Diethylaminophenyl, 4-Aminophenyl, Phenylsulfonylphenyl, Methyloxycarbonyl, Ethyloxycarbonyl, Propyloxycarbonyl, Acetylamino, Propionylamino, Butanoylamino und Pentanoylamino.The following should be emphasized as compounds I with substituted phenyl groups:
Tolyl, 2,3- or 4-chlorophenyl, 2,3- or 4-bromophenyl, 2,3- or 4-fluorophenyl, 2,3- or 4-ethylphenyl, 2,3- or 4-propylphenyl, 2,3 - or 4-iso-propylphenyl, 2,3- or 4-dodecylphenyl, 2,3- or 4-methoxyphenyl, 2,3- or 4-ethoxyphenyl, 2,3- or 4-propoxyphenyl, 2,3- or 4 -Butoxyphenyl, 4-nitrosophenyl, 4-hydroxyphenyl, 4-dimethylaminophenyl, 4-diethylaminophenyl, 4-aminophenyl, phenylsulfonylphenyl, methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, acetylamino, propionylamino, butanoylamino and pentanoylamino.
Die den Komplexen zugrundeliegenden N-Nitrosohydroxylamine sind bekannt oder in bekannter Weise erhältlich, z.B. durch Einwirkung nitrosierender Mittel wie Alkalimetallnitriten auf N-monosubstituierte Hydroxylamine (DE-A 10 19 657). Das gleiche gilt für die Herstellung der Komplexe.The N-nitrosohydroxylamines on which the complexes are based are known or can be obtained in a known manner, e.g. by the action of nitrosating agents such as alkali metal nitrites on N-monosubstituted hydroxylamines (DE-A 10 19 657). The same applies to the production of the complexes.
Da die Beeinträchtigung der Lichtechtheit der Polyamide von der chemischen Natur des Farbstoffs praktisch nicht abhängt, kommen als Farbstoffe alle diejenigen in Betracht, die sich für die Färbung von Polyamiden eignen, darunter vor allem Farbstoffe mit sauren Gruppen und Dispersionsfarbstoffe.Since the impairment of the lightfastness of the polyamides practically does not depend on the chemical nature of the dye, all those which are suitable for dyeing polyamides are suitable as dyes, including in particular dyes with acidic groups and disperse dyes.
Als Farbstoffe kommen Azo- und Anthrachinonfarbstoffe, deren Metallkomplexe sowie auch sonstige Metallkomplexfarbstoffe in Betracht.Suitable dyes are azo and anthraquinone dyes, their metal complexes and also other metal complex dyes.
Unter den Azofarbstoffen eignen sich besonders Mono- und Bisazofarbstoffe der Benzol-azo-naphthalin-, Benzol-azo-1-phenylpyrazol-5-on, Benzol-azo-benzol-, Naphthalin-azo-benzol-, Benzol-azo-aminonaphthalin-, Naphthalin-azo-naphthalin-, Naphthalin-azo-1-phenylpyrazol-5-on-, Benzol-azo-pyridon-, Benzol-azo-aminopyridin-, Naphthalin-azo-pyridon-, Napthalin-azo-aminopyridin und der Stilben-azo-benzol-reihe.Among the azo dyes, mono- and bisazo dyes of benzene-azo-naphthalene, benzene-azo-1-phenylpyrazol-5-one, benzene-azo-benzene, naphthalene-azo-benzene, benzene-azo-aminonaphthalene are particularly suitable. , Naphthalene-azo-naphthalene, naphthalene-azo-1-phenylpyrazol-5-one, benzene-azo-pyridone, benzene-azo-aminopyridine, naphthalene-azo-pyridone, naphthalene-azo-aminopyridine and the stilbene -azo-benzene series.
Weitere Farbstoffe dieser Art sind der einschlägigen Fachliteratur Colour Index und K. Venkataraman "The Chemistry of Synthetic Dyes", Vol. VI, Academic Press, New York, London, 1972 zu entnehmen. Solche aus der Klasse der Anthrachinonfarbstoffe sind in K. Venkataraman, Vol. II, Academic Press, New York, 1952 beschrieben.Further dyes of this type can be found in the relevant specialist literature Color Index and K. Venkataraman "The Chemistry of Synthetic Dyes", Vol. VI, Academic Press, New York, London, 1972. Those from the class of anthraquinone dyes are described in K. Venkataraman, Vol. II, Academic Press, New York, 1952.
Als Dispersionsfarbstoffe eignen sich vor allem Metallkomplexfarbstoffe, beispielsweise 1:1- oder vorzugsweise 1:2-Komplexe von metallisierten Azo-, Azomethin- und Phthalocyaninfarbstoffen.Particularly suitable disperse dyes are metal complex dyes, for example 1: 1 or preferably 1: 2 complexes of metallized azo, azomethine and phthalocyanine dyes.
Azo- und Azomethinfarbstoffe komplexieren bevorzugt Chrom oder Kobalt, Phthalocyanine insbesondere Kupfer und Nickel. Beispiele der letztgenannten Farbstoffklasse sind in F.H. Moser, D.L. Thomas :The Phthalocyanines", Vol. II, CRC Press, Boca Raton, Florida 1983 aufgeführt.Azo and azomethine dyes preferentially complex chromium or cobalt, phthalocyanines especially copper and nickel. Examples of the latter class of dyes are described in F.H. Moser, D.L. Thomas: The Phthalocyanines ", Vol. II, CRC Press, Boca Raton, Florida 1983.
Selbstverständlich eignen sich auch Mischungen verschiedener Farbstoffe.Mixtures of different dyes are of course also suitable.
Das erfindungsgemäße Verfahren eignet sich zum Färben beliebiger Polyamide, also z.B. auch natürlichen Polyamiden wie Wolle und Seide, hat vor allem aber praktische Bedeutung für das Färben von synthetischen Polyamiden wie Nylon 6, Nylon 6.6 und Nylon 12 oder Materialien, welche diese Polyamide enthalten.The process according to the invention is suitable for dyeing any polyamides, e.g. also natural polyamides such as wool and silk, but is of particular practical importance for dyeing synthetic polyamides such as nylon 6, nylon 6.6 and nylon 12 or materials containing these polyamides.
Die Substrate können grundsätzlich von beliebiger Form sein - erwähnt seien beispielsweise Spritzgußartikel, Folien, Bänder und Fasern, jedoch kommen in erster Linie Fasergebilde wie Garne, Vliese und hauptsächlich Textilien in Betracht.In principle, the substrates can be of any shape - for example injection molded articles, foils, tapes and fibers, but primarily fiber structures such as yarns, nonwovens and mainly textiles come into consideration.
Man nimmt das Färbeverfahren unter den für die jeweiligen Farbstoffe empfohlenen Bedingungen wie üblich aus wäßrigem Bade vor, so daß sich detaillierte Ausführungen hierzu erübrigen.The dyeing process is carried out under the conditions recommended for the respective dyes, as usual, from an aqueous bath, so that detailed explanations for this are unnecessary.
Handelt es sich um wasserunlösliche Farbstoffe oder Kupferkomplexe, verwendet man zweckmäßigerweise ein Dispergiermittel mit.If it is water-insoluble dyes or copper complexes, it is advisable to use a dispersant.
Die Menge der erfindungsgemäß zu verwendenden Kupferkomplexe liegt im Falle von Polyamidtextilgut je nach Art des Stoffes und der aufgebrachten Farbstoffmenge im allgemeinen zwischen 0,01 und 2 Gew.-% Kupfer, bezogen auf die Menge des Polyamidanteils im Textilgut. Nach dieser Menge richtet sich die Konzentration des Komplexes im Färbebad, die wegen des hervorragenden Aufziehvermögens zweckmäßigerweise so bemessen wird, daß das verbrauchte Färbebad nur noch 0,001 bis 1 Gew.-% Kupfer in Form der Komplexe enthält. Im Falle anderer Substrate sind die jeweils wirksamen Mengen von Farbstoffen und Komplexen durch einige Vorversuche zu ermitteln.The amount of copper complexes to be used according to the invention, in the case of polyamide textile goods, is generally between 0.01 and 2% by weight of copper, depending on the type of fabric and the amount of dye applied, based on the amount of the polyamide content in the textile goods. The concentration of the complex in the dyebath depends on this amount, which is expediently dimensioned in such a way that the used dyebath contains only 0.001 to 1% by weight of copper in the form of the complexes because of the excellent absorption capacity. In the case of other substrates, the effective amounts of dyes and complexes can be determined by means of a few preliminary tests.
Normalerweise nimmt man die Ausrüstung mit den Kupferkomplexen gleichzeitig mit dem Färbevorgang vor, jedoch ist es auch möglich, die Komplexe vor oder nach der Färbung aus einem gesonderten Bad auf das Substrat aufzubringen.The copper complexes are normally finished at the same time as the dyeing process, but it is also possible to apply the complexes to the substrate from a separate bath before or after the dyeing.
Für den Fall der gleichzeitigen Applikation ist es zweckmäßig, hierfür gebrauchsfertige Farbstoffzubereitungen bereitzustellen, welche die Farbstoffe, gegebenenfalls Dispersionsmittel und sonst übliche Hilfsmittel sowie die Komplexe enthalten.In the case of simultaneous application, it is expedient to provide ready-to-use dye preparations which contain the dyes, optionally dispersants and other customary auxiliaries and the complexes.
Das erfindungsgemäße Verfahren hat große Bedeutung für die Färbung von Textilien aus Polyamiden, die nicht nur im besonderen Maße dem Licht sondern auch der Wärme ausgesetzt werden, wobei es sich vornehmlich um Stoffe für die Sitze und Innenauskleidungen von Autos handelt. Die geringere Eigenfarbe der Komplexe ermöglicht die Färbung der Stoffe in klareren Farbtönen als bisher.The process according to the invention is of great importance for the dyeing of textiles made of polyamides, which are not only exposed to light to a special degree but also to heat, which are primarily fabrics for the seats and interior linings of cars. The lower intrinsic color of the complexes enables the fabrics to be colored in clearer shades than before.
100 g eines Garns aus Nylon 6.6 wurden für die Dauer von 60 Minuten bei Siedetemperatur in 2 l einer wäßrigen, mit Essigsäure auf pH 5 gestellten Flotte gefärbt, die
- 0,5 g
- des dunkelblauen 1:2-Chrom-Komplex-Farbstoffes der Colour Index Nr. 15707
- 0,05 g
- des grünen Anthrachinon-Farbstoffes der Colour Index Nr. 61570
- 0,45 g
- des blauen Anthrachinon-Farbstoffes N,N'-Bis(4-amino-3-sulfo-anthrachinonyl)-4,4'-diaminodiphenylmethan
- 0,5 g
- Dispergiermittel (Oleylamin, oxethyliert mit 12 mol Ethylenoxid) und
- 0,05 g
- (= 0,009 g Cu) des Kupferkomplexes von N-Nitroso-cyclohexylhydroxylamin (I, R = Cyclohexyl)
enthielt.100 g of a yarn made of nylon 6.6 were dyed for 60 minutes at boiling temperature in 2 l of an aqueous liquor which had been brought to pH 5 with acetic acid and which
- 0.5 g
- of the dark blue 1: 2 chromium complex dye of Color Index No. 15707
- 0.05 g
- of the green anthraquinone dye, Color Index No. 61570
- 0.45 g
- of the blue anthraquinone dye N, N'-bis (4-amino-3-sulfo-anthraquinonyl) -4,4'-diaminodiphenylmethane
- 0.5 g
- Dispersant (oleylamine, oxyethylated with 12 mol ethylene oxide) and
- 0.05 g
- (= 0.009 g Cu) of the copper complex of N-nitroso-cyclohexylhydroxylamine (I, R = cyclohexyl)
contained.
Das so gefärbte Garn zeichnet sich durch hohe Lichtechtheit und eine brillante Färbung aus.The yarn dyed in this way is characterized by high light fastness and brilliant coloring.
100 g eines Gewebes aus Nylon 6.6 wurden während 40 Minuten bei einer Temperatur von 115°C in einem Autoklaven mit einer auf pH 4,5 eingestellten Flotte gefärbt, die
- 0,7 g
- des gelben 1:2-Chrom-Komplex-Farbstoffes der Formel
- 0,3 g
- des rotvioletten 1:2-Chrom-Komplex-Azofarbstoffes der Colour Index Nr. 18762 und
- 0,5 g
- Dispergiermittel (Oleylamin, oxethyliert mit 12 mol Ethylenoxid)
enthielt.100 g of a nylon 6.6 fabric were dyed for 40 minutes at a temperature of 115 ° C. in an autoclave with a liquor adjusted to pH 4.5
- 0.7 g
- of the yellow 1: 2 chromium complex dye of the formula
- 0.3 g
- of the red-violet 1: 2 chromium complex azo dye of Color Index No. 18762 and
- 0.5 g
- Dispersant (oleylamine, oxyethylated with 12 mol ethylene oxide)
contained.
Nach anschließendem Spülen und Trocknen wurde das Gewebe mit einer Flotte imprägniert, die pro Liter Wasser 1 g (= 0,188 g Cu) des Kupferkomplexes von N-Nitroso-phenylhydroxylamin (I, R = Phenyl) enthielt.After subsequent rinsing and drying, the fabric was impregnated with a liquor which contained 1 g (= 0.188 g Cu) of the copper complex of N-nitroso-phenylhydroxylamine (I, R = phenyl) per liter of water.
Die so erhaltene orange-braune Färbung zeigte gegenüber einer nicht nachbehandelten Färbung eine deutlich verbesserte Lichtechtheit gemäß Fakrotest DIN 75 202.The orange-brown dyeing obtained in this way showed a significantly improved light fastness in accordance with the fakrotest DIN 75 202 compared to a dyeing which had not been post-treated.
100 g einer Flocke aus Nylon 6 wurden für die Dauer von 60 Minuten bei Siedetemperatur in 2 l einer wäßrigen, mit Mononatriumphosphat und Essigsäure auf pH 6 gestellten Flotte gefärbt, die
- 0,04 g
- des braunen 1:2-Chrom-Mischkomplex-Azofarbstoffes der Formel
- 0,04 g
- des olivfarbenen 1:2-Cobalt-Komplex-Azofarbstoffes der Formel
- 0,5 g
- Dispergiermittel (Oleylamin, oxethyliert mit 12 mol Ethylenoxid) und
- 0,1 g
- (= 0,018 g Cu) des Kupferkomplexes von N-Nitroso-cyclohexylhydroxylamin (I, R = Cyclohexyl)
enthielt.100 g of a flake made of nylon 6 were dyed for 60 minutes at boiling temperature in 2 l of an aqueous liquor which had been adjusted to pH 6 with monosodium phosphate and acetic acid
- 0.04 g
- of the brown 1: 2 chromium mixed complex azo dye of the formula
- 0.04 g
- of the olive-colored 1: 2 cobalt complex azo dye of the formula
- 0.5 g
- Dispersant (oleylamine, oxyethylated with 12 mol ethylene oxide) and
- 0.1 g
- (= 0.018 g Cu) of the copper complex of N-nitroso-cyclohexylhydroxylamine (I, R = cyclohexyl)
contained.
Die so hergestellte graue Färbung zeigte gemäß Fakrotest DIN 75 202 eine wesentlich verbesserte Lichtechtheit gegenüber einer entsprechenden Färbung ohne Zusatz des Kupferkomplexes.The gray color produced in this way showed, according to the facotest DIN 75 202, a significantly improved light fastness compared to a corresponding color without the addition of the copper complex.
Claims (5)
- A process for dyeing a polyamide substrate from an aqueous bath with a suitable dye and with a copper complex.as light stabilizer for the dyed polyamide, which comprises using the copper complex of an organic N-nitrosohydroxylamine.
- A process as claimed in claim 1, wherein the copper complex used has the formula I
- A process as claimed in claim 2, wherein R is phenyl or cyclohexyl.
- A process as claimed in any of claims 1 to 3, wherein the polyamide substrate is a sheetlike structure consisting of or containing polyamide fiber material.
- A dye formulation for dyeing a polyamide substrate, which contains a copper complex of an organic N-nitrosohydroxylamine as light stabilizer for the dyed polyamide.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3941295 | 1989-12-14 | ||
DE3941295A DE3941295A1 (en) | 1989-12-14 | 1989-12-14 | METHOD FOR COLORING POLYAMIDE SUBSTRATES |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0432597A1 EP0432597A1 (en) | 1991-06-19 |
EP0432597B1 true EP0432597B1 (en) | 1993-11-18 |
Family
ID=6395454
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90123037A Expired - Lifetime EP0432597B1 (en) | 1989-12-14 | 1990-12-01 | Process for dyeing polyamide substrates |
Country Status (4)
Country | Link |
---|---|
US (1) | US5076808A (en) |
EP (1) | EP0432597B1 (en) |
JP (1) | JPH03185186A (en) |
DE (2) | DE3941295A1 (en) |
Families Citing this family (40)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
US5643356A (en) | 1993-08-05 | 1997-07-01 | Kimberly-Clark Corporation | Ink for ink jet printers |
US5865471A (en) | 1993-08-05 | 1999-02-02 | Kimberly-Clark Worldwide, Inc. | Photo-erasable data processing forms |
US6017661A (en) | 1994-11-09 | 2000-01-25 | Kimberly-Clark Corporation | Temporary marking using photoerasable colorants |
US6017471A (en) | 1993-08-05 | 2000-01-25 | Kimberly-Clark Worldwide, Inc. | Colorants and colorant modifiers |
US5700850A (en) | 1993-08-05 | 1997-12-23 | Kimberly-Clark Worldwide | Colorant compositions and colorant stabilizers |
CA2120838A1 (en) | 1993-08-05 | 1995-02-06 | Ronald Sinclair Nohr | Solid colored composition mutable by ultraviolet radiation |
US6211383B1 (en) | 1993-08-05 | 2001-04-03 | Kimberly-Clark Worldwide, Inc. | Nohr-McDonald elimination reaction |
US5645964A (en) | 1993-08-05 | 1997-07-08 | Kimberly-Clark Corporation | Digital information recording media and method of using same |
US5733693A (en) | 1993-08-05 | 1998-03-31 | Kimberly-Clark Worldwide, Inc. | Method for improving the readability of data processing forms |
US5721287A (en) | 1993-08-05 | 1998-02-24 | Kimberly-Clark Worldwide, Inc. | Method of mutating a colorant by irradiation |
US6242057B1 (en) | 1994-06-30 | 2001-06-05 | Kimberly-Clark Worldwide, Inc. | Photoreactor composition and applications therefor |
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 |
US5739175A (en) | 1995-06-05 | 1998-04-14 | Kimberly-Clark Worldwide, Inc. | Photoreactor composition containing an arylketoalkene wavelength-specific sensitizer |
US6008268A (en) | 1994-10-21 | 1999-12-28 | Kimberly-Clark Worldwide, Inc. | Photoreactor composition, method of generating a reactive species, and applications therefor |
US5811199A (en) | 1995-06-05 | 1998-09-22 | Kimberly-Clark Worldwide, Inc. | Adhesive compositions containing a photoreactor composition |
US5849411A (en) | 1995-06-05 | 1998-12-15 | Kimberly-Clark Worldwide, Inc. | Polymer film, nonwoven web and fibers containing a photoreactor composition |
US5798015A (en) | 1995-06-05 | 1998-08-25 | Kimberly-Clark Worldwide, Inc. | Method of laminating a structure with adhesive containing a photoreactor composition |
EP0830638B1 (en) | 1995-06-05 | 2000-08-23 | Kimberly-Clark Worldwide, Inc. | Pre-dyes and compositions comprising them |
US5747550A (en) | 1995-06-05 | 1998-05-05 | Kimberly-Clark Worldwide, Inc. | Method of generating a reactive species and polymerizing an unsaturated polymerizable material |
US5786132A (en) | 1995-06-05 | 1998-07-28 | Kimberly-Clark Corporation | Pre-dyes, mutable dye compositions, and methods of developing a color |
ATE206150T1 (en) | 1995-06-28 | 2001-10-15 | Kimberly Clark Co | DYE-STABILIZED COMPOSITIONS |
US6391065B1 (en) | 1995-11-03 | 2002-05-21 | Boehme Filatex, Inc. | UV light absorber composition and method of improving the lightfastness of dyed textiles |
DE69620428T2 (en) | 1995-11-28 | 2002-11-14 | Kimberly-Clark Worldwide, Inc. | LIGHT-STABILIZED FABRIC COMPOSITIONS |
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 |
US6099628A (en) | 1996-03-29 | 2000-08-08 | 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 |
EP1062285A2 (en) | 1998-06-03 | 2000-12-27 | Kimberly-Clark Worldwide, Inc. | Neonanoplasts and microemulsion technology for inks and ink jet printing |
EP1000090A1 (en) | 1998-06-03 | 2000-05-17 | Kimberly-Clark Worldwide, Inc. | Novel photoinitiators and applications therefor |
WO2000004104A1 (en) | 1998-07-20 | 2000-01-27 | Kimberly-Clark Worldwide, Inc. | Improved ink jet ink compositions |
US6045592A (en) * | 1998-09-08 | 2000-04-04 | Leanne Paquin | Method and kit for dyeing shaped nylon plastics |
BR9914123B1 (en) | 1998-09-28 | 2010-11-30 | photoinitiators and applications therefor. | |
DE60002294T2 (en) | 1999-01-19 | 2003-10-30 | Kimberly-Clark Worldwide, Inc. | DYES, COLOR STABILIZERS, INK COMPOSITIONS AND METHOD FOR THE PRODUCTION THEREOF |
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 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB815537A (en) * | 1956-08-16 | 1959-06-24 | Basf Ag | Improvements in the production of n-nitroso-n-alkyl- and n-nitroso-n-cycloalkyl-hydroxylamines |
DE2054661A1 (en) * | 1970-11-06 | 1972-05-10 | Badische Anilin & Soda Fabrik AG, 6700 Ludwigshafen | N-nitrosa-n-aryl-hydroxylamines prepn - from nitrosa-arenes and nitrogen oxide |
DE2357598A1 (en) * | 1973-11-19 | 1975-05-22 | Basf Farben & Fasern | POLYESTER FORM OR COATING DIMENSIONS |
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 |
US4707161A (en) * | 1983-07-23 | 1987-11-17 | Basf Aktiengesellschaft | Lightfastness of dyeings obtained with acid dyes or metal complex dyes on polyamides: treatment with copper hydroxamates |
DE3573626D1 (en) * | 1984-05-22 | 1989-11-16 | Ciba Geigy Ag | Process for the photochemical stabilisation of materials containing polyamide fibres |
DE3622864A1 (en) * | 1986-07-08 | 1988-01-21 | Bayer Ag | METHOD FOR IMPROVING THE LIGHT FASTNESS OF POLYAMIDE COLORS |
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 |
-
1989
- 1989-12-14 DE DE3941295A patent/DE3941295A1/en not_active Withdrawn
-
1990
- 1990-11-26 JP JP2318184A patent/JPH03185186A/en active Pending
- 1990-12-01 DE DE90123037T patent/DE59003545D1/en not_active Expired - Fee Related
- 1990-12-01 EP EP90123037A patent/EP0432597B1/en not_active Expired - Lifetime
- 1990-12-07 US US07/623,568 patent/US5076808A/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JPH03185186A (en) | 1991-08-13 |
DE59003545D1 (en) | 1993-12-23 |
EP0432597A1 (en) | 1991-06-19 |
US5076808A (en) | 1991-12-31 |
DE3941295A1 (en) | 1991-06-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0432597B1 (en) | Process for dyeing polyamide substrates | |
DE1154069B (en) | Process for the production of water-insoluble azo dyes on structures made of aromatic polyesters, in particular polyethylene terephthalates, synthetic polyamides and polyurethanes | |
DE3142609A1 (en) | NAVY BLUE DISPERSION DYE MIXTURES | |
EP0376086B1 (en) | Mixtures of disperse azo dyes | |
EP0546372B1 (en) | Reactive dye mixtures | |
DE3686609T2 (en) | WATER-INSOLUBLE DISPERSION DYE PREPARATION. | |
DE1146030B (en) | Process for dyeing and printing fiber material made from aromatic polyesters | |
DE2343823A1 (en) | PROCESS FOR DYING TEXTILE GOODS BASED ON ACID-MODIFIED POLYESTERS AND NEW THIAZOLAZO COMPOUNDS AND THEIR USE FOR DYING | |
EP0046250B1 (en) | Dyestuff preparation and its use as a warning and signalling colour | |
EP0147783A2 (en) | Mixtures of blue disperse azo dyes for the dyeing of synthetic fibres | |
DE2330622A1 (en) | PROCESS FOR ISOTHERMAL COLORING OF HYDROPHOBIC ORGANIC POLYESTER MATERIAL | |
EP0330967A2 (en) | Process for dyeing synthetic fibrous materials | |
DE1049821B (en) | Process for dyeing fibers or films made of polyesters, polyacrylonitrile or cellulose acetate | |
DE2364608A1 (en) | MONOAZO DYES | |
DE2819197C2 (en) | ||
DE3901724A1 (en) | METHOD FOR COLORING SYNTHETIC FIBER MATERIALS | |
DE1469868B2 (en) | Use of heterocyclic dyes for dyeing polyamides in bulk | |
DE949649C (en) | Process for dyeing and printing polyacrylonitrile fibers | |
DE3600889A1 (en) | METHOD FOR DYING POLYAMIDE FIBERS | |
EP0793692A1 (en) | Mixtures of azo dyes for black hues | |
CH635605A5 (en) | SULPHONIC ACID-FREE BASIC DYES, THEIR PRODUCTION AND USE. | |
EP0735181A2 (en) | Multicolor dyeing with manganese compounds of fibrous materials containing polyamide fibres | |
DE2041846C3 (en) | Quinophthalone dyes | |
DE1165789B (en) | Process for the preparation of styryl dyes | |
CH456520A (en) | Process for the optical brightening of synthetic textile fibers |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19901227 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): BE CH DE FR GB IT LI NL |
|
17Q | First examination report despatched |
Effective date: 19930426 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19931115 Year of fee payment: 4 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19931116 Year of fee payment: 4 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE CH DE FR GB IT LI NL |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19931215 Year of fee payment: 4 |
|
REF | Corresponds to: |
Ref document number: 59003545 Country of ref document: DE Date of ref document: 19931223 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19931224 Year of fee payment: 4 |
|
ITF | It: translation for a ep patent filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19931231 Year of fee payment: 4 |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19931202 |
|
ET | Fr: translation filed | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19941201 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Effective date: 19941231 Ref country code: CH Effective date: 19941231 Ref country code: BE Effective date: 19941231 |
|
BERE | Be: lapsed |
Owner name: BASF A.G. Effective date: 19941231 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19950701 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19941201 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Effective date: 19950831 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 19950701 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19950901 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20051201 |