US3317273A - Metallizing azoic dyeings and prints - Google Patents
Metallizing azoic dyeings and prints Download PDFInfo
- Publication number
- US3317273A US3317273A US360436A US36043664A US3317273A US 3317273 A US3317273 A US 3317273A US 360436 A US360436 A US 360436A US 36043664 A US36043664 A US 36043664A US 3317273 A US3317273 A US 3317273A
- Authority
- US
- United States
- Prior art keywords
- solution
- metallizing
- metallization
- ammonium
- azoic
- 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
- 238000004043 dyeing Methods 0.000 title description 22
- 150000001875 compounds Chemical class 0.000 claims description 20
- 150000003863 ammonium salts Chemical class 0.000 claims description 15
- 239000002657 fibrous material Substances 0.000 claims description 14
- -1 METALA COMPOUND Chemical class 0.000 claims description 12
- 150000004696 coordination complex Chemical class 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 230000003381 solubilizing effect Effects 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 150000004679 hydroxides Chemical class 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 description 36
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 30
- 238000001465 metallisation Methods 0.000 description 28
- 238000000034 method Methods 0.000 description 21
- 239000000975 dye Substances 0.000 description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 13
- 239000000908 ammonium hydroxide Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 229960000583 acetic acid Drugs 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 12
- 229920000742 Cotton Polymers 0.000 description 11
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 11
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 10
- 229910000365 copper sulfate Inorganic materials 0.000 description 10
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 10
- JFGQHAHJWJBOPD-UHFFFAOYSA-N 3-hydroxy-n-phenylnaphthalene-2-carboxamide Chemical class OC1=CC2=CC=CC=C2C=C1C(=O)NC1=CC=CC=C1 JFGQHAHJWJBOPD-UHFFFAOYSA-N 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 230000008878 coupling Effects 0.000 description 9
- 238000010168 coupling process Methods 0.000 description 9
- 238000005859 coupling reaction Methods 0.000 description 9
- 239000000835 fiber Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 238000011282 treatment Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 235000011054 acetic acid Nutrition 0.000 description 6
- 239000012362 glacial acetic acid Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical class CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- GVBHRNIWBGTNQA-UHFFFAOYSA-N 2-methoxy-4-nitroaniline Chemical compound COC1=CC([N+]([O-])=O)=CC=C1N GVBHRNIWBGTNQA-UHFFFAOYSA-N 0.000 description 2
- ALKYHXVLJMQRLQ-UHFFFAOYSA-N 3-Hydroxy-2-naphthoate Chemical compound C1=CC=C2C=C(O)C(C(=O)O)=CC2=C1 ALKYHXVLJMQRLQ-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229940051880 analgesics and antipyretics pyrazolones Drugs 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- YNTQKXBRXYIAHM-UHFFFAOYSA-N azanium;butanoate Chemical compound [NH4+].CCCC([O-])=O YNTQKXBRXYIAHM-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001735 carboxylic acids Chemical group 0.000 description 2
- LDZGISULMSUOIK-UHFFFAOYSA-L copper acetic acid sulfate Chemical compound S(=O)(=O)([O-])[O-].[Cu+2].C(C)(=O)O LDZGISULMSUOIK-UHFFFAOYSA-L 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 150000003460 sulfonic acids Chemical group 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- AVYGCQXNNJPXSS-UHFFFAOYSA-N 2,5-dichloroaniline Chemical compound NC1=CC(Cl)=CC=C1Cl AVYGCQXNNJPXSS-UHFFFAOYSA-N 0.000 description 1
- VLZVIIYRNMWPSN-UHFFFAOYSA-N 2-Amino-4-nitrophenol Chemical compound NC1=CC([N+]([O-])=O)=CC=C1O VLZVIIYRNMWPSN-UHFFFAOYSA-N 0.000 description 1
- DOPJTDJKZNWLRB-UHFFFAOYSA-N 2-Amino-5-nitrophenol Chemical compound NC1=CC=C([N+]([O-])=O)C=C1O DOPJTDJKZNWLRB-UHFFFAOYSA-N 0.000 description 1
- XMGLDIXPHWXKFY-UHFFFAOYSA-N 2-aminophenol;benzene-1,3-diol Chemical compound NC1=CC=CC=C1O.OC1=CC=CC(O)=C1 XMGLDIXPHWXKFY-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- HGIDRHWWNZRUEP-UHFFFAOYSA-N 2-hydroxydibenzofuran Chemical compound C1=CC=C2C3=CC(O)=CC=C3OC2=C1 HGIDRHWWNZRUEP-UHFFFAOYSA-N 0.000 description 1
- QWRCZQZZFQIUEF-UHFFFAOYSA-N 2-hydroxydibenzofuran-3-carboxylic acid Chemical compound O1C2=CC=CC=C2C2=C1C=C(C(=O)O)C(O)=C2 QWRCZQZZFQIUEF-UHFFFAOYSA-N 0.000 description 1
- XTTIQGSLJBWVIV-UHFFFAOYSA-N 2-methyl-4-nitroaniline Chemical compound CC1=CC([N+]([O-])=O)=CC=C1N XTTIQGSLJBWVIV-UHFFFAOYSA-N 0.000 description 1
- DPJCXCZTLWNFOH-UHFFFAOYSA-N 2-nitroaniline Chemical compound NC1=CC=CC=C1[N+]([O-])=O DPJCXCZTLWNFOH-UHFFFAOYSA-N 0.000 description 1
- OCFRAVIOHQUKOV-UHFFFAOYSA-N 3-amino-n-butyl-4-hydroxybenzenesulfonamide Chemical compound CCCCNS(=O)(=O)C1=CC=C(O)C(N)=C1 OCFRAVIOHQUKOV-UHFFFAOYSA-N 0.000 description 1
- PNPCRKVUWYDDST-UHFFFAOYSA-N 3-chloroaniline Chemical compound NC1=CC=CC(Cl)=C1 PNPCRKVUWYDDST-UHFFFAOYSA-N 0.000 description 1
- CWDZPKXDNSSELJ-UHFFFAOYSA-N 3-hydroxy-9H-carbazole-2-carboxylic acid Chemical compound OC=1C(=CC=2NC3=CC=CC=C3C2C1)C(=O)O CWDZPKXDNSSELJ-UHFFFAOYSA-N 0.000 description 1
- YZJSKRBKHCLMQC-UHFFFAOYSA-N 3-hydroxy-n-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound OC1=CC2=CC=CC=C2C=C1C(=O)NC1=CC=CC([N+]([O-])=O)=C1 YZJSKRBKHCLMQC-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- LTVUZBRCIRNMNO-UHFFFAOYSA-N 4-amino-n,n-diethyl-3-methoxybenzenesulfonamide Chemical compound CCN(CC)S(=O)(=O)C1=CC=C(N)C(OC)=C1 LTVUZBRCIRNMNO-UHFFFAOYSA-N 0.000 description 1
- WOXLPNAOCCIZGP-UHFFFAOYSA-N 4-chloro-2-methoxyaniline Chemical compound COC1=CC(Cl)=CC=C1N WOXLPNAOCCIZGP-UHFFFAOYSA-N 0.000 description 1
- VKYZDCTWJGBFDW-UHFFFAOYSA-N 4-chloro-2-methylaniline;hydron;chloride Chemical compound Cl.CC1=CC(Cl)=CC=C1N VKYZDCTWJGBFDW-UHFFFAOYSA-N 0.000 description 1
- WDNUBHWYZLEDRD-UHFFFAOYSA-N 4-chloro-N-phenylnaphthalene-1-carboxamide Chemical compound ClC1=CC=C(C2=CC=CC=C12)C(=O)NC1=CC=CC=C1 WDNUBHWYZLEDRD-UHFFFAOYSA-N 0.000 description 1
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 1
- RBLUJIWKMSZIMK-UHFFFAOYSA-N 4-n-(4-methoxyphenyl)benzene-1,4-diamine Chemical class C1=CC(OC)=CC=C1NC1=CC=C(N)C=C1 RBLUJIWKMSZIMK-UHFFFAOYSA-N 0.000 description 1
- MHHOZFQQQPZLFE-UHFFFAOYSA-N 5-aminoquinolin-6-ol Chemical compound C1=CC=C2C(N)=C(O)C=CC2=N1 MHHOZFQQQPZLFE-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical group N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical group [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- SUZRRICLUFMAQD-UHFFFAOYSA-N N-Methyltaurine Chemical compound CNCCS(O)(=O)=O SUZRRICLUFMAQD-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 108010077895 Sarcosine Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical group [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- XJMWHXZUIGHOBA-UHFFFAOYSA-N azane;propanoic acid Chemical group N.CCC(O)=O XJMWHXZUIGHOBA-UHFFFAOYSA-N 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000004648 butanoic acid derivatives Chemical class 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- IRPXADUBAQAOKL-UHFFFAOYSA-N chembl1408927 Chemical class C1=CC=C2C(N=NC3=C4C=CC(=CC4=CC(=C3O)S(O)(=O)=O)S(O)(=O)=O)=CC=C(S(O)(=O)=O)C2=C1 IRPXADUBAQAOKL-UHFFFAOYSA-N 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- RHCJOJDSMWJGMV-UHFFFAOYSA-N diazanium acetate hydroxide Chemical compound [NH4+].[NH4+].[OH-].CC([O-])=O RHCJOJDSMWJGMV-UHFFFAOYSA-N 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DADSZOFTIIETSV-UHFFFAOYSA-N n,n-dichloroaniline Chemical compound ClN(Cl)C1=CC=CC=C1 DADSZOFTIIETSV-UHFFFAOYSA-N 0.000 description 1
- SHLTXWFNRJQZTQ-UHFFFAOYSA-N n-chloro-2-methylaniline Chemical class CC1=CC=CC=C1NCl SHLTXWFNRJQZTQ-UHFFFAOYSA-N 0.000 description 1
- KUDPGZONDFORKU-UHFFFAOYSA-N n-chloroaniline Chemical compound ClNC1=CC=CC=C1 KUDPGZONDFORKU-UHFFFAOYSA-N 0.000 description 1
- YZMHQCWXYHARLS-UHFFFAOYSA-N naphthalene-1,2-disulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(S(=O)(=O)O)=CC=C21 YZMHQCWXYHARLS-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical compound COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229940043230 sarcosine Drugs 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 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
- 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
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
- D06P3/64—Natural or regenerated cellulose using mordant dyes or metallisable dyes
Definitions
- the present invention relates to, in general, the metallization of azoic dyeings and prints and, in particular, to an improved method for the metallization of azoic dyeings on the fiber.
- Afurther object of this invention resides in tthe provision of an improved method for the metallization of azoic dyeings and prints which can be carried out in a continuous fashion.
- Yet another object of this invention is to provide azoic printings and dyeings of improved light fastness which are substantially free of light breaks and fading.
- Still another object of this invention contemplates the provision of improved metallizing compositions suitable for metallizing azoic dyeings and printed fibers.
- X represents a member selected from the group consisting of hydroxyl, hydrogen and alkyls having 1 to 4 carbon atoms and such amount of ammonium hydroxide as is necessary to maintain the pH of the solution in said range.
- the metallizing compounds capable of forming a metal complex with said azoic dyeing or printing which can be 3,317,273 Patented May 2, 1967 advantageously employed are the water-soluble or dispersible salts and hydroxides of copper, nickel or cobalt, usually in the form of the chlorides, sulfates, nitrates, formates, acetates, propionates and butyrates.
- the amount of metallizing compound which may be employed will usually depend upon the degree of metallization desired. While molar ratios are required for complete metallization, the amount employed can be varied from an equivalent to an excess of one equivalent of metal per equivalent of dye.
- the metallizing compound is coordinated by the addition to an aqueous solution thereof of an ammonium salt characterized by the formula above.
- This ammonium salt can be added as such or if desired, can be added as the corresponding free acid and ammonium hydroxide be then added to form the ammonium salt by neutraliza tion; in any event sufiicient ammonium hydroxide must be employed to bring the alkalinity to a pH of above 7 to 9 (preferably about 9).
- Representative lower aliphatic monocarboxylic acids and salts which can be advantaa geously employed are formic acid, acetic acid, propionic acid, butyric acid, the corresponding ammonium salts as will as carbonic acid and its corresponding ammonium sa t.
- the amount of metal salt which is employed in the treating solution can vary from 0.05 ounce per gallon to 10 ounces per gallon.
- the metallization treatment in accordance with this invention is applicable to fibrous materials having thereon an azoic dyeing in which the dye molecule contains an airomatic configuration which lends itself to the production of an o,o-dihydroxy type of metallization.
- azoic dyeings may be produced in situ on the fiber in any conventional manner; e.g., by impregnating the fiber with an azoic coupling component and then dyeing with a solution which contains an active diazo either in the form of a freshly prepared diazo or as a Fast Color salt solution.
- the dyeing may also be produced by printing the fiber with a paste which comprises a mixture of the diazo amino compound and coupling component and exposing the printed fiber to conditions suitable for coupling.
- the diazos and the coupling components employed are those which are free from solubilizing groups such as sulfonic and carboxylic acids and which produce dyes having hydroxy groups ortho to the azo linkage or groups which are convertible into hydroxy groups such 'as lower alkoxy, i.e., methoxy, ethoxy, propoxy and 'butoxy.
- the diazos employed in this invention are those produced from any aromatic diazotizable amine which does not contain solubilizing groups such as sulfonic and carboxylic acids and includes all of the conventional aromatic and 'heterocyclic amines that are customarily employed in the preparation of azoic dyes. Unless the coupler to be used contains the o,o-dihydroxy configuration the amine should also have an o-hydroxy or lower alkoxy group ortho to the amine group.
- diazotizable amines the following are illustrative:
- o-dianisidine 4-benzamido-2,S-dimethoxyaniline; 2,5-dimethoxy-4-(p-nitrobenzeneazo)aniline; 4-cyano-2,S-diinethoxyaniline; 5-diethylsulfamyl-o-anisidine; 4-phenylamino-o-anisidine; 5-n-butylsulfamyl-o-hydroxyaniline; 5-amino-6-hydroxyquinoline; 2-hydroxy-4-nitroaniline; 2-hydroxy-5-nitroaniline; chlorotoluidines;
- dichloroaniline trifiuoromethylchloroaniline; 4-nitro-o-anisidine; 4-chloro-o-anisidine; -chloro-4-nitro-o-anisidine; credisine;
- the coupling component contains the o,o'-dihydroxy configuration
- the above may be used, as also those free from the o-hydroxy and alkoxy configuration, e.g., p-chloroaniline, p-anisidine and benzidine.
- the coupling components may, in general, be selected from the Naphthol AS compounds which are arylides of 2-hydroxy-3-naphthoic acid and related fl-hydroxy carboxylic acid derivatives, acetoacetarylides and related B-oxocarboxylic acid arylides and pyrazolones.
- other compounds may be employed which are capable of coupling to yield a component having the required metallizable group in ortho position to the azo linkage.
- the following coupling components may be employed: 1
- 2-hydroxy-3-dibenzofurancarboxylic acid arylides such as 2-hydroxy-3-dibenzofuran 2,5 -dimethoxy carboxanilide, bis(acetoacet)benzidide, bis(acetoacet)-tolidide, acylacetarylides such as acetoacet-4-chloro-2,S-dimethoxyanilide, 3-hydroxy-2-carbaZole-carboxylic acid arylides such as 3-hydroxy-2-carbazole-(p-chloro)carboxyanilide, terephthaloyl bisacetoacet-(3-chloro-2',4-dimethoxy)-anilide, pyrazolones, such as l-phenyl-3-methyl-5-pyrazolone, 3-hydroxy-2-naphthoic acid arylides, o-hydroxy-aniline resorcinol, 2-hydroxy-5-nitro-aniline resorcinol.
- any ordinary diazo compounds may be employed, such as m-chloroaniline, o-nitroaniline, l-amino-anthraquinone and 2-amino-4,4-dichlorodiphenyloxide.
- Other azo couplers such as the metallized compounds disclosed in United States Patent 2,135,433 and the unmetallized products thereof, and the like can also be employed.
- the diazo may be supplied by an amine freshly diazotized by treatment with nitrite in the customary manner, or the diazo may be stabilized diazo, i.e., in the form of diazonium chloride or sulfate, or in the form of the diazo stabilized as a double salt, i.e., as a zinc chloride, boron trifiuoride, tin chloride, naphthalenedisulfonic acid, etc.
- the dyed or printed material is metallized in accordance with the method of the invention for a period of time of from about 5 seconds to 10 minutes depending on the degree of metallization desired, at a temperature in the range of from to 212 F.
- the metallizing solution contains per 1 part of metal salt, 1-4 parts of carbonic acid or a lower aliphatic carboxylic acid and 2-15 parts of ammonium hydroxide to provide an alkalinity to the solution of a pH of from above 7-9, and preferably closer to pH 9.
- the same result may be accomplished by the employment of the ammonium salts of the corresponding acids and any additional ammonium hydroxide necessary to control and maintain the pH of the solution in the range aforesaid.
- Copper solution Parts Copper sulfate Water 280 Ammonium hydroxide, 26 B. 430
- Glacial acetic acid 220 A cotton print produced in the usual manner from tetrazotized dianisidine and Naphthol AS was treated in 2 ounces of the above solution plus /2 ounce of ammonium hydroxide per gallon of added water at 150 F. for seconds, rinsed and dried.
- Example 15 A print is made on cotton in the usual manner fiom 4-benzamido-5-methyl-oanisidine diazotized and stabilized with sarcosine and Naphthol AS. This print is treated for 10 seconds at 200 F. in the copper solution of Example 1. Metallization was eificient as determined by the color and light fastness of the print.
- Example 16 A metallization was made as in Example 15, employing a print made in the usual manner from tetrazotized and stabilized dianisidine and Naphthol AS. The metallization was efiicient as determined by shade and light fastness tests.
- Example 17 A metallization was made as in Example 15, employing a print made in the usual manner from diazotized and stabilized S-methyl-o-anisidine and coupled with 3'- nitro-3-hydroxy-2-naphthanilide. The metallization was efiicient as determined by shade and light fastness tests.
- Example 18 A metallization was made as in Example 15, employing a print made in the usual manner from 4-benzarnid0- S-methyl-o-anisidine diazotized and stabilized with methyltaurine and coupled with 4-(S-chloro-2-hydroxyphenyl- Watter (gallon) Copper sulfate (oz.) Ammonium acetate Ammonium hydroxide 26 B- Ammonium carbonate Acetic acid Ammonium formate Ammonium propionata Ammonium butyrate.
- cotton dyed with tetrazotized dianisidine coupled with Naphthol AS is treated in the solution at 200 F. 'for 1 minute, rinsed and dried.
- cotton dyed with tetrazotized dianisidine coupled with Naphthol AS is treated in the solution at 200 F. for 1 minute, rinsed and dried. In no case was a good metallization obtained as the solution tended to become unstable and precipitate.
- Example 19 Cotton was padded in the usual manner with a solution which consisted of 1.0 parts of the coupler of the formula:
- Example 21 Cotton material was padded as in Example 19 with a solution of coupler differing only in that 1.0 part of the coupler of the formula:
- the solution consisted of 2.0 parts dianisidine tetrazotized and stabilized with zinc chloride, 1.0 part Diazopon SS 833, 0.5 part acetic acid 50 percent solution and 2.0 parts sodium acetate in 133 parts of water. After rinsing and drying, the material was metallized at 200 F. in the copper bath of Example 1 for 1 minute, rinsed and dried. The metallized reddish blue dyeing was much faster to light and washing than a similar dyeing metallized in the usual manner in a copper sulfate-acetic acid solution.
- Example 22 A cobalt solution was made up as follows:
- Metallization was eflicient and the dyeing had a better shade and improved light fastness over a similar metallization made using 0.5 part of cobalt chloride and 0.5 part acetic acid in 133 parts of water at 200 F. for 10 seconds.
- Example 23 A nickel solution was made up as follows:
- Metallization was elficient and the dyeing had a better shade and improved light fastness over a similar metallization made using a solution of only 0.5 part nickel chloride, and 0.5 part acetic acid in 133 parts water at 200 F. for 10 seconds.
- X represents a member selected from the group consisting of hydroxyl, hydrogen and alkyls having 1 to 4 carbon atoms and, (3) such amount of ammonium hydroxide as is necessary to maintain the pH of the solution in said range.
- T he method of claim 2 in which the dyed fibrous material is treated with the solution at a temperature of about 100-212 F. for about 5 seconds to ten minutes.
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Description
United States Patent 3,317,273 METALLIZING AZOIC DYEINGS AND PRINTS Clemens Streck, Loudonville, N.Y., assignor to General Aniline & Film Corporation, New York, N.Y., a corporation of Delaware No Drawing. Filed Apr. 16, 1964, Ser. No. 360,436 14 Claims. (Cl. 8-42) This application is a continuation-in-part of application Ser. No. 175,799, of Clemens Streck, filed Feb. 26,
The present invention relates to, in general, the metallization of azoic dyeings and prints and, in particular, to an improved method for the metallization of azoic dyeings on the fiber.
Previous arrangements and methods heretofore considered practical contemplated pre-metallization of watersoluble dyes in an alkali metal ion-containing dye bath solution and subsequently dyed on or into the fiber. The conditions under which dyeing of fibers with pre-metallized dyes are usually very stringent involving boiling of the fabric to be dyed for several hours. Metallization treatments of previously dyed fibrous materials, on the other hand, is preferable since dyeings are obtained having improved light fastness and improved shades. Also such treatments lend themselves to continuous operations. However, such metallization treatments are delicate and certain precautions must be exercised since the treatment must be sufficiently drastic to efiect metallization but insufiicient to tender or damage the fiber. Additionally, in order for such treatments to be adapted to continuous operations a sufficiently loose metal complex must be employed. Yet the metal complex must be sufficiently stable under the conditions of application so as not to precipitate out of solution.
Accordingly, it is an object of this invention to provide an improved method for the metallization of azoic dyeings and prints.
Afurther object of this invention resides in tthe provision of an improved method for the metallization of azoic dyeings and prints which can be carried out in a continuous fashion.
Yet another object of this invention is to provide azoic printings and dyeings of improved light fastness which are substantially free of light breaks and fading.
Still another object of this invention contemplates the provision of improved metallizing compositions suitable for metallizing azoic dyeings and printed fibers.
Other objects and advantages of the invention will become further apparent hereinafter as the'description of the invention proceeds.
, It has now been discovered that the aforesaid objects can be readily accomplished by treating'a fibrous material dyed with a water-insoluble azoic dye free of solubilizing groups and containing in o,o-positions relative to an azo linkage groups capable of conversion to a complex metal compound with an alkali-ion-free aqueous alkaline solution, having a pH in the range of above 7-9, containing a metallizing compound of the group consisting of salts and hydroxides of copper, cobalt, and nickel capable of forming a metal complex with said azoic dye and ammonium salt of the formula:
wherein X represents a member selected from the group consisting of hydroxyl, hydrogen and alkyls having 1 to 4 carbon atoms and such amount of ammonium hydroxide as is necessary to maintain the pH of the solution in said range.
' The metallizing compounds capable of forming a metal complex with said azoic dyeing or printingwhich can be 3,317,273 Patented May 2, 1967 advantageously employed are the water-soluble or dispersible salts and hydroxides of copper, nickel or cobalt, usually in the form of the chlorides, sulfates, nitrates, formates, acetates, propionates and butyrates.
The amount of metallizing compound which may be employed will usually depend upon the degree of metallization desired. While molar ratios are required for complete metallization, the amount employed can be varied from an equivalent to an excess of one equivalent of metal per equivalent of dye.
The metallizing compound is coordinated by the addition to an aqueous solution thereof of an ammonium salt characterized by the formula above. This ammonium salt can be added as such or if desired, can be added as the corresponding free acid and ammonium hydroxide be then added to form the ammonium salt by neutraliza tion; in any event sufiicient ammonium hydroxide must be employed to bring the alkalinity to a pH of above 7 to 9 (preferably about 9). Representative lower aliphatic monocarboxylic acids and salts which can be advantaa geously employed are formic acid, acetic acid, propionic acid, butyric acid, the corresponding ammonium salts as will as carbonic acid and its corresponding ammonium sa t.
The amount of metal salt which is employed in the treating solution can vary from 0.05 ounce per gallon to 10 ounces per gallon.
The metallization treatment in accordance with this invention is applicable to fibrous materials having thereon an azoic dyeing in which the dye molecule contains an airomatic configuration which lends itself to the production of an o,o-dihydroxy type of metallization. Such azoic dyeings may be produced in situ on the fiber in any conventional manner; e.g., by impregnating the fiber with an azoic coupling component and then dyeing with a solution which contains an active diazo either in the form of a freshly prepared diazo or as a Fast Color salt solution. The dyeing may also be produced by printing the fiber with a paste which comprises a mixture of the diazo amino compound and coupling component and exposing the printed fiber to conditions suitable for coupling.
The diazos and the coupling components employed are those which are free from solubilizing groups such as sulfonic and carboxylic acids and which produce dyes having hydroxy groups ortho to the azo linkage or groups which are convertible into hydroxy groups such 'as lower alkoxy, i.e., methoxy, ethoxy, propoxy and 'butoxy.
The diazos employed in this invention are those produced from any aromatic diazotizable amine which does not contain solubilizing groups such as sulfonic and carboxylic acids and includes all of the conventional aromatic and 'heterocyclic amines that are customarily employed in the preparation of azoic dyes. Unless the coupler to be used contains the o,o-dihydroxy configuration the amine should also have an o-hydroxy or lower alkoxy group ortho to the amine group. As examples of such diazotizable amines, the following are illustrative:
o-anisidine;
S-chloro-o-anisidine; S-nitro-o-anisidine;
o-dianisidine; 4-benzamido-2,S-dimethoxyaniline; 2,5-dimethoxy-4-(p-nitrobenzeneazo)aniline; 4-cyano-2,S-diinethoxyaniline; 5-diethylsulfamyl-o-anisidine; 4-phenylamino-o-anisidine; 5-n-butylsulfamyl-o-hydroxyaniline; 5-amino-6-hydroxyquinoline; 2-hydroxy-4-nitroaniline; 2-hydroxy-5-nitroaniline; chlorotoluidines;
chloroaniline;
dichloroaniline; trifiuoromethylchloroaniline; 4-nitro-o-anisidine; 4-chloro-o-anisidine; -chloro-4-nitro-o-anisidine; credisine;
5- butylsulfamyl) -o-anisidine; 4-benzamido-2,S-diethoxyaniline; 4-benzamido-5 -methy1-o-a'nisidine.
In the case where the coupling component contains the o,o'-dihydroxy configuration, the above may be used, as also those free from the o-hydroxy and alkoxy configuration, e.g., p-chloroaniline, p-anisidine and benzidine.
.The coupling components may, in general, be selected from the Naphthol AS compounds which are arylides of 2-hydroxy-3-naphthoic acid and related fl-hydroxy carboxylic acid derivatives, acetoacetarylides and related B-oxocarboxylic acid arylides and pyrazolones. However, other compounds may be employed which are capable of coupling to yield a component having the required metallizable group in ortho position to the azo linkage. Thus, in addition to the coupling components specifically set forth in the examples, the following coupling components may be employed: 1
Z-naphthol,
3 -hydroxy-2- 2',5 '-dimethoxy naphthanilide, 3-hydroxy-2- N-naphthyl naphthamide,
3-hydroxy -2- (4-chloro naphthanilide,
3-hydroxy-2- N-2-methoxy-3-dibenzofuryl naphthamide, 3-hydroxy-anthraquinone-Z-carbox-o-toluidide,
2-hydroxy-3-dibenzofurancarboxylic acid arylides such as 2-hydroxy-3-dibenzofuran 2,5 -dimethoxy carboxanilide, bis(acetoacet)benzidide, bis(acetoacet)-tolidide, acylacetarylides such as acetoacet-4-chloro-2,S-dimethoxyanilide, 3-hydroxy-2-carbaZole-carboxylic acid arylides such as 3-hydroxy-2-carbazole-(p-chloro)carboxyanilide, terephthaloyl bisacetoacet-(3-chloro-2',4-dimethoxy)-anilide, pyrazolones, such as l-phenyl-3-methyl-5-pyrazolone, 3-hydroxy-2-naphthoic acid arylides, o-hydroxy-aniline resorcinol, 2-hydroxy-5-nitro-aniline resorcinol. In the case of the couplers in the last two examples listed, wherein the o-hydroxyazo linkage is present in the coupler per se, any ordinary diazo compounds may be employed, such as m-chloroaniline, o-nitroaniline, l-amino-anthraquinone and 2-amino-4,4-dichlorodiphenyloxide. Other azo couplers, such as the metallized compounds disclosed in United States Patent 2,135,433 and the unmetallized products thereof, and the like can also be employed.
The diazo may be supplied by an amine freshly diazotized by treatment with nitrite in the customary manner, or the diazo may be stabilized diazo, i.e., in the form of diazonium chloride or sulfate, or in the form of the diazo stabilized as a double salt, i.e., as a zinc chloride, boron trifiuoride, tin chloride, naphthalenedisulfonic acid, etc.
, As illustrative examples of Fast Color Salts, the following are illustrative:
Fast Blue Salt BN l 0 C11: 0 CH3 Fast Blue Salt ZBN (IJC Hs 4 Fast Red Salt BN OCH:
Fast Red Salt TRN Fast Black Salt K OCHa )CHs Fast Bordeaux Salt BD OCH;
l OCHa Variamine Blue Salt BD Fast Red Salt RL OzN- Fast Red Salt FR conventional manner with naphthol, hydroextracted or salt rinsed to remove excess naphthol and excess alkali, developed with a diazo solution and finished in customary manner. Alternatively, the textile material may be printed with a Rapidogen and then developed in acid or neutral steam.
After the dyeing or printing is completed, the dyed or printed material is metallized in accordance with the method of the invention for a period of time of from about 5 seconds to 10 minutes depending on the degree of metallization desired, at a temperature in the range of from to 212 F. The metallizing solution contains per 1 part of metal salt, 1-4 parts of carbonic acid or a lower aliphatic carboxylic acid and 2-15 parts of ammonium hydroxide to provide an alkalinity to the solution of a pH of from above 7-9, and preferably closer to pH 9. The same result may be accomplished by the employment of the ammonium salts of the corresponding acids and any additional ammonium hydroxide necessary to control and maintain the pH of the solution in the range aforesaid.
The following examples will serve to illustrate some of the preferred embodiments of the invention; it being clearly understood, however, that these examples arev merely illustrative and are not to be considered as a limitation of the invention.
Example] A metallizing solution was made up as follows:
Copper solution: Parts Copper sulfate Water 280 Ammonium hydroxide, 26 B. 430
Glacial acetic acid 220 A cotton print produced in the usual manner from tetrazotized dianisidine and Naphthol AS was treated in 2 ounces of the above solution plus /2 ounce of ammonium hydroxide per gallon of added water at 150 F. for seconds, rinsed and dried.
In comparison, a similar cotton print was treated in 1 a solution which contained 0.5 ounce copper sulfate and 0.5 ounce 'acetic acid in 1 gallon water at 200 F. for 10 seconds, rinsed and dried. This method constitutes normal metallizing procedure as it is now practiced.
Metallization in case of the ammonia-containing metallizing bath was more efficient than in the case of the other bath as shown by better light fastness.
Examples 2-10 A cotton print produced from tetrazotized dianisidine and Naphthol AS was treated at 200 F. for 1 minute in the following baths:
6 Example 15 A print is made on cotton in the usual manner fiom 4-benzamido-5-methyl-oanisidine diazotized and stabilized with sarcosine and Naphthol AS. This print is treated for 10 seconds at 200 F. in the copper solution of Example 1. Metallization was eificient as determined by the color and light fastness of the print.
Example 16 A metallization was made as in Example 15, employing a print made in the usual manner from tetrazotized and stabilized dianisidine and Naphthol AS. The metallization was efiicient as determined by shade and light fastness tests.
Example 17 A metallization was made as in Example 15, employing a print made in the usual manner from diazotized and stabilized S-methyl-o-anisidine and coupled with 3'- nitro-3-hydroxy-2-naphthanilide. The metallization was efiicient as determined by shade and light fastness tests.
Example 18 A metallization was made as in Example 15, employing a print made in the usual manner from 4-benzarnid0- S-methyl-o-anisidine diazotized and stabilized with methyltaurine and coupled with 4-(S-chloro-2-hydroxyphenyl- Watter (gallon) Copper sulfate (oz.) Ammonium acetate Ammonium hydroxide 26 B- Ammonium carbonate Acetic acid Ammonium formate Ammonium propionata Ammonium butyrate.
In the above set of examples, cotton dyed with tetrazotized dianisidine coupled with Naphthol AS is treated in the solution at 200 F. 'for 1 minute, rinsed and dried.
In all cases, metallization was satisfactory as shown by light fastness tests.
Examples 11-14 Example Water (gallon) 1. 0 1 0 1. 0 1 0 Copper sulfate (02.) 0.6 0 5 0. 5 0 5 Ammonium hydroxide 26 Be 2. 0 0 6 0. 5 0 5 Ammonium sulfate 3. O Ammonium chloride 2. 5
In the above set of examples, cotton dyed with tetrazotized dianisidine coupled with Naphthol AS is treated in the solution at 200 F. for 1 minute, rinsed and dried. In no case was a good metallization obtained as the solution tended to become unstable and precipitate. The
metallizations were dull, several tended to be bronzy and the dyeings lacked the high degree of light fastness imparted by the teachings of this invention.
' This set of examples demonstrates that ammonium hydroxide alone or in combination with the stronger inorganic acid salts, is not satisfactory.
azo) resorcinol. The metallization was efficient as determined by shade and light fastness tests.
Example 19 Cotton was padded in the usual manner with a solution which consisted of 1.0 parts of the coupler of the formula:
OH OH 2.0 parts glycol monoethyl ether, 1.6 parts caustic flake and 133 parts water. The material was dried and padded with a solution consisting of 4.0 parts 4-nitro-o-anisidine diazotized and stabilized with 1,S-naphthalene-disulfonic Example 20 Cotton material was padded as in Example 19 with a solution of coupler differing only in that 1.0 part of the coupler of the formula:
OH HaCO OCHa OH was substituted for the coupler of Example 19. In padding with diazo, the solution consisted for 4.5 parts 2,5- dichloroaniline diazotized and stabilized with zinc chloride, 1 part Diazopon SS 83 3, 1 part acetic acid 50 percent solution and 1.5 parts sodium acetate in 133 parts of water. After rinsing and drying, the material was metallized at 200 F. in the copper bath of Example 1 for 1 minute, rinsed and dried. The metallized reddish brown dyeing was much faster to light and washing than a similar dyeing metallized in the usual manner in a copper sulfate-acetic acid solution.
Example 21 Cotton material was padded as in Example 19 with a solution of coupler differing only in that 1.0 part of the coupler of the formula:
was substituted for the coupler of Example 19. In padding with diazo, the solution consisted of 2.0 parts dianisidine tetrazotized and stabilized with zinc chloride, 1.0 part Diazopon SS 833, 0.5 part acetic acid 50 percent solution and 2.0 parts sodium acetate in 133 parts of water. After rinsing and drying, the material was metallized at 200 F. in the copper bath of Example 1 for 1 minute, rinsed and dried. The metallized reddish blue dyeing was much faster to light and washing than a similar dyeing metallized in the usual manner in a copper sulfate-acetic acid solution.
Example 22 A cobalt solution was made up as follows:
Parts Cobalt chloride 70 Water 280 Ammonium hydroxide, 26 B. 430 Glacial acetic acid 220 As in Example 1, a cotton print produced from tetrazotized dianisidine and Naphthol AS was treated in 2 parts of the above solution and A; part of ammonia in 133 parts of water at 150 F. for seconds, rinsed and dried.
Metallization was eflicient and the dyeing had a better shade and improved light fastness over a similar metallization made using 0.5 part of cobalt chloride and 0.5 part acetic acid in 133 parts of water at 200 F. for 10 seconds.
Example 23 A nickel solution was made up as follows:
Parts Nickel chloride 70 Water 280' Ammonium hydroxide 26 Be. 430 Glacial acetic acid 220 As in Example 1, a cotton print produced from tetrazo tized dianisidine and Naphthol AS was treated in 2 parts of the above solution plus /2 part ammonia in 133 parts of water at 150 F. for 10 seconds, rinsed and dried.
Metallization was elficient and the dyeing had a better shade and improved light fastness over a similar metallization made using a solution of only 0.5 part nickel chloride, and 0.5 part acetic acid in 133 parts water at 200 F. for 10 seconds.
Various modifications of the invention will occur to persons skilled in the art. Thus, it is evident in lieu of the compounds of the specific examples, any of the compounds mentioned above can be employed with similar results. Therefore, it is not intended that the invention be limited in the patent granted except as necessitated by the appended claims.
What is claimed is:
1. In the method of after-treating fibrous materials dyed with an azoic dye free of solubilizing groups and containing in o,o'-positions relative to an azo linkage groups capable of conversion to a complex metal compound, the improvement which comprises treating said dyed fibrous material with an alkali-ion-free aqueous alkaline solution having a pH in the range of above 7-9, containing (1) a metallizing compound of the group consisting of salts and hydroxides of copper, cobalt and nickel capable of forming a metal complex with said azoic dye, (2) an ammonium salt of the formula:
wherein X represents a member selected from the group consisting of hydroxyl, hydrogen and alkyls having 1 to 4 carbon atoms and, (3) such amount of ammonium hydroxide as is necessary to maintain the pH of the solution in said range. I
2. In the method of after-treating fibrous materials dyed with an azoic dye free of solubilizing groups and containing in o,o-positions relative to an azo linkage groups capable of conversion to a complex metal compound, the improvement which comprises treating said dyed fibrous material with an alkali-ion-free aqueous alkaline solution having a pH in the range of above 7- 9, containing (1) a metallizing compound of the group consisting of salts and hydroxides of copper, cobalt and nickel capable of forming a metal complex with said azoic dye and, (2) ammonium salts of acids selected from the group consisting of carbonic acid and lower aliphatic monocarboxylic acids.
3. In the method of after-treating fibrous materials dyed with an azoic dye free of solubilizing groups and containing in o,o'- positions relative to an azo linkage groups capable of conversion to a complex metal compound, the improvement which comprises treating said dyed fibrous material with an alkali-ion-free aqueous alkaline solution having a pH in the range of above 7-9, containing (1) a metallizing compound of the group consisting of s alts and hydroxides of copper, cobalt and nickel capable of forming a metal complex with said azoic dye, (2) ammonium salts of acids selected from the group consisting of carbonic acid and lower aliphatic monocarboxylic acids and, (3) ammonium hydroxide in an amount sufficient to provide the aforesaid alkalinity.
4. The method according to claim 2 wherein the metallizing compound is copper sulfate and the ammonium salt is ammonium acetate.
5. The method according to claim 2 wherein the metallizing compound is copper sulfate and the ammonium salt is ammonium carbonate.
6. The method according to claim 2 wherein the meta1- lizing compound is copper sulfate and the ammonium salt is ammonium formate.
7. The method according to claim 2 wherein the metallizing compound is copper sulfate and the ammonium salt is ammonium propionate.
8. The method according to claim 2 wherein the metallizing compound is copper sulfate and the ammonium salt is ammonium butyrate.
9. The method according to claim 3 wherein the metallizing compound is copper sulfate and the acid is glacial acetic acid.
10. The method according to claim 3 wherein the metallizing compound is cobalt chloride and the acid is glacial acetic acid.
11. The method according to claim 3 wherein the metallizing compound is nickel chloride and the acid is glacial acetic acid.
12, The method of claim 1 in which the dyed fibrous material is treated with the solution at a temperature of about 10()212 F. for about 5 seconds to ten minutes.
13. T he method of claim 2 in which the dyed fibrous material is treated with the solution at a temperature of about 100-212 F. for about 5 seconds to ten minutes.
14. The method of claim 3 in which the dyed fibrous material is treated with the solution at a temperature of about 100212 F. for about 5 seconds to ten minutes.
1 0 References Cited by the Examiner UNITED STATES PATENTS 1,853,418 4/1932 Hentrich et a1 8-42 r 2,148,659 2/1939 Straub et a1. 842 2,673,200 3/1954 Ruchstuhl et a1. 874X 2,768,055 10/1956 Streck 8--42 NORMAN G. TORCHIN, Primary Examiner.
10 D. LEVY, Assistant Examiner.
Claims (1)
1. IN THE METHOF OF AFTER-TREATING FIBROUS MATERIALS DYED WITH AN AZOIC DYE FREE OF SOLUBILIZING GROUPS AND CONTAINING IN O,O''-POSITIONS RELATIVE TO AN AZO LINKAGE GROUPS CAPABLE OF CONVERSION TO A COMPLEX METALA COMPOUND, THE IMPROVEMENT WHICH COMPRISES TREATING SAID DYED FIBROUS MATERIAL WITH AN ALKALI-ION-FREE AQUEOUS ALKALINE SOLUTION HAVING A PH IN THE RANGE OF ABOVE ALKALINE SOLUTION HAVING A PH IN THE RANGE OF ABOVE 7-9, CONTAINING (1) A METALLIZING COMPOUND OF THE GROUP CONSISTING OF SALTS AND HYDROXIDES OF COPPER, COBALT AND NICKEL CAPABLE OF FORMING A METAL COMPLEX WITH SAID AZOIC DYE, (2) AN AMMONIUM SALT OF THE FORMULA:
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1853418A (en) * | 1923-02-27 | 1932-04-12 | Gen Aniline Works Inc | Dyeing of viscose |
US2148659A (en) * | 1935-04-06 | 1939-02-28 | Soc Of Chemical Ind | Process for the production of fast tints on cellulosic fibers |
US2673200A (en) * | 1950-06-21 | 1954-03-23 | Sandoz Ag | Azo dyestuffs |
US2768055A (en) * | 1952-11-15 | 1956-10-23 | Gen Aniline & Film Corp | Composition for aftertreatment of dyeings |
-
1964
- 1964-04-16 US US360436A patent/US3317273A/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1853418A (en) * | 1923-02-27 | 1932-04-12 | Gen Aniline Works Inc | Dyeing of viscose |
US2148659A (en) * | 1935-04-06 | 1939-02-28 | Soc Of Chemical Ind | Process for the production of fast tints on cellulosic fibers |
US2673200A (en) * | 1950-06-21 | 1954-03-23 | Sandoz Ag | Azo dyestuffs |
US2768055A (en) * | 1952-11-15 | 1956-10-23 | Gen Aniline & Film Corp | Composition for aftertreatment of dyeings |
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