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
  • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
  • D06P5/02—After-treatment
  • D06P5/10—After-treatment with compounds containing metal
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
  • D06P1/642—Compounds containing nitrogen
  • D06P1/6423—Compounds containing azide or oxime groups
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • 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
  • D06P1/673—Inorganic compounds
  • D06P1/67333—Salts or hydroxides
  • D06P1/67341—Salts or hydroxides of elements different from the alkaline or alkaline-earth metals or with anions containing those elements
• • 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
  • D06P3/32—Material containing basic nitrogen containing amide groups leather skins

Definitions

• the present invention relates to a process for improving the light fastness of leather dyed with anionic dyes, which is characterized in that the leather is treated with a compound of nickel, cobalt or copper before, during or after the dyeing.
• connections of nickel, cobalt or copper come e.g. Salts of inorganic or organic acids and compounds which contain the metals mentioned in complexed form. Mixtures of these compounds are also suitable.
• Compounds of copper are preferred, e.g. the following: salts of inorganic acids such as e.g. Copper chloride, sulfate, phosphate or nitrate; Organic acid salts such as e.g. Copper acetate, tartrate or salicylate, mixtures of different copper salts or mixtures of a copper salt and another acid, e.g. Mixtures of copper acetate and salicylic acid can be used.
• salts of inorganic acids such as e.g. Copper chloride, sulfate, phosphate or nitrate
• Organic acid salts such as e.g. Copper acetate, tartrate or salicylate, mixtures of different copper salts or mixtures of a copper salt and another acid, e.g. Mixtures of copper acetate and salicylic acid can be used.
• Copper salts of salicylic acid derivatives or mixtures of the above-mentioned copper salts of inorganic or organic acids with salicylic acid derivatives are also suitable.
• Useful salicylic acid derivatives are, for example 2- H ydroxy-5-sulfobenzoic acid or compounds of formula I
• W 1 and W 2 independently of one another are hydrogen, C 1 -C 4 -alkyl, hydroxy- C 1 -C 4 alkyl or phenyl optionally substituted by sulfo or carboxy.
• complex compounds e.g. optionally copper, cobalt or nickel complexes containing sulfo groups of bisazomethines, acylhydrazones, semicarbazones and thiosemicarbazones of aromatic aldehydes or ketones.
• Bisazomethines of aromatic aldehydes and ketones are understood to mean Schiff bases of aliphatic or aromatic diamines, the aldehydes and ketones having an OH group in the o-position to the formyl or acyl radical.
• the bond with the metal atom takes place via these two OH groups and the two nitrogen atoms in the bisazomethine part. Accordingly, these are tidentate ligands.
• the ligands preferably contain one or more sulfo groups which are located in the aldehyde or ketone part and / or in the bisazomethine bridge.
• the benzene rings A and B can also, independently of one another, be substituted or also have further fused rings. In addition, the benzene rings A and B can also be heterocyclic rings.
• R 1 denotes an optionally substituted alkyl radical
• a C 1 to C 8 alkyl radical in particular a C 1 to C 4 alkyl radical into consideration, which can be branched or unbranched and optionally substituted, specifically by halogen, such as fluorine, chlorine or bromine, C 1 to C 4 alkoxy, such as methoxy or ethoxy, by a phenyl or carboxyl radical, by C 1 to C 4 -alkoxycarbonyl, such as the acetyl radical or by hydroxy or a mono- or dialkylated amino group.
• the cyclohexyl radical can also be used, which can also be substituted, for example by C 1 to C 4 alkyl or C 1 to C 4 alkoxy.
• R 1 is an optionally substituted aryl group, so in particular a phenyl or naphthyl radical is concerned, which may be substituted by C l -C 4 alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl, C 1 -C 4 alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy and tert-butoxy, halogen, such as fluorine, chlorine and bromine, C 2 -C 5 Alkanoylamino such as acetylamino, propionylamino and butyrylamino, nitro, cyano, sulfo or a mono- or dialkylated amino group.
• C l -C 4 alkyl such as methyl, ethyl, propyl, isopropyl, but
• Y is an alkylene radical, it is primarily a C 2 to C 4 alkylene radical, in particular a —CH 2 —CH 2 bridge.
• a C 2 to C 8 alkylene chain which is interrupted by oxygen or, in particular, nitrogen is also suitable, in particular the - (CH 2 ) 3 -NH- (CH 2 ) 3 bridge.
• Y is an arylene radical, it is primarily a phenylene radical, in particular an o-phenylene radical. This can also be substituted by C 1 to C 4 alkyl or C 1 to C 4 alkoxy.
• Possible substituents for the benzene rings A and B are: C to C 4 alkyl, C to C 4 alkoxy, halogen, such as fluorine, chlorine or bromine, and also the cyano or nitro group.
• the copper, cobalt and nickel complexes containing sulfo groups of acylhydrazones of aromatic aldehydes and ketones are primarily complexes of the formula III wherein R 1 has the meaning given above under formula II, Q is oxygen or NH and n is zero or 1, and R 2 is hydrogen or an optionally substituted alkyl or aryl radical.
• R 1 has the meaning given above under formula II
• Q is oxygen or NH and n is zero or 1
• R 2 is hydrogen or an optionally substituted alkyl or aryl radical.
• the symbol Me in turn denotes copper, cobalt or nickel.
• R 2 is an alkyl radical, this can be branched or unbranched and has a chain length of preferably 1 to 8, in particular 1 to 4, carbon atoms.
• Suitable substituents are halogen, such as fluorine, chlorine or bromine, C 1 to C 4 alkoxy, such as methoxy or ethoxy, also phenyl or carboxyl, C 1 to C 4 alkoxycarbonyl, such as acetyl or hydroxy, mono- or dialkylamino .
• R 2 is an optionally substituted aryl radical, a phenyl or naphthyl radical, which can be substituted by C 1-4 alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert .-Butyl, C1-4-alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy and tert-butoxy, halogen, such as fluorine, chlorine and bromine, C 2-S- alkanoylamino, such as Acetylamino, propionylamino and butyrylamino, nitro, cyano, sulfo or a mono- or dialkylated amino group.
• C 1-4 alkyl such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and
• Complexes of the formula III are preferably used in which R 1 is hydrogen and R 2 is hydrogen, methyl or in particular the phenyl radical and which contain copper as metal, especially the complexes in which the sulfo group in turn is in the p-position to the oxygen located.
• Copper, cobalt and nickel complexes of semicarbazones or thiosemicarbazones are primarily understood to mean complexes of the formula IV wherein R 1 has the meaning already given in connection with the formula I and X represents oxygen or sulfur.
• Me denotes copper, cobalt or nickel.
• the ligands of which are derived from sulfosalicylaldehyde or the corresponding phenyl ketones, e.g. also those in which instead of mononuclear, multinuclear aromatic aldehydes and ketones, such as 2-Hydroxy-l-naphthaldehyde sulfonic acids were used to construct the ligand.
• the fourth coordination point of the metal atom in the complexes of the formulas III and IV by e.g. Water is occupied as a neutral ligand.
• Suitable alkyl radicals are those with 1 to 4 carbon atoms.
• Suitable cycloalkyl radicals are cyclohexyl and methylcyclohexyl radicals.
• Suitable substituents in ring A are, for example, methyl, methoxy or chlorine. However, this ring is preferably unsubstituted.
• rings A and B can be substituted by C 1 -C 4 alkyl, cycloalkyl, C 1 -C 4 alkoxy, halogen or OH or other fused rings can have.
• rings A and B can also be heterocyclic rings.
• the complex compounds mentioned which have sulfo groups, are preferably used as the alkali, especially sodium, or amine salt.
• the preferred compounds for the process according to the invention are copper (II) chloride, sulfate, nitrate or acetate and mixtures of these salts with tartaric acid or salicylic acid.
• the metal compounds are expediently applied from an aqueous bath in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on the weight of the leather.
• the treatment with the metal compound can take place before, during or after the coloring.
• an aftertreatment is preferably carried out in a fresh, aqueous liquor containing the metal compound and, if appropriate, acids and / or salts to set a certain pH.
• Treatment takes place, for example, at a pH between 3 and 7 at 20 to 100 ° C for about 10 to 60 minutes.
• the dyeings of the leather can be produced in a conventional manner with the usual anionic leather dyes.
• the anionic dyes are, for example, salts of heavy metal-containing or metal-free mono-, dis- or polyazo dyes including the azomethine and formazan dyes as well as the anthraquinone, xanthene, nitro, triphenylmethane, naphthoquinone imine and phthalocyanine dyes.
• the anionic character of these dyes can be caused by metal complex formation alone and / or by acidic, salt-forming substituents, such as carboxylic acid groups, sulfuric acid and phosphonic acid ester groups, phosphonic acid groups, alkylsulfone, sulfonamido or sulfonic acid groups.
• the 1: 1 or 1: 2 metal complex dyes are preferred.
• the 1: 1 metal complex dyes preferably have one or two sulfonic acid groups. As metal they contain a heavy metal atom such as Copper, nickel, iron or especially chrome.
• the 1: 2 metal complex dyes contain a heavy metal atom such as z . B. an iron, ' cobalt or in particular a chromium atom.
• Two complex-forming components are connected to the central atom, at least one of which is a dye molecule, but preferably both are dye molecules.
• the two dye molecules involved in the complex formation can be the same or different from one another.
• the 1: 2 metal complex dyes can contain, for example, two azomethine molecules, one azo and one azomethine dye or two azo dyes, where these dyes can be substituted with further arylazo and / or arylazoarylenazo groups.
• Aryl here means above all benzene or naphthalene residues, which may be substituted, for example by nitro, sulfo, halogen, alkyl or alkoxy.
• the azo or azomethine dye molecules can have water-solubilizing groups such as, for example, acid amide, alkylsulfonyl or the acid groups mentioned above. Preference is given to 1: 2 cobalt or 1: 2 chromium complexes of monoazo dyes which have acid amide, alkylsulfonyl or sulfonic acid groups.
• the cationic dyes are metal-free or metal-containing dyes.
• dyes can belong to different classes of dyes.
• they are salts, for example chlorides, sulfates, onium chlorides or metal halides, for example zinc chloride salts of azo dyes, such as monoazo dyes or hydrazone dyes, anthraquinone, diphenylmethane, triphenylmethane, methine or azomethine dyes, ketonimine, cyanine, azine, oxazine - or thiazine dyes.
• azo dyes such as monoazo dyes or hydrazone dyes, anthraquinone, diphenylmethane, triphenylmethane, methine or azomethine dyes, ketonimine, cyanine, azine, oxazine - or thiazine dyes.
• Suitable dyes of the formula VII are both symmetrical and asymmetrical 1: 2 azo or 1: 2 azomethine complexes and 1: 2 complexes which contain an azo and an azomethine dye bonded to the metal.
• dyes of the formula VII those in which X is oxygen are preferably used.
• dyes of the formula VII have several groups Y, these can be the same or different. However, preferably all Y S0 represent 3 H groups.
• dyes of the formula VII in which p is 1 and those in which m is 1 to 3, preferably 2, are preferably used.
• radicals A and C can also be further substituted by groups Y, in particular with C 1 -C 4 -alkyl or -alkoxy, chlorine or nitro.
• Suitable diazo components A and C are, for example: anthranilic acid, 4- or 5-sulfoanthranilic acid, 2-amino-l-hydroxybenzene, 4-chloro- and 4,6-dichloro-2-amino-1-hydroxybenzene, 4- or 5-nitro -2-amino-l-hydroxybenzene, 4-chloro and 4-methyl-6-nitro-2-amino-l-hydroxybenzene, 6-chloro-4-nitro-2-amino-l-hydroxybenzene, 4-cyano- 2-amino-1-hydroxybenzene, 4-methoxy-2-amino-1-hydroxybenzene, 4-methoxy-5-chloro-2-amino-l-hydro xybenzene, 4-methyl-2-amino-l-hydroxybenzene, 4-chloro-5-nitro-2-amino-1-hydroxybenzene, 3,4,6-trichloro-2-amino-l-hydroxybenzene, 4,6- Dinitro-2-amino
• a and C preferably each independently represent the radical of a 1-hydroxy-2-aminobenzene, which is optionally substituted one or more times by identical or different substituents from the series nitro, sulfo, chlorine, methyl or methoxy, and in particular the radical a 1-hydroxy-2-aminobenzene which carries a nitro group in the 4- or 5-position or the remainder of an l-hydroxy-2-aminobenzene which carries a nitro group in the 4-position and a sulfo group in the 6-position, or the Residue of a 1-hydroxy-2-aminobenzene, which carries a sulfo group in the 4-position and a nitro group in the 6-position.
• the radicals B and D are preferably derived from the following groups of coupling components: phenols which are substituted in the o-position and which are optionally substituted by low molecular weight alkyl or alkoxy, amino or acylamino, where acylamino is C 1 -C 4 -alkanoylamino-, C 1 -C 4 Alkylsulfonylamino, C 1 -C 4 -alkoxycarbonylamino, aroylamino or arylsulfonylamino residues, Resorcinol, m-phenylenediamine, optionally substituted in the 4-position by sulfo, chlorine, methyl or methoxy, naphthols, which are optionally substituted by C 1 -C 4 -alkyl or alkoxy, chlorine, amino, acylamino or sulfo, where acylamino has the same meaning which is stated above,
• 5-pyrazolones or 5-aminopyrazoles which have a phenyl or naphthyl radical which is optionally substituted by chlorine, nitro, C 1 -C 4 -alkyl or alkoxy groups or sulfo groups in the 1-position and a C 1 -C 4 - in the 3-position
• a phenyl or naphthyl radical which is optionally substituted by chlorine, nitro, C 1 -C 4 -alkyl or alkoxy groups or sulfo groups in the 1-position and a C 1 -C 4 - in the 3-position
• Examples of such coupling components are: 2-naphthol, 1,3- or 1,5-dihydroxynaphthalene, 1-naphthol, 1-acetylamino-7-naphthol, 1-propionylamino-7-naphthol, 1-carbomethoxyamino-7-naphthol, 1- Carboethoxyamino-7-naphthol, 1-carbopropoxyamino-7-naphthol, 6-acetyl-2-naphthol, 2-naphthol-3-, -4-, -5-, -6-, -7- or -8- sulfonic acid, 1-naphthol-3-, -4- or -5-sulfonic acid, 1-naphthol-3,6-disulfonic acid, 1-naphthol-4,8-disulfonic acid, 1-naphthol-3,8-disulfonic acid, 2-
• B or D is preferably a 1- or 2-naphthol, optionally substituted with a sulfo group, m-phenylenediamine, resorcinol, p-alkyl (C1-C4) -phenol, l-phenyl-3-methyl-S-pyrazolone or acetoacetic anilide represents, wherein the phenyl group in the latter two compounds may be substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, chlorine or sulfo.
• B or D represents the residue of an o-hydroxyaldehyde, preferably an o-hydroxybenzaldehyde or o-hydroxynaphthaldehyde.
• Suitable aldehydes are, for example: 2-hydroxy-l-naphthaldehyde, 1-hydroxy-2-naphthaldehyde, 2-hydroxy-benzaldehyde, 3- and 5-methyl-2-hydroxybenzaldehyde, 3,5-dimethyl-2-hydroxybenzaldehyde, 5- Butyl-2-hydroxybenzaldehyde, 5-chloro or 5-bromo-2-hydroxybenzaldehyde, 3-chloro-2-hydroxybenzaldehyde, 3,5-dichloro-2-hydroxybenzaldehyde, 5-sulfo-2-hydroxybenzaldehyde, 3-methyl-5 -chloro-2-hydroxybenzaldehyde, 5- (phenylazo) -2-hydroxybenzaldehyde, 5- (2 '-, 3'- or 4'
• Particularly preferred dyes correspond to formula IX wherein q is an integer from 0 to 2, Me1 cobalt or chromium, Ka ⁇ is a cation and Y is methyl, -CONH 2 or -CO-NHR, where R is an alkyl group with 1 to 4 C atoms,
• the dyeings on leather with the dyes described above are improved in lightfastness, e.g. when evaluating the light fastness according to SNV No. 95.809 by approx. 1 to 2 notes.
• the process according to the invention is particularly suitable for improving the light fastness of leather dyeings which have been obtained with a mixture of a yellow, a red and a blue dye of the type indicated above (i.e. with a trichrome).
• tanning agent A formaldehyde condensation product of phenolic sulfonic acids
• tanning agent B condensation product of a urea derivative with phenolic sulfonic acids
• the leather is then rinsed and then neutralized in a fresh liquor of 200 parts of water, 2 parts of a neutralizing agent based on ammonium salts of aromatic sulfonic acids and aliphatic dicarboxylic acids and 2.5 parts of sodium bicarbonate at 30 ° for a total of 60 minutes.
• the leather is subsequently dyed in a new, with formic acid to p H 4.5 made of 200 parts of water at 50 ° and 3 parts of a mixture of copper and salicylic acid in a molar ratio 1: 2 treated existing after-treatment bath for 30 minutes. It is then finished as usual and a section of the aftertreated dyeing together with a section of a similar but not aftertreated dyeing is exposed in a Xenotest 450 from the quartz lamp company Hanau (FRG) for 200 hours. The light fastness is assessed with the aid of an ISO blue scale, which is also exposed at the same time, with 8 colorations graded in light fastness. It can be seen that the coloring aftertreated with the copper compound has a significantly improved light fastness.
• the resulting brown color is then post-treated with 3 parts of a mixture of copper acetate and salicylic acid as described in Example 1 and then exposed simultaneously to a corresponding non-post-treated color under identical conditions in the Xenotest 450. After completion of the exposure, the two colorings are compared, which shows that the coloration aftertreated with the copper compound has a significantly better lightfastness.
• the retanned furniture leather is dyed in a manner analogous to that in Example 1, but using 0.7 part of the dye of the formula instead of the yellow dye 1: 2 cobalt complex be used.
• the yellow-brown color is then aftertreated with 3 parts of copper tartrate as described in Example 1 and then exposed to determine the light fastness in the Xenotest 450.
• the lightfastness of the aftertreated dye is significantly better than the lightfastness of the nontreated dye.
• a dyeing liquor is prepared from 200 parts of water at 50 °, 1 part of ammonia 24% and 1 part of the neutralizing agent mentioned above.
• the neutralized leather is left to run for 10 minutes in this liquor. Then 0.9 parts of the black dye of the formula
• a fatty compound mixture consisting of 2 parts of sulfited marine oil, 2 parts of sulfited fatty acid esters and animal fatty substances and 2 parts of a formulation based on sulfated hydrocarbons, fatty acids and their derivatives is added.
• 4 parts of white tanning agent condensation product of a urea derivative with phenolic sulfonic acids
• 1.25 parts of 85% formic acid are added.
• the liquor is drained off and replaced by a new one consisting of 0.4 part of the black dye listed above and 200 parts of water at 50 °. It is dyed for another 20 minutes. Then 2 parts of fatliquor based on natural and modified oils and fats as well as n-alkyl derivatives and 1.5 parts of a grip improver consisting of a fatty acid-polyamide condensation product are added. After a further 20 minutes, acidification is carried out with 1 part of formic acid and then dyed another 20 minutes.
• the black leather dyeing is then treated as described in Example 1 in a fresh bath with 3 parts of the mixture of copper acetate and salicylic acid at 50 °. Then the leather is finished as usual and exposed in the Xenotest.
• the lightfastness of the aftertreated dye is significantly better than the lightfastness of a nontreated dye.
• 100 parts of non-intermediate-dried furniture leather are retanned for 90 minutes in a fleet consisting of 200 parts of water at 50 ° and 8 parts of a condensation product of formaldehyde and phenolic sulfonic acids.
• the leather is then washed in 500 parts of water at 30 ° for 15 minutes and then in a liquor composed of 300 parts of water at 30 ° and 1.5 parts of sodium formate, to which 2.5 parts of sodium bicarbonate are also added after 10 minutes, 80 Neutralized for minutes. Following neutralization, there is again a 10-minute washing operation in 500 parts of 40 ° water.
• the leather treated in this way is then dyed in a liquor consisting of 200 parts of water, 2 parts of 24% ammonia and 1.0 part of the yellow dye used in Example 1 for 30 minutes at 40 °. Then a coloring agent mixture consisting of 8 parts of a formulation of sulfited hydrocarbons, fatty acids and their derivatives and 4 parts of sulfited oil and, after a further 90 minutes, 3 parts of 85X formic acid are added to the dye liquor. The dyeing is then continued for 30 minutes at the same temperature.
• the dyed and greased leather is then in a new aftertreatment bath adjusted to pH 5 with formic acid, consisting of 200 parts of water at 50 ° and 1.0 part of the copper compound of the formula Treated for 30 minutes. It is then finished as usual and a section of the post-treated dye is exposed together with a similar but not post-treated dye for 100 hours in a Xenotest 450 exposure apparatus. It can be determined that the coloring aftertreated with the copper compound has a significantly better light fastness.
• the aftertreatment is not carried out in a new bath as described above but immediately after dyeing and greasing in the dye bath itself, a similar improvement in light fastness is obtained.
• the pH of the treatment liquor is approximately 4 and the temperature is 40 °, due to the dyeing process.

Landscapes

• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Inorganic Chemistry (AREA)
• Coloring (AREA)

Applications Claiming Priority (2)

Publications (2)

Family

ID=4292743

Family Applications (1)

Country Status (10)

Cited By (2)

Families Citing this family (2)

Citations (6)

Family Cites Families (14)

• 1985
  • 1985-11-04 EP EP85810512A patent/EP0181836B1/fr not_active Expired
  • 1985-11-04 DE DE8585810512T patent/DE3566915D1/de not_active Expired
  • 1985-11-07 CA CA000494757A patent/CA1281508C/fr not_active Expired - Lifetime
  • 1985-11-08 ES ES549314A patent/ES8802331A1/es not_active Expired
  • 1985-11-08 ZA ZA858604A patent/ZA858604B/xx unknown
  • 1985-11-08 BR BR8505624A patent/BR8505624A/pt not_active IP Right Cessation
  • 1985-11-08 PT PT81460A patent/PT81460B/pt not_active IP Right Cessation
  • 1985-11-09 JP JP60249977A patent/JPS61119785A/ja active Pending
  • 1985-11-11 MX MX000569A patent/MX168486B/es unknown
• 1987
  • 1987-09-17 US US07/097,269 patent/US4818246A/en not_active Expired - Fee Related

Patent Citations (6)

Non-Patent Citations (4)

Also Published As

Similar Documents

Legal Events