GB2024236A - Reactive dyes, their preparation and use - Google Patents
Reactive dyes, their preparation and use Download PDFInfo
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- GB2024236A GB2024236A GB7920991A GB7920991A GB2024236A GB 2024236 A GB2024236 A GB 2024236A GB 7920991 A GB7920991 A GB 7920991A GB 7920991 A GB7920991 A GB 7920991A GB 2024236 A GB2024236 A GB 2024236A
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- 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
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
- C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
- C09B62/08—Azo dyes
- C09B62/095—Metal complex azo dyes
Abstract
The present invention relates to reactive dyes of the formula <IMAGE> in which R4 is C1-4-alkyl, C1-4-alkoxy, C1-4-alkoxyalkoxy, acetylamino, ureido, carboxyl, halogen, sulfo, sulfomethyl, trifluoromethyl, sulfamoyl, carbamoyl, nitro or hydroxyl and R5 is a hydrogen atom or one of the substituents named under R4, and if several substituents R4 are present these can be identical or different, or in which R2 and R3 together with the N atom form a six-membered heterocyclic radical, and the radical or radicals of the formula <IMAGE> in which A is a benzene or naphthalene radical which can contain further substituents, the benzene radical B can contain further substituents, R1 and R2 independently of one another are each a hydrogen atom or a substituted or unsubstituted alkyl radical having 1 to 4 carbon atoms and R3 is a hydrogen atom, a substituted or unsubstituted alkyl radical having 1 to 4 carbon atoms, a substituted or unsubstituted benzyl, cyclohexyl or naphthyl radical, an unsubstituted phenyl radical or a substituted phenyl radical of the formula <IMAGE> is or are bonded to A and/or to the naphthalene nucleus, which carries one of the two complex-forming oxygen atoms.
Description
SPECIFICATION
Reactive dyes, their preparation and use.
The invention relates to reactive dyes of the formula
in which A is a benzene or naphthalene radical which can contain further substituents, the benzene radical B can contain further substituents, R1 and R2 independently of one another are each a hydrogen atom or a substituted or unsubstituted alkyl radical having 1 to 4 carbon atoms and R3 is a hydrogen atom, a substituted or unsubstituted alkyl radical having 1 to 4 carbon atoms, substituted or unsubstituted benzyl, cyclohexyl or naphthyl radical, an unsubstituted phenyl radical or a substituted phenyl radical of the formula
In which R4 is C1 4-alkyl, C1.4-alkoxy, C1.4-alkoxyalkoxy, acetylamino, ureido, carboxyl, halogen, sulfo, sulfomethyl, trifluoromethyl, sulfamoyl, carbamoyl, nitro or hydroxyl and Rg is a hydrogen atom or one of the substituents named under R4, and if several substituents R4 are present these can be identical or different, or in which R2 and R3 together with the N atom form a six-membered heterocyclic radical, and the radical or radicals of the formula
is or are bonded to A and/orto the napthalene nucleus, which carries one of the two complex-forming oxygen atoms.
The radicals A and B can contain the substituents customary in azo dyes. The following are examples of further substituents: alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl and butyl, alkoxy groups having 1 ta 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy and butoxy, acylamino groups having 1 to 6 carbon atoms, such as acetylamino, propionylamino and benzoylamino, amino groups, such as -NH2, methylamino and ethylamino, the ureido hydroxyl and carboxyl group, halogen, such as fluorine, chlorine and bromine, and the sulfonic acid group.
The radical A contains in particular one or more sulfonic acid groups as further substituents. The radical B contains a further substituent in particular in the para-position relative to the complex-forming oxygen atom.
Alkyl radicals R1 and R2 can be substituted, for example by chlorine, hydroxyl, cyano, caboxyl and sulfo.
Examples of R1 and R2 are: methyl, ethyl propyl, isopropyl, butyl, isobutyl, sec.-butyl, tert.-butyl,ss-hydroxyethyl, p-chloroethyl, B-cyanoethyl, B-cyanomethyl,y-cyanopropyl, ss- carboxyetheyl, sulfomethyl and p-sulfoethyl. Examples of R3 are: hydrogen, the same substituted and unsubstituted alkyl radicals as mentioned above for R1 and R2, alkoxyalkyl having 1 to 4 carbon atoms in the alkoxy radical and 1 to 4 carbon atoms in the alkyl radical, such as methoxyethyl, methoxypropyl, ethoxyethyl, ethoxypropyl and methoxybutyl, cyclohexyl, benzyl, 4-sulfobenzyl, 4-methylbenzyl and especially phenyl, which can be substituted by C1.4-alkyl, C14-alkoxy, acetylamino, ureido, carboxyl, halogen, sulfo, sulfomethyl, trifluoromethyl, sulfamoyl and carbamoyl, in which case the conditions given in the explanation of the formula (1 ) apply, or naphthyl, which can be substituted by sulfo; furthermore R2 and Rg can be cyclised to a six-membered N-heterocyclic ring, which can contain a further hetero-atom such as nitrogen, oxygen and sulfur.Examples of the amino radical -NR2R3 in the formula (1 ) are: -N H2, methylamino, ethylamino, propylamino, isopropylamino, butylamino, P-methoxyethylamino, y- methoxypropylamino, N,N-dimethylamino, N,N-diethylamino, N-methyl-N-phenylamino, N-ethyl-N
phenylamino, B-chioroethylamino, (3-hydroxyethylamino, y-hydroxypropylamino, benzylamino, cyclohexy lamino, morpholino, piperidino, piperazino and in particular aromatic amino groups, such as phenylamino, toluidino, xylidino, chloroanilino, anisidino, phenetidino, 3- and 4-sulfoanilino, 2,5-disulfoanilino, sulfomethylanilino, N-sulfomethylanilino, 3- and 4-carboxyphenylamino, 2-carboxy-5-sulfophenylamino, 2 carboxy-4-sulfophenylamino, 4-sulfonaphth-l-yl-amino, 3,6-disulfonaphth-l-yl-amino, 3, 6, 8-trisulfo-naphth- I-yl-amino and 4, 6, 8-trisulfonaphth-l-yl-amino.
The reactive dyes of the formula (1 ) can contain one radical or two radicals of the formula (2). if a reactive dye of the formula (1 ) contains only one radical of the formula (2) this is bonded eitherto A ortho the
naphthalene nucleus which carries one of the two complex forming oxygen atoms; however, if the dye
contains two radicals of the formula (2) one of these radicals is bonded to A and the other is bonded to the abovementioned naphthalene nucleus.
Preferred reactive dyes are those of the formula
in which X is hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms or halogen and
A, R" R2 and R3 are as defined under formula (1), and especially reactive dyes of the formula (3) in which A is a benzene radical, which can be substituted by sulfo, methyl, methoxy, carboxyl and chlorine, or a naphthalene radical, which can be substituted bysulfo, R1 is hydrogen, methyl or P-hydroxyethyl, R2 is hydrogen, methyl or ethyl, R3 is hydrogen, methyl, ethyl, butyl, methoxypropyl, B-hydroxyethyl, P-sulfoethyl, phenyl, which can be substituted by sulfo, methyl, methoxy, ethoxy, acetylamino, ureido, carboxyl, chlorine, bromine, sulfomethyl, trifluoromethyl, sulfamoyl and carbamoyl, in which case the conditions given in the explanation of the formula (1 ) apply, or naphthyl, which can be substituted by sulfo, and Xis hydrogen, methyl, ethyl, methoxy, ethoxy, or chlorine.
Preferred reactive dyes are in particular those oftheformula
in which R1 is hydrogen or methyl, R2 is hydrogen, methyl or ethyl, R3 is hydrogen, phenyl, which can be substituted by sulfo, methyl, ethyl, methoxy, ethoxy, acetylamino, carboxyl, chlorine, sulfamoyl and carbamoyl, in which case the conditions given in the explanation of the formula (1 ) apply, or naphthyl, which can be substituted by sulfo, and X is hydrogen, methyl, ethyl, methoxy, ethoxy or chlorine.
A valuable reactive dye of the category defined by the formula (4) is the reactive dye of the formula
ne preparation of the reactive dyes of the formula (1 ) comprises subjecting a dye of the formula
in which the amino group or groups of the formula
is or are bonded to A and/or to the naphthalene nucleus which carries one of the two complex-forming oxygen atoms, 1 or 2 mols of 2, 4, 6-trifluoro-s-triazine of the formula
and or 1 ar 2 mols of an amino compound of the formula
to condensation reactions with one another, the said reactions being carried out in any order.
In a preferred embodiment the starting materials used are dves of the formula
in which Xis hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms or halogen and
A and R1 are as defined under formula (1).
The starting materials used are in particular dyes of the formula (10) in which A is a benzene radical, which can be substituted by sulfo, methyl, methoxy, carboxyl and chlorine, or a naphthalene radical, which can be substituted by sulfo, R1 is hydrogen, methyl or ss-hydroxyethyl and X is hydrogen, methyl, ethyl, methoxy, ethoxy, or chlorine, and amino compounds of the formula (9) in which R2 is hydrogen, methyl or ethyl and R3 is hydrogen, methyl, ethyl, butyl, methoxypropyl, P-hydroxyethyl, p-sulfoethyl, phenyl, which can be substituted by sulfo, methyl, methoxy, ethoxy, acetylamino, ureido, carboxyl, chlorine, bromine, sulfomethyl, trifluoromethyl, sulfamoyl and carbamoyl, in which case the conditions given in the explanation of the formula (1) apply, or napthyl, which can be substituted by sulfo.
The preferred reactive dyes of the formula (4) are obtained by subjecting a dye of the formula
2, 4, 6-trifluoro-s-triazine of the formula (8) and an amino compound of the formula (9) to condensation reactions with one another, the said reactions being carried out in any order and R1, R2, R3 and X in the formulae (11) and (9) being as defined under formula (4).
Since the individual process steps indicated above, i.e. multiple condensation reactions in different orders, can, if desired, in some cases also be carried out simultaneously, different process variants are possible. The starting materials to be used for each partial reaction can be seen from formula (1). In general, the reaction is carried out in successive steps, and the order of the simple reactions between the individual reactants of the formulae (6), (8) and (9) can be freely chosen.
The two most important process variants comprise
1. subjecting a dye of the formula (6) to a condensation reaction with 1 or 2 mols of 2,4, 6-trifluoro-s-triazine of the formula (8) and subjecting the resulting mono- or di-primary condensation product to a condensation reaction with 1 or 2 mols of an amino compound of the formula (9); and
2. subjecting 2, 4, 6-trifluoro-s-triazine of the formula (8) to a condensation reaction with an amino compound of the formula (9) and subjecting 1 or 2 mols of the resulting primary condensation product to a condensation reaction with a dye of the formula (6).
The preferred procedure for the preparation of the dye of the formula (5) comprises subjecting the dye of the formula
to a condensation rection with 2, 4, 6-trifluoro-s-triazine and subjecting the resulting primary condensation product to a condensation reaction with ammonia.
The dyes of the formula (6) which are to be used as starting materials are obtained by coupling a diazotised aminobenzene or aminonaphthalenef which can be further substituted as indicated above, with an ortho-alkoxy- or -hydroxy-aminobenzene, which likewise can be further substituted as indicated above, such as o-anisidine, cresidine, 2, 5-dimethoxyaniline, or 2-acetylaminophenol, diazotising the resulting monaozo compound, if necessary after saponifying the amino group to be diazotised, and coupling the resulting product with a naphtholsulfonic acid or aminonaphtholsulfonic acid and preparing the copper complex of the resulting disazo dye, especially with dealkylation, by reaction with copper donors.
The diazotisation of the diazo components is as a rule effected by the action of nitrous acid in aqueous/mineral acid solution at low temperature and the coupling reaction with the coupling components is carried out at weakly acid or neutral to weakly alkaline pH values.
Salts which contain copper as the cation, for example copper sulfate, copper chloride or copper acetate, can be used as the copper donor. In some cases it is advantageous to use complex copper compounds, for example in the form of copper/ammine complexes, such as copper tetraammine sulfates obtained from copper sulfate and ammonia, pyridine or monoethanolamine, or in the form of compounds which contain the copper bonded as a complex, for example complex copper compounds of the alkali metal salts of aliphatic aminocarboxylic acids or hydroxy-carboxylic acids, such as of glycocoll, of lactic acid and, in particular, of tartaric acid, such as sodium coppertartrate.
The treatment with the copper donor is carried out in an aqueous or organic-aqueous medium, for example at room temperature if the starting compounds are easily metallisable or, if dealkylation has to take place at the same time as metallisation, by warming to temperatures between 50 and 1 20"C in an open vessel, for example under reflux, or, if necessary, in a closed vessel under pressure, the pH conditions being determined by the nature of the metallisation process chosen; for example, the copper complex is prepared at an acid pH using copper sulfate and at an alkaline pH using copper tetraammine sulfate.
If desired, solvents, such as, for example, alcohol, dimethylformamide and the like, can also be added during the metallisation.
Examples of starting compounds for the preparation of the dyes of the formula (6) are:
a) aminobenzenes and aminonaphthalenes (radical A):aniline, o-,m- and p-toluidines, o-,m- and p-anisidines, o-,m- and p-chloroanilines, 2, 5-dichloroaniline, Ct- and B-napthylzmine, 2,5-dimethylaniline, 5-nitro-2-amino-anisole, 4-aminodiphenyl, aniline-2-, -3- and -4-carboxylic acids, 2-aminodiphenyl ether, 2-, 3-or 4-aminobenzene-sulfonamide or -sulfomono-methyl- or -ethyl-amides or-sulfonyldimethyl- or -sulfony
Idiethyl-amides, aniline-2-, -3- and -4-sulfonic acid, aniline-2,5-disulfonic acid, 2,4-dimethylaniline-6-sulfonic acid, 4-chloro-5-methyl-aniline-2-sulfonic acid, aniline-2,4-disulfonic acid, aniline-3,5-disulfonic acid, 1amino-4- or -5- sulfobenzoic acid, 2-methylaniline-3, 5, disulfonic acid, 2-methylaniline-5-sulfonic acid, 2-methoxyaniline-3,5-disulfonic acid, 2-chloroaniline-4-sulfonic acid, 2, 3-dimethylaniline-4,6-disulfonic acid, 2,5-dimethylaniline-4,6-disulfonic acid, 5-chloro-4-methylaniline-2-sulfonic acid, 3-acetylamino,aniiine-6- sulfonic acid, 4-acetylaminoaniline-2-sulfonic acid, 4-chloroaniline-2-sulfonic acid, 3-4-dichloroaniline-6sulfonic acid, 4-methylaniline-2-sulfonic acid, 3-methylaniline-6-sulfonic acid, 2,4-dimethoxyaniline-6sulfonic acid, 4-methoxyaniline-2-sulfonic acid, 5-methoxyaniline-2-sulfonic acid, 2,5-dichloroaniline-4sulfonic acid, 2, 4-dimethylaniline-5-sulfonic acid, 2-methoxyaniline-5-sulfonic acid, 2-methylaniline-4sulfonic acid, 4-nitroaniline-2-sulfonic acid, 4-ethoxyaniline-2-sulfonic acid, 4-ethylaniline-2-sulfonic acid, 4-acetylaminoaniline, 4-ethoxyaniline-3-sulfonic acid, 3,4-dichloroaniline, o-,m- and p-nitroaniline, m- and p-aminoacetanilide, 4-amino-2-acetyl-aminotoluene-5-sulfonic acid, 4-methoxyaniline-3-sulfonic acid, Iaminonaphthalene-2-, -4-, -5-, -6-, -7- or -8 sulfonic acid, 2-aminonaphthalene-1 -, -5- or -6- sulfonic acid, 1-aminonaphthalene-3,6- or -5,7-disulfonic acid, 2-aminonaphthalene-1, 5-, -1,7-, -3,6-,-5,7-, -4,8- or -6,8-disulfonic acid, 1-aminonaphthalene-2,5,7-trisulfonic acid, 2-aminonaphthalene-1 ,5,7-, -3,6,8- or--4,6,8trisulfonic acid, 1-amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid, 2-amino-I ,hydroxynaphthalene-4,8- disulfonic acid, 1-amino-3-acetylaminobenzene (saponified), l-amino-3,acetylaminobenzene-5- or -6 sulfonic acid (saponified), 1-amino-4-acetylaminobenzene-2-sulfonic acid (saponified), 1-amino-3-(N-acetyl- N-methylamino)- benzene (saponified), 3-or 4-nitroaniline (reduced), 2-methyl-4- or -5-nitroaniline (reduced), 2-methoxy-3- nitro-5-methylaniline (reduced) and 2-methoxy-3-nitro-5-chloroaniline.
b) o-Alkoxy- or o-hydroxy-aminobenzenes (radical B0:1 -amino-2-methoxy-5-methylbenzene, 1-amino-2, 5-dimethoxybenzene, 1-amino-2-methoxybenzene, 1-amino-2-methoxy-5-chlorobenzene, 1 -amino-2- methoxy-5-ethyl benzene, 1 -amino-2,5-diethoxybenzene, 1 -amino-2-ethoxybenzene and 2acetylaminophenol (saponified).
c) Naphtholsulfonic acids and aminonaphtholsulfonic acids :2-amino-8-hydroxynaphthalene-6-sulfonic acid, 2-amino-6-hydroxynaphthalene-8-sulfonic acid, 2-amino-5-hydroxynaphthalene-7-sulfonic acid, 2 amino-S-hydroxynaphthalene-1 7-disulfonic acid, 2-aminobenzoylamino-5-hydroxynaphthalene-7-sulfonic acid, 1-(4'-aminophenylamino)-5-hydroxynaphthalene-3',7-disulfonic acid, 2-amino-8-hydroxynaphthalene3,6-disulfonic acid, 1 -aminobenzoyl-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 2-amino-S- hydroxynaphthalene-4,8-disulfonic acid, 1 -amino-8-hydrnxy-naphthalene-3,6- or -4,6-disulfonic acid, 2-N phenylamino-5-hydroxynaphthalene-7-sulfonic acid, 2-N-acetyl-N-methyl-amino-5-hydroxynaphthalene-7sulfonic acid, 2-N(2'-hydroxyethylamino)-5-hydroxynaphthalene-7-sulfonic acid,2-N-methylamino-8hydroxynaphthalene-6-sulfonic acid, 3-amino-2-hydroxynaphthalene-7-sulfonic acid, 1hydroxynaphthalene-3,6-disulfonic acid, 1-hydroxynaphthalene-4,8-disulfonic acid, 1 -hydroxynaphthalene 3,8-disulfonic acid, 1-hydroxynaphthalene-3, 6, 6, 8-trisulfonic acid and 1 -hydroxynaphthalene-4-, -5- or -8- sulfonic acid.
The preparation of the dyes of the formula (6) is not described in every case in the illustrative examples given below, but is obvious from what has been stated above.
Further starting materials which can be used for the preparation of the reactive dyes of the formula (1 ) are 2, 4, 6-trifluoro-s-triazine of the formula (8) (cyanuric fluoride) and also, for example, the following amino compounds of the formula (9)- ammonia, methylamine, dimethylamine, ethylamine, diethylamine, propylamine, isopropylamine, butylamine, dibutylamine, isobutylamine, sec.-butyl-amine, tert.-butylamine, methoxyethylamine, ethoxyethylamine, methoxypropylamine, chloroethylamine, hydroxyethylamine, dihdroxyethylamine, hydroxypropylamine, aminoethanesulfonic acid, B-sulfatoethylamine, benzylamine, cyclohexylamine, aniline, m- and p-toluidine, 2,3-, 2,4- 2,5-, 2,6-, 3,4- and 3, 5-dimethylaniline, m- and p-chloroaniline, N-methylaniline, N-ethylaniline, 3-or 4-acetylaminoaniline, m- and p-nitroaniline, m- and p-aminophenol, 2-methyl-4-nitroaniline, 2-methyl-5-nitroaniline, 2,5- dimethoxyaniline, 3-methyl-4nitroaniline, 2-nitro-4-methylaniline, 3-nitro-4-methylaniline, 3-amino-4-methyl-aniline, 4-amino-3methylaniline, 2-amino-4-methylaniline, m- and p-anisidine, m- and p-phenetidine, 2-methoxy-5methylaniline, 2-ethoxy-5-methoxyaniline, 4-bromoaniline, 3-aminobenzamide, 4-aminophenysulfamide, 3-trifluoro methylaniline, 3- and 4- aminophenylurea, 1-naphthylamine, 2-naphthylamine, 2-amino-2hydroxynaphthalene, 1-amino-4-hydroxynaphthalene, 1-amino-8-hydroxynaphthalene, 1-amino-2hydroxynaphthalene, 1-amino-7-hydroxynaphthalene, methanilic acid, sulfanilic acid, aniline-2,4-disulfonic acid, aniline-2,5-disulfonic acid, aniline-3,5-disulfonic acid, m- and p-aminobenzoic acid, 4aminophenylmethanesulfonic acid, aniline -N-methanesulfonic acid, 2-amino-toluene-4-sulfonic acid, 2-aminotoluene-5-sulfonic acid,-p-aminosalicylic acid, 1-amino-4-carboxy-benzene-3-sulfonic acid, 1-amino 2-corboxy-benzene-5-sulfonic acid, 1 -amino-5-carboxy-benzene-2-sulfonic acid,1 -naphthylamine-2-, -3-, -4-, -5-,6-, -7- and 8-sulfonic acid, 2-naphthylamine-1-, -3-, -4-, -5-, -6-, -7-, and -8- sulfonic acid, 1-naphthylamine- 1,4-, -2,5-, -2,7-, -2,8-, -3,5-, -3,6-, -3,7-, -3,8-, -4,6-, -4,7-, -4,8-and -5,8-disulfonic acid, 2-naphthylamine-1,5-, -1,6-, -1,7-, -3,6-, -3,7-, -4,7-, -4,8-, -5,7-and -6,8-disulfonic acid, 1 ,-naphthylamine-2,4,6-, -2,4,7, -2,5k7-, -3,5,7-, -3,6,8- and -4,6,8- trisulfonic acid, 2-naphthylamine-1 ,3,7-, -1,5,7-, -3,5,u-, -3,6,7-, -3,6,8- and -4,6,8- trisulfonic acid, morpholine, piperidine and piperazine.
The condensation reactions of the 1 ,4,6-trifluoro-s-triazine of the formula (8) with the dyes of the formula (6) and the amino compounds of the formula (9) are preferably carried out in aqueous solution orsuspension, at low temperature and at a weakly acid or neutral to weakly alkaline pH value and in such a way that at least one fluorine atom still remains as a detachable radical in the finished reactive dye of the formula (1).
Advantageously, the hydrogen fluoride liberated during the condensation reaction is neutralised continuously by adding aqueous alkali metal hydroxides, carbonates or bicarbonates.
The copper complex dyes of the formula (1 ) are fibre-reactive since they contain a detachable fluorine atom in s-triazine radical or in each of the two s-triazine radicals.
Fibre-reactive compounds are to be understood as meaning those which are able to react with the hydroxyl groups of cellulose or with the amino groups of natural or synthetic polyamides with the formation of covalent chemical bonds.
The reactive dyes of the formula (1) can be isolated and processed to usable, dry dye preparations.
Isolation is preferably effected at temperatures which are as low as possible, by salting out and filtering. The dyes filtered off can be dried, if desired after adding extenders and/or buffers, for example after adding a mixture of equal parts of monosodium phosphate and disodium phosphate; preferably, drying is carried out at temperatures which are not too high and under reduced pressure. In certain cases the dry preparations according to the invention can be prepared direct, i.e. without intermediate isolation of the dyes, by spray-drying the entire preparation mixture.
The reactive dyes of the formula (1 ) are novel. They are distinguished by high reactivity and yield dyeings which have good wet fastness properties and good fastness to light. It should be pointed out in particular that the dyes have good solubility and electrolyte solubility coupled with good exhaustion characteristics and high dye fixation and that the non-fixed portions can be removed easily.
The reactive dyes of the formula (1 ) are suitable for dyeing and printing very diverse materials, such as silk, leather, wool, high molecularweight polyamidefibres and high molecularweight polyamide/urethanes, but especially cellulose-containing materials having a fibrous structure, such as linen, cellulose, regenerated cellulose and in particular cotton. they are suitable both for the exhaustion process and for dyeing by the pad dyeing method, according to which the goods are impregnated with aqueous dye solutions, which if desired can also contain salts, and the dyes are fixed after an alkali treatment or in the presence of alkali, if necessary under the action of heat.
They are also suitable for printing, especially on cotton, but likewise also for printing nitrogen-containing fibres, for example wool, silk or mixed fabrics containing wool.
It is advisable to subject the dyeings and prints to thorough rinsing with cold and hot water, if necessary with the addition of an agent which acts as a dispersant and promotes the diffusion of the non-fixed portions.
In the following examples, parts are by weight and temperatures are in degrees centigrade.
Example 1
10 parts of the dye of the formula
are dissolved in 70 parts of water at pH 7 and the solution is cooled to O" by adding 40 parts of ice.
2 parts of 2,4, 6-trifluorotriazine are added dropwise, with good stirring, a pH value of 6.5 being maintained by adding sodium carbonate solution atthe same time.
3 parts by volume of concentrates aqueoua ammonia solution are then added and the mixture is stirred for 2 hours at 5 to 10 . The resulting reactive dye is precipitated by sprinkling in sodium chloride and filtered off, the dye paste is mixed with an aqueous solution of disodium phosphate and the mixture is dried.
The resulting dye dyes cotton from a long liquor in intense navy blue shades.
Navy blue dyes with similar characteristics are obtained when the amines listed in the table below are used in place of amonia.
Example Amines
2 N-methylamine
3 N-methylaniline
4 3,5-dimethylaniline
5 4-methoxyaniline
6 3-aminobenzenesulfonic acid
7 4-aminobenzoic acid
8 4-methylaniline
9 3-methylaniline
10 4-aminobenzenesulfonic acid
11 2-amino-4-methylmethoxybenzene
12 3-trifluoromethylaniline
13 4-aminobenzylsulfonic acid
14 butylamine
15 2-aminoethanesulfonic acid
16 2-aminoethanol
17 aniline
18 3-aminoacetanilide
19 4-aminophenylurea
20 2-aminonaphthalene-6-sulfonic acid
21 2-aminonaphthalene-4,8-disulfonic acid
Example 22
25.3 parts of aniline-2,4-disulfonic acid are diazotised in a conventional manner and the resulting product is coupled in weakly acid solution with 13.7 padrts of 3-amino-4-methoxytoluene. The resulting aminoazo dye is precipitated by adding sodium chloride, filtered off and dissolved in water again.It is diazotised by adding hydrochloric acid and sodium nitrite and the resulting product is coupled at a pH value of 8 to 8.5 with 29.5 parts of N-acetyl-N-methyl-2-amino-5-hydroxynaphthalene-7-sulfonic acid. 100 parts by volume of concentrated aqueous ammonia solution and 140 parts by volume of 1 N copper sulfate solution are now added to the resulting deep violet solution and the mixture is stirred under reflux at 95 for 12 hours. The copper complex is precipitated from the deep blue solution by adding sodium chloride and is filtered off with suction. In order to saponify the acetyl group, the dye is warmed in 1 N sodium hydroxide solution for 2 hours at 85 ; after cooling to 25 , the mixture is acidified to pH 3 with hydrochloric acid and the product is filtered off with suction.
35.5 parts of the copper complex dye are dissolved in 250 parts of water to give a neutral solution and the solution is cooled to 0 . 150 parts of ice are added and 7.1 parts of 2,4,64rifluoro-1 3,5-triazine are added dropwise to the solution at a pH of 6 to 7. After the condensation reaction has gone to completion, a solution of 5.4 parts of 4-aminotoluene in acetone is added and the condensation reaction is carried out at 5 to 100 and pH 7.5. the dye is isolated as a blue-black powder by evaporating the reaction mixture to dryness. It dyes cotton in fast navy blue shades.
Copper complexes of aminodisazo dyes are obtained analogously from the components A = starting component, B = middle component and N =final component, by two coupling reactions and preparation of the copper complex with demethylation, and, on a condensation reaction with cyanuric fluoride and a second triazine substituent T, these copper complexes yield further fast dyes.
No. A = Starting component B = Middle component N = Final component T = Triazine Colour substituent shade on cotton 23 Aniline-2,4-disulfonic 3-Amino-4-methoxytoluene 2-N-Methylamino-5-hydroxy- Ammonia navy blue acid naphthalene-7-sulfonic acid 24 " " 2-N-(2'-Hydroxyethylamino)- Aniline " 5-hydroxynaphthalene-7sulfonic acid 25 Aniline-2,5-disulfonic " 2-Amino-5-hydroxynaphtha- 3-Aminotoluene " acid lene-1,7-disulfonic acid 26 " 2-Amino-1,4-dimethoxy " 4-Aminobenzoic acid " benzene 27 " 2-Aminoanisole 2-Amino-5-hydroxynaphtha- n-Butylamine " lene-7-sulfonic acid 28 " 3-Amino-4-methoxytoluene 2-Amino-8-hydroxynaphtha- 2-Aminoethanol " lene-6-sulfonic acid 29 " " 2-Methylamino-8-hydroxy- 2-Amino-1,4-dimethyl- " naphthalene-6-sulfonic acid benzene 30 Aniline-3-sulfonic acid " 2-N-Methylamino-5-hydroxy- Aniline-3-sulfonic acid " naphthalene-7-sulfonic acid 31 Aniline-4-sulfonic acid " " Aniline-3,5-disulfonic " acid 32 Aniline-3,5-disulfonic " " 4-Aminoanisole " acid 33 2-Amino-5-sulfobenzoic " " 4-Chloroaniline " acid 34 2-Amino-4-sulfobenzoic " " 4-Aminoacetanilide " acid 35 5-Amino-4-methylbenzene- " 2-Amino-8-hydroxynaphtha- 3-Aminophenylurea " 1,3-disulfonic acid lene-3,6-disulfonic acid 36 2-Aminonaphthalene-1,5- " 2-Amino-8-hydroxynaphtha- 3-Aminobenzamide blue-black disulfonic acid lene-6-sulfonic acid 37 1-Aminonaphthalene- " 2-Amino-5-hydroxynaphtha- 4-Aminophenyl " 2,5,7-trisulfonic acid lene-7-sulfonic acid sulfamide 38 2-Aminotoluene-4- 3-Amino-4-methoxy- 2-Amino-hydroxynaphtha- 3-Methoxypropylamine navy blue sulfonic acid chlorobenzene. lene-1,7-disulfonic acid
No. A B N T Colour shade on cotton 39 2-Amino-5-methylbenzene- 3-Amino-4-methoxytoluene 2-Amino-5-hydroxynaphtha- Ethylamine dark blue sulfonic acid lene-4,8-disulfonic acid 40 5-Amino-4-methoxyben- 3-Amino-4-methoxyethyl- 3-Amino-2-hydroxynaphtha- N-Methylaniline blue zene,1,3-disulfonic acid benzene lene-7-sulfonic acid 41 4-Amino-3-chlorobenzene- 2-Acetylaminophenol 8-Amino-1-hydroxynaphtha- 4-Bromoaniline blue sulfonic acid (saponified) lene-3,6-disulfonic acid 42 4-Amino-3-methylbenzene- 3-Amino-4-methoxytoluene 8-Amino-1-hydroxynaphtha- Diethylamine blue sulfonic acid lene-3,5-disulfonic acid 43 2-Aminobenzene- " 2-N-Metylamino-5- 4-Aminophenyl- navy blue sulfonic acid hydroxynaphthalene-7- methanesulfonic acid 44 4-Aminobenzene- " " 1-Amino-3,4-dimethyl- " sulfonic acid benzene 45 " " " 1-Amino-4-methoxy- " ethoxybenzene 46 2-Aminobenzene-1,4- " " 4-Aminoethoxybenzene " disulfonic acid 47 " 2-Aminoanisole " 4-Methylaniline " 48 " 2-Amino-1,4-dimethoxy- " Ammonia " benzene 49 " 2-Amino-1,4-diethoxy- " 3-Aminotoluene " benzene
Example 50
14 parts of the copper complex disazo dye of the formula
(in the form of the trisodium salt) are dissolved in 100 parts of water and the solution is cooled to 0 by adding ice. 1.4 parts of disodium hydrogen phosphate are added and 2.75 parts of 2,4,6-tri-fluoro-1,3,5-triazine are now added dropwise, with good stirring, the pH value of the reaction solution being kept at 6.5 by adding sodium hydroxide solution at the same time. After the reaction, which is followed by thin layer chromatography, has gone to completion, 2.2 parts of 3-aminotoluene are added and the mixture is allowed to warm to 20 , the hydrogen fluoride liberated during the condensation reaction again being neutralised continuously. A dark dye powder is obtained by concentrating the resulting dye solution in vacuo.The dye dyes materials made of cellulose fibres in fast blue shades.
Example 51
10 parts of the coppercomples disazo dye of the formula
are dissolved in 100 parts of water at pH 7. A solution of 3.3 parts of the 2-(4'-methylphenylamino)-4,6difluoro-1 ,3,5-triazine in 15 parts of acetone is added and the mixture is stirred for 8 hours at 15 , the pH value being kept at 6.5 to 7 by the dropwise addition of 1 N sodium hydroxide. After the indicated reaction time, no further starting material is detectable by chromatography. The dye is precipitated by sprinkling sodium chloride into the solution and is filtered off and dried. It is identical to the product obtained according to.
Example 8.
Example 52
14 parts of 2A,6-trifluoro-1 ,3,5-triazine are added dropwise, at 0 , to a solution of 34.6 parts of the disodium salt of the dye of the formula
in 600 parts of water, with good stirring, the pH value being kept at 6 by adding sodium bicarbonate solution.
After the reaction has gone to completion, 19 parts of 3-aminobenzenesulfonic acid are added and the mixture is stirred for 3 hours at pH 7.5 and a temperature of 25o. The resulting dye of the formula
dyes cotton in fast dark blue shades.
Dyeing Instructions I
2 parts of the dye obtained according to Example 1 are dissolved in 100 parts of water with the addition of 0.5 part of sodium m-nitrobenzenesulfonate. A cotton fabric is impregnated with the resulting solution so that its liquor pick-up is 75% and then dried.
The fabric is then impregnated with a solution which is at 20 and contains, per litre, 5 grams of sodium hydroxide and 300 grams of sodium chloride and squeezed off to a liquor pick-up of 75% and the dying is steamed for 30 seconds at 100 to 101 , rinsed, soaped for a quarter of an hour in a 0.3% boiling solution of a non-ionic detergent, rinsed and dried.
Dyeing Instructions II
2 parts of the dye obtainable according to Example 1 are dissolved in 100 parts of water.
The solution is added to 1,900 parts of cold water, 60 parts of sodium chloride are added and 100 parts of a cotton fabric are put into this dyebath.
The temperature is raised to 40 and after 30 minutes 4 parts by volume' of 30% sodium hydroxide solution, 10 parts of calcined sodium carbonate and a further 60 parts of sodium chloride are added. The temperature is kept at 40 for 30 minutes and the dyeing is then rinsed and soaped for 15 minutes in a 0.3% boiling solution of a non-ionic detergent, rinsed and dried.
Claims (1)
1. A reactive dye of the formula
in which A is a benzene or napthalene radical which can contain further substituents, the benzene radical B can contain further substituents, R1 and R2 independently of one another are each a hydrogen atom or a substituted or unsubstituted alkyl radical having 1 to 4 carbon atoms and R3 is a hydrogen atom, a substituted or unsubstituted alkyl radical having 1 to 4 carbon atoms, a substituted or unsubstituted benzyl, cyclohexyl or naphthyl radical, an unsubstituted phenyl radical or a substituted phenyl radical of the formula
in which R4 is C1.4-alkyl, C1.4-alkoxy, C1.4-alkoxyalkoxy, acetylamino, ureido, carboxyl, halogen, sulfo, sulfomethyl, trifluoromethyl, sulfamoyl, carbamoyl, nitro or hydroxyl and Rg is a hydrogen atom or one of the substitutents named under R4, and if several substituents R4 are present these can be identical or different or in which R2 and R3 together with the N atom form a six-membered heterocyclic radical, and the radical or radicals of the formula
is or are bonded to A and/or to the naphthalene nucleus, which carries one of the two cpmplex-forming oxygen atoms.
2. A reactive dye according to claim 1, of the formula
in which X is hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms or halogen and
A, R1, R2 and R3 are as defined in claim 1.
3. A reactive dye according to claim 2, in which A is a benzene radical, which can be substituted by sulfo, methyl, methoxy, carboxyl and chlorine, or a naphthalene radical, which can be substituted by sulfo, R1 is hydrogen, methyl or p-hydroxyethyl, R2 is hydrogen, methyl or ethyl, R3 is hydrogen, methyl, ethyl, butyl, methoxypropyl, 13-sulfoethyl, phenyl, which can be substituted by sulfo, methyl, methoxy, ethoxy, acetylamino, ureido, carboxyl, chlorine, bromine, sulfomethyl, trifluoromethyl, sulfamoyl and carbamoyl, in which case the conditions given in claim 1 apply, or naphthyl, which can be substituted by sulfo, and Xis hydrogen, methyl, ethyl, methoxy, ethoxy or chlorine.
4. A reactive dye according to claim 2, of the formula
in which R1 is hydrogen or methyl, R2 is hydrogen, methyl or ethyl, R3 is hydrogen, phenyl, which can be substituted by sulfo, methyl, ethyl, methoxy, ethoxy, acetylamino, carboxyl, chlorine, sulfamoyl and carbamoyl, in which case the conditions given in claim 1 apply, or naphthyl, which can be substituted by sulfo, and X is hydrogen, methyl, ethyl, methoxy, ethoxy or chlorine.
5. The reactive dye according to claim 4, of the formula
S03H acu o (4N=N4NN N so3 > =J jazzH + S03H CH3 H035 CH Nffi ,N (5) CH3 6. A process for the preparation of a reactive dye of the formula F
in which A is a benzene or naphthalene radical which can contain further substituents, the benzene radical B can contain further substituents, R1 and R2 independently of one another are each a hydrogen atom or a substituted or unsubstituted alkyl radical having 1 to 4 carbon atoms R3 is a hydrogen atom, a substituted or unsubstituted alkyl radical having 1 to 4 carbon atoms, a substituted or unsubstituted benzyl, cyclohexyl or naphthyl radical, an unsubstituted phenyl radical or a substituted phenyl radical ofthe formula
in which R4 is C1.4-alkyl, C1.4-alkoxy, C1.4-alkoxyalkoxy, acetylamino, ureido, carboxyl, halogen, sulfo, sulfomethyl, trifluoromethyl, sulfamoyl, carbamoyl, nitro or hydroxyl and R5 is a hydrogen atom or one of the substituents named under R4, and if several substituents R4 are present these can be identical or different, or in which R2 and R3 together with the N atom form a six-membered heterocyclic radical, and the radical or radicals of the formula
is or are bonded to A and/or to the naphthalene radical, which carries one of the two complex-forming oxygen atoms, which comprises subjecting a dye of theformula
in which the amino group or groups of the formula
is or are bonded to A and/or to the naphthalene nucleus which carries one of the two complex-forming oxygen atoms, 1 or 2 mols of 2,4,6-trifluoro-s-triazine of the formula
and 1 or 2 mols of an amino compound of the formula
to condensation reactions with one another, the said rections being carried out in any order.
7. A process according to claim 6, wherein the starting material used is a dye of the formula
in which X is hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms or halogen and
Aand R1 are as defined in claim 6.
8 A process according to claim 7, wherein the starting materials used are a dye of the formula (10) in which A is a benzene radical, which can be substituted by sulfo, methyl, methoxy, carboxyl and chlorine, or a naphthalene radical, which can be substituted by sulfo, R1 is hydrogen, methyl or ss-hydroxyethyi and Xis hydrogen, methyl, ethyl, methoxy, ethoxy or chlorine, and an amino compound of the formula (9) in which R2 is hydrogen, methyl or ethyl and R3 is hydrogen, methyl, ethyl, butyl, methoxpropyl, p-hydrnxyethyl, (3-sulfoethyl, phenyl, which can be substituted by sulfo, methyl, methoxy, ethoxy, acetylamino, ureido, carboxyl, chlorine, bromine, sulfomethyl, trifluoromethyl, sulfamoyl and carbamoyl, in which case the conditions given in claim 6 apply, or naphthyl, which can be substituted by sulfo.
9. A process according to Claim 7, for the preparation of a reactive dye of the formula
in which R1 is hydrogen or methyl, R2 is hydrogen, methyl ar ethyl, R3 is hydrogen, phenyl, which can be substituted by sulfa, methyl, ethyl, methoxy, ethoxy, acetylamino, carboxyl, chlorine, sulfamoyl and carbamoyl, in which case the conditions given in claim 6 apply, or naphthyl, which can be substituted by sulfo, and X is hydrogen, methyl, ethyl, methoxy, ethoxy ar chlorine, which comprises subjecting a dye of the formula
2,4,6-trifluoro-s-triazine of the formula (8) and an amino compound of the formula (9), in which R2 and R3 are as defined above, to condensation reactions with one another, the said reactions being carried out in any order.
16. A process according to claim 9, for the preparation of the reactive dye of the formula
which comprises subjecting the dye of the formula
to a condenSation reaction with 2,4,6-tribluoro-s-triazine and subjecting the resulting primary condensation product to a condensation reaction with ammonia.
11. The reactive dyes obtained according to the examples.
12. Processes according to the examples given.
13. The reactive dyes obtainable according to claims 6 to 10.
14. Processes according to the dyeing and printing examples.
15. The use of a reactive dye according to claims 1 to 5 or of a reactive dye obtained according to claims 6 to 10, for dyeing or printing.
16. A process for dyeing or printing using a reactive dye according to claim 1.
17. A process according to claim 16, for dying cellulose fibres.
18. A dyeing or printing preparation which contains a reactive dye according to claims 1 to 5.
19. The material, especially textile material, dyed or printed according to claim 16 or 17.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH658078A CH635860A5 (en) | 1978-06-16 | 1978-06-16 | REACTIVE DYES AND THEIR PRODUCTION. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2024236A true GB2024236A (en) | 1980-01-09 |
| GB2024236B GB2024236B (en) | 1983-02-23 |
Family
ID=4311838
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7920991A Expired GB2024236B (en) | 1978-06-16 | 1979-06-15 | Reactive dyes their preparation and use |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS55796A (en) |
| BE (1) | BE877007A (en) |
| BR (1) | BR7903811A (en) |
| CA (1) | CA1117937A (en) |
| CH (1) | CH635860A5 (en) |
| CS (1) | CS205148B2 (en) |
| DE (1) | DE2924000C2 (en) |
| ES (1) | ES481610A1 (en) |
| FR (1) | FR2428664A1 (en) |
| GB (1) | GB2024236B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4523925A (en) * | 1982-06-09 | 1985-06-18 | Ciba-Geigy Corporation | Process for dyeing or printing cellulose textile fiber materials with reactive dyes containing fluoro-triazine |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3145728A1 (en) * | 1981-11-19 | 1983-05-26 | Bayer Ag, 5090 Leverkusen | COPPER-CONTAINING BISAZOREACTIVE DYES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR COLORING AND PRINTING HYDROXYL AND / OR NITROGEN-CONTAINING MATERIALS |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1029437A (en) * | 1950-12-13 | 1953-06-02 | Improvements to elastic forks for cycles | |
| GB863758A (en) * | 1958-10-31 | 1961-03-29 | Ici Ltd | New triazine azo dyestuffs |
| FR1256740A (en) * | 1960-04-29 | 1961-03-24 | Geigy Ag J R | New reactive dyes containing in particular residues of cyclic polycarbimides, and their preparation |
| DE1419829C3 (en) * | 1961-08-26 | 1974-03-07 | Bayer Ag, 5090 Leverkusen | Metal-containing azo dyes and process for their preparation |
| CH465087A (en) * | 1963-03-14 | 1968-11-15 | Ciba Geigy | Process for the preparation of new disazo dyes |
| GB1084202A (en) * | 1963-09-12 | |||
| FR1390548A (en) * | 1964-03-09 | 1965-02-26 | Ciba Geigy | New disazo dyes, their preparation process and their use |
| CH486535A (en) * | 1966-02-07 | 1970-02-28 | Ciba Geigy | Process for the production of fiber-reactive azo dyes |
| FR1541026A (en) * | 1966-08-18 | 1968-10-04 | Ciba Geigy | Novel disazo dyes, their preparation process and their use |
| DE1644171A1 (en) * | 1966-09-10 | 1970-07-30 | Bayer Ag | Reactive dyes and processes for their preparation |
| DE1644203B2 (en) * | 1967-03-25 | 1977-11-17 | Bayer Ag, 5090 Leverkusen | REACTIVE COLORS |
| DE1644208C3 (en) * | 1967-04-19 | 1978-06-01 | Bayer Ag, 5090 Leverkusen | Reactive dyes |
| GB1320921A (en) * | 1970-03-02 | 1973-06-20 | Ici Ltd | Fibre-reactive dyestuffs |
| BE787621A (en) * | 1971-08-16 | 1973-02-16 | Sandoz Sa | PROCESS FOR PREPARING REAGENT DISAZOIC COMPOUNDS USED IN PARTICULAR FOR DYING CELLULOSIC FIBERS |
| DE2549570C2 (en) * | 1975-11-05 | 1983-05-19 | Bayer Ag, 5090 Leverkusen | Azo reactive dyes |
| LU75328A1 (en) * | 1976-07-08 | 1978-02-08 |
-
1978
- 1978-06-16 CH CH658078A patent/CH635860A5/en not_active IP Right Cessation
-
1979
- 1979-06-13 DE DE19792924000 patent/DE2924000C2/en not_active Expired
- 1979-06-13 CS CS409179A patent/CS205148B2/en unknown
- 1979-06-15 BR BR7903811A patent/BR7903811A/en unknown
- 1979-06-15 ES ES481610A patent/ES481610A1/en not_active Expired
- 1979-06-15 BE BE0/195761A patent/BE877007A/en not_active IP Right Cessation
- 1979-06-15 FR FR7915478A patent/FR2428664A1/en active Granted
- 1979-06-15 CA CA000329858A patent/CA1117937A/en not_active Expired
- 1979-06-15 GB GB7920991A patent/GB2024236B/en not_active Expired
- 1979-06-16 JP JP7519679A patent/JPS55796A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4523925A (en) * | 1982-06-09 | 1985-06-18 | Ciba-Geigy Corporation | Process for dyeing or printing cellulose textile fiber materials with reactive dyes containing fluoro-triazine |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2024236B (en) | 1983-02-23 |
| CS205148B2 (en) | 1981-04-30 |
| FR2428664B1 (en) | 1984-06-22 |
| DE2924000C2 (en) | 1983-12-29 |
| JPS6250509B2 (en) | 1987-10-26 |
| DE2924000A1 (en) | 1980-01-17 |
| CH635860A5 (en) | 1983-04-29 |
| BR7903811A (en) | 1980-02-05 |
| FR2428664A1 (en) | 1980-01-11 |
| JPS55796A (en) | 1980-01-07 |
| BE877007A (en) | 1979-12-17 |
| ES481610A1 (en) | 1980-07-01 |
| CA1117937A (en) | 1982-02-09 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19920615 |