US3630656A - Process for the dyeing and printing of metal-containing polyolefin textile materials - Google Patents

Process for the dyeing and printing of metal-containing polyolefin textile materials Download PDF

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US3630656A
US3630656A US867916A US3630656DA US3630656A US 3630656 A US3630656 A US 3630656A US 867916 A US867916 A US 867916A US 3630656D A US3630656D A US 3630656DA US 3630656 A US3630656 A US 3630656A
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methoxy
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hydrazide
metal
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Gerhard Wolfrum
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/72—Hydrazones
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B26/00—Hydrazone dyes; Triazene dyes
    • C09B26/02—Hydrazone 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
    • Y10S8/92—Synthetic fiber dyeing
    • Y10S8/928—Polyolefin fiber

Definitions

  • the individual process according to the invention is carried out in such a manner that the compounds of the general formula (l) are applied on to the materials to be treated, particularly fibers and fabrics, from acidic, neutral or weakly alkaline suspensions, dispersions, pastes or solutions, preferably with the use of dispersing agents, emulsifiers, dyeing accelerators, thickening agents and/or levelling auxiliaries, from a dyebath, a padding liquoror by means of a printing paste.
  • a dyeing liquor is used, this is brought to an elevated temperature for a certain time by gradually raising the temperature in the course of the dyeing process, for example, to temperatures of about 90l40 C., preferably to temperatures of about 95l 10 C.
  • the fabric is likewise subjected to a heat treatment after printing.
  • the heat treatment may be carried out either by hot air or by steam, at temperatures of, for example, l00l40 C.
  • duration of the treatment is generally about 1 -l0 minutes.
  • the resistance to rubbing of the dyeings obtained can some times be improved by an alkaline after-treatement of the dyed material, or by an after-treatment with reducing agents, such as sulfites or formaldehyde/sulphite addition products in an alkaline medium, optionally with the addition of an emulsifier.
  • reducing agents such as sulfites or formaldehyde/sulphite addition products in an alkaline medium, optionally with the addition of an emulsifier.
  • Suitable dispersing or emulsifying agents which are advantageously added to the compounds of the formula (I) to be used according to the invention are commercially available products, such as sulfite cellulose waste liquor products, condensation products of higher alcohols and ethylene oxide, soaps, polyglycol ethers of fatty acid amides, formaldehyde condensation products of aromatic sulfonic acids or mixtures of such compounds.
  • the customary thickening agents such as methyl cellulose, carob bean flour, crystal gurn, alginates or tragacanth can be used.
  • the printing pastes may also contain the usual additives, such as urea, thiourea, thiodiglycol, methylated alcohols, sodiumm-nitrobenzosulphonate or aqueous emulsions of sulfonated oils.
  • The' dyed orprinted materials preferably obtained from met'a'l ctSntaining polypropylene, can be after-treated in usual manner, subsequently to the dyeing or printing process, for example, by washing, brightening, decatizing or heat settmg.
  • the process according to the invention is preferably used for the dyeing and printing of metal-containing, preferably nickel-containing. polypropylene fiber materials.
  • metal-containing polypropylene fiber materials comprises those fiber materials whieh contain the metals either as such or in the form of their salts, but preferablyin the form of chelates.
  • Suitable metal chelates are particularly nickel chelates or nickel compounds of phenols, bis-(alkyphenol)-monosulfides, bis-(p-alkylphenol)-sulphoxides, bis-(p-alkylphenol) sulphones dithiocarbamates, o-hydroxyphenyl-benztriazoles, hydroxamic acids, and nickel dimethyl dioxime and nickel acetylacetone, at concentrations of 0.0l to 3 percent, preferably 0.1 to 2 percent.
  • Thenickelcomplexes can be used by themselves or in admixture withother nickel complexes or nickel salts.
  • the polypropylene materials may also contain salts or chelates of zinc, aluminum, magnesium, cobalt, copper or chromium by themselves or in admixture with one another.
  • the last-mentionedn etalsalts.or chelates may also be present together in the polypropylene fiber materials in admixture with the above-mentioned-salts or chelates of nickel.
  • o-hydroxyaldehydes may be used; for example: Z-hydroxy-benzaldehyde, 3-methoxy-2-hydroxy-benzaldehyde, 5-,chloro-2-hydroxybenzaldehyde, 3,5-dichloro-2- hydroxybenzaldehyde, 5-.br orn0-2-hydroxybenzaldehyde, 2- hydroxy-naphthaldehyd e-( l l.-hydroxy-naphthaldehyde-(2 2-hydroxy-naphthaldehyde-(3.), 5-chloro-2-hydroxynaphthaldehyd e-(l), 6-ehloro- 2-hydroxy-naphthaldehydel -c -Z- y r ya thald y e-( I 6-.
  • o-alkoxy-earboxylic acid hydrazides may be used, for example: 2-methoxybenzoie acid hydrazide, Z-ethoxybenzoic acid hydrazide, 2-propoxybenzoic acid hydrazide, 2- n-butyloxybenzoic acid hydrazide, 2-methoxy-5-methylbenzoic acid hydrazide, 2-methoxy-4-methylbenzoic acid hydrazide, 2-methoxy-S-tertiary-butyl-benzoi c acid hydrazide, 2-methoxy-4-n-butyl benzoic acid hydrazide, 2-methoxy-5-' chloro-benzoic acid hydrazide, 2-methoxy-4-chloro-benzoic acid
  • All Preferred compounds of the general formula (I) are those in 16 H same as above U which A stands for a naphthalene radical substituted as indicaled, and B stands for a benzene ring substituted as indicated; as well A as B may contain the further substituents 113C 0 C11 mentloned above.
  • the dyeings obtained by the process according to the invention are distinguished by outstanding fastness to washing, solvents and heat setting as well as by very good fastness to light.
  • the subject matter of the invention further comprises com pounds of the formula in which X stands for a 2-methoxyphenyl, 2-methoxy-4- methylphenyl, 2-methoxy-5-methylphenyl, 2-methoxy-2- tert.-butylphenyl, 2-methoxy'5-chlorophenyl or 2- methoxy-naphtyl radical.
  • X stands for a 2-methoxyphenyl, 2-methoxy-4- methylphenyl, 2-methoxy-5-methylphenyl, 2-methoxy-2- tert.-butylphenyl, 2-methoxy'5-chlorophenyl or 2- methoxy-naphtyl radical.
  • the printed fabric is dried and subsequently steamed at 100 C. for 30 minutes. After thoroughly rinsing and an aftertreatment at 50-80 C. with 0.5 parts, per liter water, of a reaction product of about 8-10 mol ethylene oxide with 1 mol nonylphenol, rinsing and drying, a clear greenish yellow print with very good fastness properties is obtained.
  • Process for the dyeing and printing of textile materials of metal-containing polypropylene which comprises applying to the textile materials a compound of the general formula (ll N N t ill 1 1 ll 40 Ull ll 0 OR in which A stands for a benzene or naphthalene radical which is unsubstituted or which is substituted by chlorine or bromine. or by alkyl radicals with one to four carbon atoms. the-OH-group and the substituent-(H N- being attached to adjacent carbon atoms; B represents a benzene or naphthalene radical which is unsubstituted or which is substituted by chlorine or bromine, or by alkyl radicals with one to four carbon atoms.
  • A stands for a benzene or naphthalene radical which is unsubstituted or which is substituted by chlorine or bromine. or by alkyl radicals with one to four carbon atoms.

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  • Organic Chemistry (AREA)
  • Coloring (AREA)

Abstract

Dyeing and printing of textile materials of metal-containing polypropylene with compounds of the general formula

IN WHICH A stands for a optionally substituted benzene or naphthalene radical the -OH-group and the substituent -CH Nbeing attached to adjacent carbon atoms; B represents a optionally substituted benzene or naphthalene the substituent -OR and the substituent

BEING ATTACHED TO ADJACENT CARBON ATOMS AND R representing an alkyl radical A and B cannot simultaneously represent radicals of the benzene series.

Description

United States Patent [72] Inventor Gerhard Wolh'um Opladen, Germany [21] Appl. No. 867,916 [22] Filed Oct. 20, 1969 [45] Patented Dec. 28, 1971 [73] As'signee Farbentabriken Bayer Aktiengesellschatt Leverkusen, Germany [32] Priority Oct. 19, 1968 [3 3] Germany [31] P 18 04 133.3
[54] PROCESS FOR TIIE DYEING AND PRINTING OF METAL-CONTAINING POLYOLEFIN TEXTILE MATERIALS 2 Claims, No Drawings [52] U.S. 8/31, 8/180, 260/558 [51] Int. Cl D06p 1/36, 00% 65/00 [50] Field of Search 8/41, 31, 180-181; 260/558 [56] References Cited UNITED STATES PATENTS 2,767,173 10/1956 Katz 260/240 3,1 10,696 11/1963 Dexter 260/45.8 3,399,027 8/1968 Siegrist et al. 8/31 3,547,646 12/1970 Hori et al 96/90 Primary Examiner-George F. Lesmes Assistant Examiner-Patricia C. Ives Attorney-Plumley, Tyner 8!. Sandt I III 011 IIOOR in which A stands for a optionally substituted benzene or naphthalene radical the -OH-group and the substituent -CH- N- being attached to adjacent carbon atoms; B represents a optionally substituted benzene or naphthalene the substituent -OR and the substituent being attached to adjacent carbon atoms and R representing an alkyl radical A and 13 cannot simultaneously represent radicals of the benzene series.
PROCESS FOR THE DYEING ANDPRINTING OF METAL- CONTAINING POLYOLEFIN TEXTILE MATERIALS It has been found that materials of metal-containing polyolefins, such as filaments, fibers, foils, woven and knitted fabrics, especially those of nickel-containing polypropylene, can be dyed and printed fast when they are treated with compounds of the general formula II on ll OR being attached to adjacent carbon atoms, R represents an alkyl radical with one to four carbon atoms; A and B cannot simultaneously represent radicals of the benzene sems.
The individual process according to the invention is carried out in such a manner that the compounds of the general formula (l) are applied on to the materials to be treated, particularly fibers and fabrics, from acidic, neutral or weakly alkaline suspensions, dispersions, pastes or solutions, preferably with the use of dispersing agents, emulsifiers, dyeing accelerators, thickening agents and/or levelling auxiliaries, from a dyebath, a padding liquoror by means of a printing paste. When a dyeing liquor is used, this is brought to an elevated temperature for a certain time by gradually raising the temperature in the course of the dyeing process, for example, to temperatures of about 90l40 C., preferably to temperatures of about 95l 10 C. When a padding liquor is used, the padded fabn'c is subsequently subjected to a heat treatment, if necessary,=
after an intermediate drying. When a printing paste is used, the fabric is likewise subjected to a heat treatment after printing. The heat treatment may be carried out either by hot air or by steam, at temperatures of, for example, l00l40 C. The
duration of the treatment is generally about 1 -l0 minutes.
The resistance to rubbing of the dyeings obtained can some times be improved by an alkaline after-treatement of the dyed material, or by an after-treatment with reducing agents, such as sulfites or formaldehyde/sulphite addition products in an alkaline medium, optionally with the addition of an emulsifier.
Suitable dispersing or emulsifying agents which are advantageously added to the compounds of the formula (I) to be used according to the invention are commercially available products, such as sulfite cellulose waste liquor products, condensation products of higher alcohols and ethylene oxide, soaps, polyglycol ethers of fatty acid amides, formaldehyde condensation products of aromatic sulfonic acids or mixtures of such compounds.
To produce printing pastes which contain the compounds of the formula (I) to be used according to the invention, the customary thickening agents, such as methyl cellulose, carob bean flour, crystal gurn, alginates or tragacanth can be used. The printing pastes may also contain the usual additives, such as urea, thiourea, thiodiglycol, methylated alcohols, sodiumm-nitrobenzosulphonate or aqueous emulsions of sulfonated oils.
The' dyed orprinted materials, preferably obtained from met'a'l ctSntaining polypropylene, can be after-treated in usual manner, subsequently to the dyeing or printing process, for example, by washing, brightening, decatizing or heat settmg.
The process according to the invention is preferably used for the dyeing and printing of metal-containing, preferably nickel-containing. polypropylene fiber materials. The term metal-containing polypropylene fiber materials comprises those fiber materials whieh contain the metals either as such or in the form of their salts, but preferablyin the form of chelates. Suitable metal chelates are particularly nickel chelates or nickel compounds of phenols, bis-(alkyphenol)-monosulfides, bis-(p-alkylphenol)-sulphoxides, bis-(p-alkylphenol) sulphones dithiocarbamates, o-hydroxyphenyl-benztriazoles, hydroxamic acids, and nickel dimethyl dioxime and nickel acetylacetone, at concentrations of 0.0l to 3 percent, preferably 0.1 to 2 percent. Thenickelcomplexes can be used by themselves or in admixture withother nickel complexes or nickel salts. Instead of the nickel compounds mentioned above, the polypropylene materials may also contain salts or chelates of zinc, aluminum, magnesium, cobalt, copper or chromium by themselves or in admixture with one another. Finally, the last-mentionedn etalsalts.or chelates may also be present together in the polypropylene fiber materials in admixture with the above-mentioned-salts or chelates of nickel.
The compounds of the general formula (I) .to be used according to the invention are obtained in known manner vby reacting o-hydroxyaldehydes of the benzene or naphthalene series with o-alkoxy=ca1:boxylicaeid hydrazidesof the benzene or naphthalene series.
The following o-hydroxyaldehydesmay be used; for example: Z-hydroxy-benzaldehyde, 3-methoxy-2-hydroxy-benzaldehyde, 5-,chloro-2-hydroxybenzaldehyde, 3,5-dichloro-2- hydroxybenzaldehyde, 5-.br orn0-2-hydroxybenzaldehyde, 2- hydroxy-naphthaldehyd e-( l l.-hydroxy-naphthaldehyde-(2 2-hydroxy-naphthaldehyde-(3.), 5-chloro-2-hydroxynaphthaldehyd e-(l), 6-ehloro- 2-hydroxy-naphthaldehydel -c -Z- y r ya thald y e-( I 6-. r m hydroxy-naphthaldehyde-('1 6-methyl-2 hydroxy-naphthaldehyde-( l 2-methoxy-2hydroxy-naphthaldehyde l The following o-alkoxy-earboxylic acid hydrazides may be used, for example: 2-methoxybenzoie acid hydrazide, Z-ethoxybenzoic acid hydrazide, 2-propoxybenzoic acid hydrazide, 2- n-butyloxybenzoic acid hydrazide, 2-methoxy-5-methylbenzoic acid hydrazide, 2-methoxy-4-methylbenzoic acid hydrazide, 2-methoxy-S-tertiary-butyl-benzoi c acid hydrazide, 2-methoxy-4-n-butyl benzoic acid hydrazide, 2-methoxy-5-' chloro-benzoic acid hydrazide, 2-methoxy-4-chloro-benzoic acid hydrazide, 2-methoxy-3-methyl-5-chloro-benzoic acid hydrazide, 2-methoxy-5-methyl-4-chloro-benzoic acid hydrazide, 2,3-dimethoxybenzoic acid hydrazide, 2-methoxy-3- methyl-benzoic acid hydrazide, 2,4-dimethoxybenzoic acid hydrazide, 2-methoxy-4,6dim ethylbenzoic acid'hydrazide, 2- ethoxy-S-methyl-benzoic acid hydrazide, 2- ethoxy4-methylbenzoic acid hydrazide, Z-ethoxy-S-tert.butyl-benzoic acid hydrazide, Z-ethoxy-S-chloro benzoic acid hydrazide, 2 ethoxy-3-methyl-5-chloro-benzoic acid hydrazide, Z-ethoxy- 5-methyl-4 -chloro-benzoic acid hydrazide, 2 ,3-diethox ybenzoic acid hydrazide, 2-n-butoxy5chloro benzoic acid hydrazide, l-methoxy-naphthalene-carboxylic acid-(2) hydrazide, 2-methoxy-naphthalene-carboxylic acid-( I )-hydrazide, 2-methoxy-naphthalene-carboxylic acid-( 3 )-hydrazide, lethoxy-naphthalene-carboxylic acid-(2 )-hydrazide, 2-ethoxynaphthalene-earboxylic acid I )-hydrazi de, 2-ethoxynaphthalene-carboxylic acid 3 )-hydraz ide.
Compounds suitable for the process according to the invention are, for example, the compounds set out in the-following Hutu Compound No. D E Compound No. D E
Ifi'ii'flj "s'aEiEiivjl jlf 66113 1 111;
18 a v 4 do OC1I3 l 4 a v M l l 11300 01 on I 3C0 on a a a r Q Smnv as uhovv. 5 Same as above 20 I I H5C20 l1 Do 0 "on 7 r do l2 Samcas abnvv ()Clla 9 sanlensabovcnnun C(CHm l Inco lhCO 10 ..d0
- -c4m U C(I) 25",, Samous abovvunr. Q
11 do c1 1 I 119040 26. new (113 IHCO 12 "dado --c1 11,00
13 4 e do .r.no
All Preferred compounds of the general formula (I) are those in 16 H same as above U which A stands for a naphthalene radical substituted as indicaled, and B stands for a benzene ring substituted as indicated; as well A as B may contain the further substituents 113C 0 C11 mentloned above.
The dyeings obtained by the process according to the invention are distinguished by outstanding fastness to washing, solvents and heat setting as well as by very good fastness to light.
The subject matter of the invention further comprises com pounds of the formula in which X stands for a 2-methoxyphenyl, 2-methoxy-4- methylphenyl, 2-methoxy-5-methylphenyl, 2-methoxy-2- tert.-butylphenyl, 2-methoxy'5-chlorophenyl or 2- methoxy-naphtyl radical. The parts or percentages given in the following examples are parts by weight or percentages by weight.
EXAMPLE I Ten parts of a commercial, nickel-containing polypropylene yarn are dyed at boiling temperature for l hour in a bath which contains, in 400 parts water, 0.] part of the finely dispersed compound of the formula Oates m i l Oil llaCt) EXAMPLE 2 A fabric of nickel-containing polypropylene is printed with a printing paste of the following composition:
20 parts of a finely dispersed compound of the formula 260 parts of water,
500 parts of a thickening agent based on tragacanth,
lOO parts of urea,
120 parts of a 50 percent aqueous ammonium sulfate solul,000 parts.
The printed fabric is dried and subsequently steamed at 100 C. for 30 minutes. After thoroughly rinsing and an aftertreatment at 50-80 C. with 0.5 parts, per liter water, of a reaction product of about 8-10 mol ethylene oxide with 1 mol nonylphenol, rinsing and drying, a clear greenish yellow print with very good fastness properties is obtained.
When the compound described in example I is replaced by one of the compounds of the formula l) obtainable by the reaction of the compounds (ll) and the compounds (lll) set out in the table below for the dyeing or printing according to example i or 2, there are obtained, on nickel-containing polypropylene, dyeings of shades specified in the last column, which also have very good fastness properties.
Shade on nickel- \o-Alkoxycarboxylic acid containing poly- 5 to-llydroxyaldehydel hydrazide) propylene 1-hydroxy-i'naphth- 'l-methoxy-hcnzoic acid Yellow.
llititiLYtit. hydrazide.
llo .anethoxy-nicthyl-lienzoic Do.
acid-hydi'azide. '2-hydroxy-t-naphth- 2-0lilOX \-i\t ll7.(\it' acid tlreenish yellow.
10 aldehyde. hydr: ide.
Do lat-hutoxy-bemoic acid Do.
hydrazide.
llo 2-incthoxy-i-methyll enzoic Ho.
acid hy 'azide.
l o l-methox i-niethylbenzoic llo.
acid hydrazide.
llo 2-inethoxy-5-teri.-hntylhen- Do.
mic acid hydrazide.
Do 'l-niet hox y-5-chlorolwnzoic Do. acid chloride.
Do lnicthoxy thnethyl-5- llo.
chloro-lwnzoic acid hydroxide.
ho 3.3-diinethoxylienzoic acid Do.
hydrazide.
llo lanethox y-3-mct hyllienzoic llo.
acid h \'dra1.ide.
U0 'l-inethoxy-4.ti-diniethylllo.
henzoit 'idhydrazide.
I-ltydroxy-2-naphth- .do Do.
aldehyde. Salieylaldehyde ,do Strongly )ll'ttlb ish yellow. Do Do.
2hydrox \'-3,5-dichloro- (lreenish yellow.
benzaldchydc. 3O 3-methoxy-LZ-hydroxylie.
benzaldehyde.
lclaim:
1. Process for the dyeing and printing of textile materials of metal-containing polypropylene. which comprises applying to the textile materials a compound of the general formula (ll N N t ill 1 1 ll 40 Ull ll 0 OR in which A stands for a benzene or naphthalene radical which is unsubstituted or which is substituted by chlorine or bromine. or by alkyl radicals with one to four carbon atoms. the-OH-group and the substituent-(H N- being attached to adjacent carbon atoms; B represents a benzene or naphthalene radical which is unsubstituted or which is substituted by chlorine or bromine, or by alkyl radicals with one to four carbon atoms. or by alkoxy groups with one to four carbon atoms. the substituent- OR and the substituent being attached to ad acent carbon atoms and R representing an alkyl radical with one to four carbon atoms; A and B cannot simultaneously represent radicals of the benzene series.
2. Process of claim I wherein said compound is of the formula \ (n N N co x in which X stands for a 2-methoxyphenyl, 2-methoxy-4- methyl-phenyl. 2-methoxy-5-methylphenyl, 2-methoxy-5- tert.-butylphenyl. 2-methoxy-5-chlorophenyl or 2- methoxy-naphthyl radical.
UNITED STATES PATENT @FFEQE QER'HWQATE @E @QRREQ'HQN Patent No. 3,630,656 Dated December 28, 1971 SN 867,916 In Gerhard Wolfrum It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below Page 1, Abstract, at second line following general formula:
I change CH- to CH= Column Line 1 20 change CH N to CH=N 2 l0 7 change "sulfones dithiocarbamates" to sulfones, dit-hiocarbamates 2 50 change "2-ethoXy4-methyl" to 2-ethoxY-4-methyl 2 77 change H CO I to 8 H3CO 2 34 change"(l) (7 to (l) 7 FORM PO-105O (10-69) USCOMM-DC 60376-1 69 U.S. GOVERNMENT PRINTING OFFICE: I969 OIJGE-SJA UNITED STATES PATENT owner CE'M MAE F CQRECEWN Patent No, 3 I656 Dat d December Gerhard Wolfrum Inventor(s) It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column Line 3 Compound change H co 3 Compound Cl 13 (E) change FORM PC3-1050 (10-69) USCOMM-DC 60376-P69 fir u.s, GOVERNMENT PRINTING OFFICE: I969 o-ass-su UNITED STATES PATENT @FFMJE QERMHQATE @i RREHN Patent No. 3 ,630 ,656 Dated December 28 1971 Inventor(s) Gerhard lfrum It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column Line 3 70 change I 5 15 change "2methoxy-2" to 2-methoxy-5- FORM PO-lOSO (10-69) USCOMM-DC 50376-P59 U.S. GOVERNMENT PRINTING OFFICE: I969 O-366-33 UNITED STATES PATENT OFFKCE CER'HFICATE 0F CQRREQ'HQN Patent No. 3 3 I656 Dated December 28 1971 Inventor(s) Gerhard Wolfrum It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column line 5 17 change "naphtyl" to naphthyl 6 Claim first formula, change 1 "A CH N N C B" to A-CH=NNCB 6 45 change "-CH N" to -CH=N- 6 52 change "(3 NH to -c-N1-I- 6 65 change formula to CH=NNCOX (not igig ced) OH H u FORM 0-1050 (10-69) USCOMM-DC 60376-P69 us. GOVERNMENT PRINTING OFFICE: 1969 o36s-az4 Patent No. 3,630 Dated December 28 1971 Gerhard Wolfrum Inventor(s) It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
The following errors were made by applicants. Our check in the amount of $15.00 is enclosed.
Column Line 1 26 change 0 NH to NH 5 10 change CH N N CO X CH N I, 1 CO X I OH H Signed and sealed this 12th day of September 1972.
(SEAL) Attest:
EDWARD MJLETCHERJR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents FORM PC4050 (w'eg) USCOMM-DC 60376-P69 h U.S. GOVERNMENT PRINTING DFFICEZ I959 0-356'33

Claims (1)

  1. 2. Process of claim 1 wherein said compound is of the formula in which X stands for a 2-methoxyphenyl, 2-methoxy-4-methyl-phenyl, 2-methoxy-5-methylphenyl, 2-methoxy-5-tert.-butylphenyl, 2-methoxy-5-chlorophenyl or 2-methoxy-naphthyl radical.
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US4144258A (en) * 1974-12-17 1979-03-13 Ciba-Geigy Corporation 1:1-Heterocyclic azo methine-metal complex dyestuffs
US4612014A (en) * 1982-03-09 1986-09-16 Ciba-Geigy Corporation Use of metal complexes of hydrazones as pigments

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DE1290354B (en) * 1965-12-24 1969-03-06 Sakamoto Yohichika Slide viewer
CH606284A5 (en) * 1974-12-17 1978-10-31 Ciba Geigy Ag
US4529804A (en) * 1982-06-24 1985-07-16 Ciba-Geigy Corporation Naphthostyril Ni or Cu complexes, a process for their preparation, and high molecular weight organic material pigmented with these metal complexes

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US2767173A (en) * 1953-04-22 1956-10-16 Schenley Ind Inc Bactericidal and fungicidal compounds
US3110696A (en) * 1962-02-28 1963-11-12 Geigy Chem Corp Polyolefin compositions stabilized against deterioration and copper wires coated with said compositions
US3399027A (en) * 1962-08-20 1968-08-27 Geigy Ag J R Dyeing nickel chelate modified polyolefin with azomethine dyes
US3547646A (en) * 1966-12-16 1970-12-15 Keuffel & Esser Co Light-sensitive imaging material containing hydrazones

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US2767173A (en) * 1953-04-22 1956-10-16 Schenley Ind Inc Bactericidal and fungicidal compounds
US3110696A (en) * 1962-02-28 1963-11-12 Geigy Chem Corp Polyolefin compositions stabilized against deterioration and copper wires coated with said compositions
US3399027A (en) * 1962-08-20 1968-08-27 Geigy Ag J R Dyeing nickel chelate modified polyolefin with azomethine dyes
US3547646A (en) * 1966-12-16 1970-12-15 Keuffel & Esser Co Light-sensitive imaging material containing hydrazones

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4144258A (en) * 1974-12-17 1979-03-13 Ciba-Geigy Corporation 1:1-Heterocyclic azo methine-metal complex dyestuffs
US4612014A (en) * 1982-03-09 1986-09-16 Ciba-Geigy Corporation Use of metal complexes of hydrazones as pigments

Also Published As

Publication number Publication date
BE740443A (en) 1970-04-01
FR2024793A7 (en) 1970-09-04
NL6914569A (en) 1970-04-21
GB1244398A (en) 1971-09-02
DE1804133A1 (en) 1970-04-30

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