GB2057479A - Reactive Dyes - Google Patents
Reactive Dyes Download PDFInfo
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- GB2057479A GB2057479A GB8012102A GB8012102A GB2057479A GB 2057479 A GB2057479 A GB 2057479A GB 8012102 A GB8012102 A GB 8012102A GB 8012102 A GB8012102 A GB 8012102A GB 2057479 A GB2057479 A GB 2057479A
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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
- C09B62/043—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 containing two or more triazine rings linked together by a non-chromophoric link
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Abstract
Reactive dyestuffs have the formula: <IMAGE> wherein: A is chromophoric residue, R<1> and R<2> are each independently H or C1-4 alkyl optionally substituted by OH or CN, Y is an optionally substituted amino group, and Dm is an aliphatic or cyclo-aliphatic group. These dyes will reactively colour active hydrogen substrates especially cellulose at relatively low temperatures and show superior resistance to loss of colour under acid a conditions ("acid-bleeding") compared with many dichlorotriazinyl dyes.
Description
SPECIFICATION
Reactive Dyestuffs
This invention relates to reactive dyestuffs in particular to those containing two triazine nucleii linked by the residue of a diamine.
It is well known to manufacture dyestuffs which contain reactive groups which permit a covalent bond to be formed between the dyestuff molecule and a substrate containing active hydrogen atoms such as cellulose.
A particular class of such reactive groups is known of the form:
where R, R1 and R2 are H or optionally substituted hydrocarbyl groups, Y may be an atom such as chlorine which is reactive towards cellulose or an unreactive group, Dm is a linking group provided by the diamine H(R1)N-Dm-N(R2)H and Q is a cellulose reactive group such as chlorotriazinyl. Various types of dyestuff in this class are described in, for example, UK Patents 1,015,931 and 2,936,071,
934,809 and 1,231,411 and French Patent 1,344,653.
Whilst these patents show various possibilities for the groups Y, Dm and 0, none specifically disc!oses the combination of Y as unreactive to cellulose, Dm as aliphatic or cycloaliphatic and Q as dichlorotriazinyl.
It has now been found that this novel combination of Y, Dm and 0 confers unexpectedly good properties on the dyestuffs. For example, the dyes have good reactivity towards cellulose at iow temperatures, e.g. 400 C, and give coloured substrates with a good resistance to "acid-bleeding". Most dichlorotriazinyl dyes show good reactivity at low temperature but are almost always associated with "acid-bleeding", i.e. loss of colour under moist acidic conditions. This effect frequently also produces loose dyestuff which can stain other substrates in the vicinity.
According to the present invention, there are provided dyestuffs of the formula:
wherein:
A is a chromophoric residue,
R1 and R2 are each independently H or Alkyl optionally substituted by OH or CN,
Y is an optionally substituted amino group, and
Dm is an aliphatic or cyclo-aliphatic group.
The symbol A may represent a chromophoric residue of any of the dyestuff series, e.g. of the azo, anthraquinone; phthalocyanine, formazan, nitroarylamine, oxazine, azine, triphenylmethane of xanthene series. The chromophoric residue A is often conveniently linked tithe triazine nucleus by a group NR where R has the meanings given above for R1 and R2 especially H.
As examples of the groups R1 and R2 there may be mentioned ethyl, n-propyl, n-butyl, 2 cyanoethyl, 2-hydroxyethyl, but it is usually preferred that they are methyl or especially H.
As examples of the group Y there may be mentioned: amino, lower alkylamino, e.g. methylamino, ethylamino, butylamino, di-(loweralkyl)amino, e.g. dimethylamino, diethylamino, methylethylamino, dibutylamino and groups of the latter two types in which the alkyl groups are substituted in particular by OH, CN or SO3H, e.g. p-hydroxyethylamino, di-(P-hydroxyethyl)amino, P-cyanoethylamino, di(P- cyanoethyl)amino, p-sulphoethylamino, p-hydroxypropylamino, (p-hydroxybutyl)ethylamino and (P- hydroxymethyl)-amino; cycloalkylamino, e.g. cyclohexylamino, naphthylamino substituted by 1,2 or 3
SO3H groups and optionally substituted phenyl amino groups.
As a particularly preferred form of the optionally substituted phenylamino groups there may be mentioned groups of the formula:
where G=H, methyl, ethyl, w-sulphomethyl, p-carboxy-, p-hydroxy- or jB-cyanoethyl and Z and X are each independently selected from H, COOH, SO3H, CH3,C2H5,OCH3, OC2H5, Cl Br CN, NO NH COCH3.
As specific examples of such groups there may be mentioned anilino, o-, m- and psulphonanilino, o-, m- and p-carboxyanilino, 4- and 5-sulpho-2-carboxyanilino, 4- and 5-sulpho-o tolylamino, 2,4-, 2,5- and 3,5-disulphoanilino, ?,4-dicarboxyanjlino, 4- and 5-sulpho-2-methoxyanilino, N-methyl-o-, ni- and p-sulphoanilino, N-w-sulphomethylanilino. N-(P-hydroxyethyl)-3- sulphoanilino.
A further preferred form of Y are cyclic amino groups such as morpholino or piperidino.
A yet further preferred form of Y is as a group of the form:
where R3, R4 and Dm1 have the meanings given above for R1, R2 and Dm respectively, i.e. the dyestuff contains two such dichlorotriazinyl diamine residues which although not necessarily so will usually be identical.
As examples of cycloaliphatic groups suitable for the group Dm there may be mentioned any nonaromatic homocyclic groups such as 1,4-cyclohexylene. However it is usually preferred that Dm is an aliphatic, i.e. non-cyclic, group such as linear or branched C1~6alkylene groups, e.g. 1,8-hexylene, 1,4- butylene, 3-methyl, 1,5-pentylene, 1B-butylene, 1,2- and 1,3-propylene and especially ethylene.
It is usually preferred that the dyestuffs of this invention have significant water-solubility, e.g. at least 5 grams/litre at 250C. This can be obtained by the dyestuff containing one or more acidic solubilizing groups such as SO3H.
The present invention also provides a process for the manufacture of dyes of formula (1) which comprises reacting an amino dyastuff of the formula:
where R1, R2, A, Dm and Y have the meanings given above with cyanuric chloride.
This reaction may conveniently be carried out in an aqueous medium at 0--2 5 0 C. If desired the cyanuric chloride may be introduced as a solution in a water-miscible solvent such as acetone. The addition of an acid-binding agent, e.g. sodium carbonate, bicarbonate or hydroxide to maintain the pH at 4 to 9 preferably 7.5 to 8.5 may be desirable in some instances.
The dyestuff prepared in the process of the invention may be isolated by any convenient known method such as spray drying or precipitation and filtration. The aqueous reaction mixture containing the dyestuff of formula (1) mav, in some instances, be conveniently employed in preparing, for example, dyeing liquors without isolation of the solid dyestuff. When, as is often the case, the dyestuff contains acidic solubilising groups such as SO3H it is usually convenient to isolate the dyestuff with these groups, at least partially, in the form of salts, e.g. sodium salts.
The cyanuric chloride will be used in amounts of 1 molar proportion or a slight excess. In those instances where a dye in which Y is of the form:
the process can be modified so that two molar proportions of cyanuric chloride are reacted with an amino dyestuff of the formula:
where A, R1, R2, R3, R4, Dm and Dm1 have the meanings given above. Though not necessarily so, R3, R4 and Dm1 will usually be identical with R1, R2 and Dm respectively.
The amino dyestuffs of formula (2) for use in the process of the present invention may be conveniently obtained by reacting a dichlorotriazinyl dyestuff of the formula:
in either order with 1 molar proportion of ammonia or an amine YH and 1 molar proportion of a diamine HN(R1)DmN(R2)H where A, Y, R1, R2 and Dm have the meanings given above.
The amino dyestuffs of formula (3) can be obtained by reacting the dichlorotriazinyl dye of formula (4) stepwise with 1 molar proportion of each of the diamines HN(R')DmN(R2)H and
HN(R3)Dm'N(R2)H. In the usual case where R3, R4 and Dm' are the same as R', R2 and Dm respectively, the reaction can be conducted in a single stage using 2 molar proportions of the diamine.
To minimise the possibility of reaction of both amino groups in the diamine thereby linking two molecules of dichlorotriazinyl dyestuff, it is often found desirable to conduct this reaction in an aqueous medium whose pH is maintained in the range 5-9.
The dichlorotriazinyl dyestuff of formula (4) may be obtained by conventional means, for example, a dyestuff bearing an amino group may be reacted with cyanuric chloride.
As examples of such dyestuff bearing an amino group there may be mentioned the following classes:
(i) Anthraquinone compounds of the formula:
wherein the anthraquinone nucleus may contain an additional sulphonic acid group in the 5-, 6-, 7- or 8-position and V represents a bridging group which is preferably a divalent radical of the benzene series, for example phenylene, diphenylene or 4,4'-divalent stilbene or azobenzene radicals. It is preferred that V should contain one sulphonic acid group for each benzene ring present. R has the meaning stated above.
(ii) Monoazo compounds of formula:
wherein D, represents a mono- or di-cyclic aryl radical which is free from azo groups and NHR groups, the -NHR group is preferably attached to the 6, 7- or 8-position of the naphthalene nucleus, and which may contain a sulphonic acid group in the 5-or 6-position of the naphthalene nucleus.
D1 may represent a radical of the naphthalene or benzene series which is free from azo substituents, for example a stilbene, diphenyl, benzthiazolylphenyl or diphenylamine radical. Also in this class are to be considered the related dyestuffs in which the NHR group, instead of being attached to the naphthalene nucleus, is attached to a benzoylamino or anilino group which is attached to the 6-, 7or 8-position of the naphthalene nucleus.
Particularly valuable dyestuffs are obtained from those wherein D1 represents a sulphonated phenyl or naphthyl radical, especially those which contain a -SO3H group in ortho position to the azo link; the phenyl radical may be further substituted, for example by halogen atoms such as chlorine, alkyl radicals such as methyl, acylamino groups such as acetyl-amino and alkoxy radicals such as methoxy.
(iii) Disazo compounds of formula (6) wherein D, stands for a radical of the azobenzene, azonaphthalene or phenylazo-naphthalene series and the naphthalene nucleus is substituted by the
NHR group, and optionally by sulphonic acid as in class (ii).
(iv) Mono- or dis-azo compounds of the formula: D1-N=N-D2-NHR (7) wherein D, stands for a radical as defined for class (ii) or class (iii) and D2 is a 1 :4-phenylene or a sulpho-1 ,4-naphthylene or a stilbene radical; the benzene nuclei in D1 and D2 may contain further substituents such as halogen atoms, or alkyl, alkoxy carboxylic acid and acylamino groups.
(v) Mono- or dis-azo compounds of the formula:
wherein D1 represents an arylene radical such as a radical of the azobenzene, azonaphthalene or phenylazonaphthalene series or, preferably, or at most, dicyclic arylene radical of the benzene or naphthalene series, and K represents the radical of a naphthol sulphonic acid or the radical of an enolised or enolisable keto-methylene compound (such as an acetoacetarylide, a 5-pyrazolone or a 6hydroxypyrid-2-one having the OH group o- to the azo group. D1 preferably represents a radical of the benzene series containing a sulphonic acid group.
(vi) Mono- or dis-azo compounds of the formula: D1-N=N-K2-NHR (9) wherein D, represents a radical of the types defined for D, in classes (ii) and (iii) above and K2 represents the radical of an enolisable keto-methylene compound such as an acetoacetarylide or a 5pyrazolone having the -OH group in a a-position to the azo group.
(vii) 1:1 metal complex, especially the copper complex, compounds of those dyes of formulae 6, 8 and 9 (wherein D1 K and K2 have all the respective meanings stated) which contain a metallisable (for example, a hydroxy, lower alkoxy or carboxylic acid) group ortho- to the azo group in D1.
(viii) Phthalocyanine compounds of the formula:
wherein Pc represents the phthalocyanine nucleus preferably of copper phthalocyanine, c.) represents a hydroxy and/or a substituted or unsubstituted amino group, V, represents a bridging group, preferably an aliphatic, cycloaliphatic or aromatic group, n represents 1, 2 or 3.
(ix) Nitro dyestuffs of the formula:
wherein B1 and B2 represents mono-cyclic aryl nuclei, the nitro group in B1 being ortho to the NH group.
(x) Formazan dyestuffs of the formula:
wherein M is Cu or Ni, D and B are mono or polynuclear ary groups in which the links shown are from carbon atoms ortho to each other, the group R' is an optionally substituted hydrocarbyl group and one of the groups D, B or R1 bears a group
(xi) Nitro-stilbene dyestuffs of the formula:
wherein n and m are each independently 1 or 2.
(xii) Phenazine dyes of the formula:
wherein n is 1 or 2,
R5 is H or optionally substituted C,C4 alkyl, R6 is optionally substituted C,, alkyl, optionally substituted aralkyl or optionally substituted aryl, and the benzene ring A1 can be further substituted, e.g. by Cl, CH3 or OCH3.
As particular examples of compounds of classes (i) to (xii), there may be mentioned:
In Class (i)
1 -amino-4-(4'-aminoanilino)anthraquinone-2,2'-disulphonic acid, 1 -amino-4-(4'-methylaminoanilino)anthraquinone-2 :3'-disulphonic acid,
1 -amino-4-(3'-amino-2' :4' :6'-trimethylanilino)anthraquinone-2,5'-disulphonic acid
In Class (ii)
6-amino-1 -hydroxy-2-(2'-sulphophenylazo)naphthalene-3-sulphonic acid,
8-a mi no- 1 -hydroxy-2-(2'-sulphophenylazo) naphthalene-3 :6-disulphonic acid, 7-amino-2-(2' : :5'-disulphophenylazo)-1 -hydroxynaphthalene-3-sulphonic acid, 7-methylamino-2-(2'-suphophenylazo)-1 -hydroxynaphthalene-3-sulphonic acid,
7-methylamino-2-(4'-methoxy-2'-sulphophenylazo)- 1 -hydroxynaphthalene-3-sulphonic acid,
8-(3'-aminobenzoylamino) 1 -hydroxy-2- (2'-sulphophenylazo)naphthalene-3 :6-disulphonic acid,
8-amino-1 -hydroxy-2 :2'-azonaphthalene-1 ' :3 :5'-6-tetrasulphonic acid, 6-amino-1 -hydroxy-2(4'-acetylamino-2'-sulphophenylazo)naphthalene-3-sulphonic acid, 6-methylamino-1 -hydroxy2-(4'-methoxy-2'-sulphophenylazo)naphthalene-3-sulphonic acid, 8-amino-1 -hydroxy-2-phenylazonaphthalene-3 :6-disulphonic acid,
8-amino-1 -hydroxy-2 :2'-azonaphthalene-1 ':3 ::6-trisulphonic acid, 6-amino-1 -hydroxy-2-(4'-methoxy-2'-sulphophenylazo)naphthalene-3-sulphonic acid, 8-amino-1 -hydroxy-2 :2'-azonaphthalene-1 ':3 :5'-trisulphonic acid,
6-amino-1 -hydroxy-2 :2'-azona phtha lene-1 ',3,5'*trisu Iphonic acid, 6-methylamino-1 -hydroxy-2 :2'-azonaphthalene-1 ':3 :5'-trisulphonic acid,
7-amino-1 -hydroxy-2:2'-azonaphthalene-1 ':3-disulphonic acid, 8-amino- 1 -hydroxy-2-(4'-hydroxy-3'-carboxyphenylazo-naphthalene-3 :6-disu Iphonic acid, 6-amino-1 -hydroxy-2-(4'-hydroxy-3'-carboxyphenylazo)naphthalene-3 ::5-disulphonic acid
In Class (iii)
8-amino-1 -hydroxy-2-[4'-(2"-sulphophenylazo)-2'-methoxy-5'-methylphenylazo]naphthalene- 3:6-disulphonic acid, 4:4'-bis(8"-a mino-1 "-hydroxy-3 " :6"-disulpho-2ff-naphththylazo)-3 :3'-dimethoxydiphenyl,
6-amino- 1 -hydroxy-2-[4'-(2"-sulphophenylazo)-2'-methoxy-5'-methylphenylazo]naphthalene- 3:5-disulphonic acid
In Class (iv) 2-(4'-a mino-2'-methylphenylazo) naphthalene-4 :8-disulphonic acid, 2-(4'-amino-2'-acetylaminophenylazo)naphthalene-5 :7-disulphonic acid,
2-(4'-amino-2'-ureidophenylazo)naphthalene-3 :6 :8-trisulphonic acid,
4-nitro-4'-(4"-methyla minophenylazo)stilbene-2 :2'-disulphonic acid, 4-nitro-4'-(4"-a mino-2"-methyl-5"-methoxyphenylazo)stilbene-2 ::2-disulphonic acid, 2-(4'-amino-2'-acetylaminophenylazo)naphthalene-4:8-disulphonic acid, 4-amino-2-methylazobenzene-2' :5 '-disulphonic acid, 4-[4'-(2",5"-disulphophenylazo)-2',5'-dimethylphenylazo]-1 -naphthylamine-8-sulphonic acid, 4-[4'-(2",5",7"-trisulphonaphth-1 "-ylazo)-2',5'-dimethylphenylazo]-1 -naphthylamine-6sulphonic acid, 4-[4'-(2n,5",7X-trisulphonaphth-1 n-ylazo)-2',5'-dimethylphenylazo]-1 -naphthylamine-7sulphonic acid, 4-[4'-(2",5",7"-trisulphonaphth-1 "-ylazo)-naphth-1 '-ylazo]-l -naphthylamine-6-sulphonic acid, 4-[4'-(2",5"-disulphophenylazo)-6'-sulphonaphth-1 -ylazo]-1 -naphthylamine-8-sulphonic acid,
4-[4'-(4"-sulphophenylazo)-2'-sulphophenylazo]-1-naphthylamine-6-sulphonic acid
In Class (v)
1 -(2',5'-dichloro-4'-sulphophenyl)-3- methyl-4-(3"-amino-4"-sulphophenylazo)-5-pyrazolone, 1 -(4'-sulphophenyl)-3-carboxy-4-(4"-amino-3"-sulphophenylazo)-5-pyrazolone,
1 -(2'-methyl-5'-sulphophenyl)-3-methyl-4-(4"-ami no-38-sulphophenylazo)-5-pyrazolone, 1 -(2'-sulphophenyl)-3-methyl-4-(3"-amino-4"-sulphophenylazo)-5-pyrazolone, 4-amino-4'-(3"-methyl-1 "-phenyl-4"-pyrazol-5"-onylazo)-stilbene-2 :2'-disu Iphonic acid, 4-amino-4'-(2"-hydroxy-3",6"-disulpho-1 "-naphthylazo)stilbene-2 ::2'-disulphonic acid,
8-acetylamino-1-hydroxy-2-(3'-amino-4'-sulphophenylazo)naphthalene-3:6-disulphonic acid,
7-(3'-sulphophenylamino)-1 -hydroxy-2- (4'-amino-2'-carboxyphenylazo,-naphthalene-3- sulphonic acid, 8-phenylamino-1 -hydroxy-2-(4'-amino-2'-sulphophenylazo)naphthalene-3 :6-disulphonic acid, 6-acetylamino-1 -hydroxy-2-(5'-amino-2'-sulphophenylazo)naphthalene-3-sulphonic acid, 6-ureido-1-hydroxy-2-(5'-amino-2'-sulphophenylazo)naphthalene-3-sulphonic acid,
8-benzoylamino-1-hydroxy-2-(5'-amino-2'-sulphophenylazo)naphthalene-3:6-disulphonic acid,
1-(4':8'-disulphonaphth-2'-yl)-3-methyl-4-(5"-amino-2"-sulphophenylazo)-5-pyrazolone,
1-(2'-sulphophenyl)-3-carboxy-4-(5"-amino-2"-sulphophenylazo)-5-pyrazolone, 1 -(2 ' ::5'-dichloro-4'-sulphophenyl)-3-methyl-4-(5ff-a "-amino-2"-sulphophenylazo)-5-pyrazolone 5-(3 '-a mino-4'-sulphophenylazo)-4-methyl-5-cyano-6-hydroxypyrid-2-one, 5-(3 '-amino-4'-sulphophenylazo)-4-methyl-5- carbona mido-6-hydroxy-N-ethylpyrid-2-one, 5-(3 -a mino-4'-su lphophenylazo)-4-methyl-6-hydroxypyrid-2-one, 5-(3 '-amino-4'-sulphophenylazo)-4-methyl-5-cyano-6-hydroxy-N-methylpyridone, 5-(4'-amino-3'-sulphophenylazo)-4-methyl-5-cyano-6-hydroxy-N-ethylpyridone, 5-(4'-amino-2',5'-disulphophenylazo)-4-methyl-5-cyano-6-hydroxy-N-ethylpyridone, 5-(3-amino-4-sulphophenylazo)-3,4-dimethyl-6-hydroxy- 1 -n-propylpyrid-2-one, 5-(4-amino-2,5-disulphophenylazo)-1 - n-butyl-6-hydroxy-4-methyl-3-sulphomethylpyrid-2-one, 5-(3-am ino-4-sulphophenylazo)-1 -ethyl-6-hydroxy-4-methyl-3-sulphopyrid-2-one,
5-(3-amino-4-sulphophenylazo)-3-chloro- 1 -ethyl-6-hydroxy-4-methylpyrid-2-one,
5-(3-am ino-4-su I phophenylazo)-3-cyano- 1 -ethyl-6-hydroxy-4-sulphomethylpyrid-2-one,
5-(3-a mino-4-sulphophenylazo)-3-aminocarbonyl-6-hydroxy-4-methyl-1 -[2-(4sulphophenyl)ethyl]pyrid-2-one
In Class (vi)
1 -(3'-aminophenyl)-3-methyl-4-(2':5'-disulphophenylazo)-5-pyrazolone, 1 -(3'-a minophenyl)-3-carboxy-4-(2'-carboxy-4'-sulphophenylazo)-5-pyrazolone, 4-amino-4'-[3"-methyl-4"-(2"' :5"'-disulphophenylazo)-l "-pyrazol-5"-onyl]stilbene-2 :2'disulphonic acid,
1 -(3'-aminophenyl)-3-carboxy-4-[4"-(2"' ::5"'-disulphophenylazo)-2"-methoxy-5"- methylphenylazo]-5-pyrazolone
In Class (vii)
The copper complex of 8-amino-1-hydroxy-2-(2'-hydroxy-5'-sulphophenylazo)naphthalene-3:6- disulphonic acid,
The copper complex of 6-amino-1 -hydroxy-2(2'-hydroxy-5'-sulphophenylazo)naphthalene-3 suiphonic acid,
The copper complex of 6-amino- 1 -hydroxy-2-(2'-hydroxy-5'-sulphophenylazo)naphthalene-3 :5- disulphonic acid,
The copper complex of 8-amino-1 ,1 '-dihydroxy-2,2'-azonaphthalene-3,4',6,8'-tetrasulphonic acid,
The copper complex of 8-amino-1 -hydroxy-2-[4'-(2"-sulphophenylazo)-2'-methoxy-5'- methylphenylazojnaphthalene-3 :6-disulphonic acid,
The copper complex of 6-amino-1 -hydroxy-2-[4'-(2"::5"-disulphophenylazo)-2'-methoxy-5'- methylphenylazo]naphthalene-3,5-disulphonic acid,
The copper complex of 1 -(3'-amino-4'-sulphophenyl)-3-methyl-4-[4ff-(2"':5"'- disulphophenylazo)-2"-methoxy-5"-methylphenylazo-5-pyrazolone,
The copper complex of 7-(4'-amino-3'-sulphoanilino)-i -hydroxy-2-[4"-(2"' ::5"'- disulphophenylazo)-2"-methoxy-5"-methylphenylazo]naphthalene-3-sulphonic acid,
The copper complex of 6-(4'-amino-3'-sulphoaniiino)-1-hydtoxy-2-(2"- carboxyphenylazo)naphthalene-3-sulphonic acid
In Class (viii)
3-(3'-amino-4'-sulphophenyl-sulphamyl copper phthalocyanine tri-3-sulphonic acid,
4-(3'-amino-4'-sulphophenyl)sulphamyl copper phthalocyanine tri-4-sulphonic acid,
3-(3'- or 4'-aminophenyl)sulphamyl copper phthalocyanine-3-sulphonamide-di-3-sulphonic acid
In Class (ix) 4-amino-2'-nitro-diphenylamine-3 ::4'-disulphonic acid
In Class (x)
The copper complex of N-(2-hydroxy-5-sulpho-3-aminophenyl)-N-(2'-carboxy-4'-sulphophenyl)- ms-phenylformazan,
The copper complex of N(2hydrnxy5sulpho3aminophenyl)-N1-(2'-carboxy-4'-sulphophenyl)- ms-(48-sulphophenyl)formazan, The copper complex of N-(2-hydroxy-5-sulphophenyl)-N1-(2'-carboxy-4'-aminophenyl)-ms-(2"sulphophenyl)formazan,
The copper complex of N-(2-hydroxy-5-sulphophenyl)-N-(2'-carboxy-4'-aminophenyl)-ms-(2"- chloro-5"-sulphenyl)formazan,
The copper complex of N-(2-hydroxy-5-sulphophenyl)-N '-(2'-carboxy-4'-sulphophenyl)-ms-(4X- aminophenyl)formazan,
The copper complex of N-(2-hydroxy-5-sulphophenyl)-N-(2'-carboxy-4'-sulphophenyl)-ms-(4"- amino-2"-sulphophenyl)furmazan, The copper cbmplex of N-(2-carboxy-4-aminophenyl)-N "-(2'-hydroxy-4'-sulphonaphth- 1 '-yl)-ms (2"-sulphophenyl)formazan In Class (xi)
4-amino-4'-nitrostilbene-2,2'-disulphonic acid, 4-(N-methylamino)acelaminostilbene-2,2-disulphonic acid
In Class (xii) Anhydro-9-(4-amino-3-sulphoanilino)-5-anilino-7-phenyl-4-sulpho or 2,4-4,11 disulphobenz[a]phenazinium hydroxide,
Anhydro-9-(4-amino-3-sulphoanilino)-5-p-toluidino-7-p-tolyl-2,4-disulphobenz[a]phenazinium hydroxide, Anhydro-9-(4-amino-3-sulphoanilino)-5-p-toluidino-7-p-methoxyphenyl-2,4- disulphobenz[a]phenazinium hydroxide,
Anhydro-3-(4-amino-3-sulphoanilino)-7-N-ethyl-N-(3 or 4-sulphobenzylamino-5-(2,3 or 4
sulphophenyl)phenazinium hydroxide,
Anhydro-3-(4-amino-3-sulphoanilino-7-N-ethyl-N-(3 or 4-sulphobenzyl)amino-1 -methyl or methoxy-5-(2-su lphophenyl)phenazinium hydroxide,
Anhydro-3-(4-amino-3-sul phoanilino)-7-N-ethyl-N-(3 or 4-sulphobenzyl)-amino-5-(4-chloro, methoxy or methyl-3-sulphophenyl)phenazium hydroxide, Anhydro-5-(4-amino-2,5-disulphoanilino)-9-diethylamino-7-phenyl- O- sulphobenz[ajphenaziniu m hydroxide,
Anhydro-3,7-bis[N-ethyl-N-(3 or 4-sulphobenzyl)j-5-(3- or 4-amino-4- or 3sulphophenyl)phenazinium hydroxide, Anhydro-3-(4-amino-3-sulphoanilino)-7-N-ethyl-N-(2-sulphoethyl)-amino-5-(2,3 or 4sulphophenyl)phenazinium hydroxide, Anhydro-3-(4-amino-3-sulphoanilino)-7-N-methyl-N-(2-sulphoethyl)-5-(3 or 4-amino-4 or 3sulphophenyl)phenazinium hydroxide.
As examples of diamines HN(R1) Dm N(R2)H which may be used to manufacture intermediates for the process of the present invention there may be mentioned:
ethylene diamine
1,2 and 1,3-propylene diamine 1 ,4-butylene diamine
1,6-hexylene diamine 1,4-diaminocyc/ohexane Specific examples of the amines YH for use in the manufacture of intermediates for the process of the present invention will be apparent from the examples of the group Y given above.
It may be found desirable to take steps to minimise the hydrolysis of the chlorine atoms on the triazine nuclei of dyestuffs of formula (1) which can occur during storage of the dyestuff or in dyebaths of printing pastes containing the dyestuff. A convenient means of effecting this stabilisation is to mix with the dyestuff certain compositions which tend to keep the pH in the region of 4-7 especially 6 to 7 e.g. mixtures of alkali metal acid phosphates and mixtures of alkali metal N,N-diethylamino benzene sulphonate and the corresponding free sulphonic acid. Mixtures of the dyestuffs of formula (1) and a stabiliser which reduces its tendency to hydrolysis are a further feature of the invention.
The dyestuffs of the present invention may be used for colouring a wide range of materials containing hydroxyl or amino groups, e.g. wool, silk, polyamide and natural or regenerated cellulose, for example, cotton or viscose rayon materials, by the conventional methods used for colouring such
materials with water-soluble reactive dyes, e.g. in the case of cellulose they are preferably applied in conjunction with a treatment with an acid-binding agent, e.g. caustic soda, sodium carbonate, phosphate, silicate or bicarbonate, which may be applied to the cellulose textile materials before, during or after the application of the dyestuff.
The process of colouration with the dyestuff of the present invention and textile materials so coloured are further features of the present invention.
The dyestuffs of the present invention are usually characterised by having a good rate of reaction with cellulose substrates e.g. dyeings may be carried out at 40 C and, in contrast to many dichlorotriazinyl dyes, give coloured material having good resistance to "acid bleeding".
Additionally the new dyestuffs also have a high degree of fixation and are particularly valuable in dyeing by exhaustion methods where they show good fixation over a wide range of liquor-to-goods ratios.
The invention is illustrated but not limited by the following Examples in which all parts are by weight unless otherwise specified.
Example 1
18.7 Parts of 2-aminonaphthalene-1 5-disulphonic acid is stirred in 100 parts of ice and water and diazotised by the addition of 20 parts of concentrated hydrochloric acid and 3.5 parts of sodium nitrate. The diazonium salt so produced is added to, at pH 7 and 50C, 20 parts of 1 -hydroxy-8acetylaminonaphthalene-3,6-disulphonic acid in 150 parts of water. After 1 hour 12 parts of sodium hydroxide is added and the temperature raised to 95--1000C and held for 2 hours. The solution is then neutralised, cooled below 50C and 10 parts of cyanuric chloride added.After 1 hour the pH is adjusted to 7 and the solution filtered from any insoluble matter. 4.25 parts of piperidine in 50 parts of water at pH 8.5 is then added and the mixture is maintained at pH 8.5 and 300C for 4 hours after which 1 5 parts of ethylene diamine in 100 parts of water at pH 8.5 is added and the mixture then maintained at 750C and pH 8.5 for 4 hours. The product is salted out hot, filtered off and washed well with brine before redissolving in 1000 parts of water, cooling to below 50C, adding 10 parts of cyanuric chloride and maintaining at below 50C and at pH 8.5 for 2 hours. The product is salted out, filtered off, dried and mixed with 10% mono/dihydrogen phosphate buffer to give 65 parts of a dyestuff which dyes cellulosic fibres in conjunction with an acid binding agent in bright red shades of excellent fastness properties, especially resistance to acid hydrolysis.
The structure of the dyestuff is (as free acid):
Example 2
18.7 parts of 2-aminonaphthalene-1 5-disulphonic acid is diazotised as in Example 1 and added to 22 parts of 1 -hydroxy-8-aminonaphthalene-3,6-disulphonic acid in 200 parts of water at pH 3.5 and below 50C. After 1 0 hours the product is salted out, filtered off and redissolved in 500 parts of water.
To this solution is added the diazonium suspension prepared by taking 12 parts of 2,4-diaminobenzene suiphonic acid in 200 parts of ice and water, adding 1 5 parts cyanuric chloride, stirring 2 hours, adjusting to pH 7 and diazotising by the addition of 5.2 parts of sodium nitrite and 20 parts of concentrated hydrochloric acid. The mixture is maintained at pH 7 and after 2 hours the product salted out and filtered off. Upon redissolving in 1000 parts of water the pH is adjusted to 8.5 and 1 5 parts of ethylene diamine in 100 parts of water at pH 8.5 is added. The mixture is stirred at 300C and pH 8.5 for 2 hours and then raised to 750C and stirred for 4 hours at this temperature and at pH 8.5.The product is salted out hot, filtered off and washed well with brine, redissolved in 2000 parts of water, cooled to below 50C and 10 parts of cyanuric chloride added. The condensation is maintained at pH 8.5 and 50C for 2 hours before salting out the product filtering off, drying and mixed with 10% mono/dihydrogen phosphate buffer to give 78 parts of a dyestuff which dyes cellulosic fibres in conjunction with an acid binding agent in blue shades of excellent fastness properties, especially resistance to acid hydrolysis.
The structure of the dye is (as free acid):
Example 3 1 8 parts of 2-aminonaphthalene-3,6,8-trisulphonic acid in 200 parts of water is diazotised at below 50C by the addition of 15 parts of concentrated hydrochloric acid and 3.5 parts of sodium nitrite and the resulting diazonium salt is added to 7.5 parts of m-ureidoaniline in 500 parts of water at pK 4.5 and 50C. On completion of the coupling 10 parts of cyanuric chloride is added and the pH adjusted to 7. After 3 hours the temperature is raised to 250C and 20 parts concentrated ammonia solution is then added and the solution stirred for 20 hours before adjusting the pH to 8.5, adding 1 5 parts of ethylene diamine in 100 parts of water at pH 8.5 and heating to 750C for 3 hours. The product is salted out, filtered off, washed well with brine, redissolved in 1000 parts of water, cooled to below 50C and condensed with 10 parts of cyanuric chloride at pH 8.5. The product is salted out, filtered off, mixed with 10% mono/dihydrogen phosphate buffer and dried to give 58 parts of a dyestuff which dyes cellulosic fibres in conjunction with an acid binding agent in yellow shades of excellent fastness properties, especially resistance to acid hydrolysis.
The structure of the dyestuff is (as free acid):
Claims (1)
- Claims1. Dyestuffs of the formula:wherein: A is a chromophoric residue, R1 and R2 are each independently H or Alkyl optionally substituted by OH or CN, Y is an optionally substituted amino group, and Dm is an aliphatic or cyclo-aliphatic group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8012102A GB2057479A (en) | 1979-07-17 | 1980-04-11 | Reactive Dyes |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7924871 | 1979-07-17 | ||
| GB8012102A GB2057479A (en) | 1979-07-17 | 1980-04-11 | Reactive Dyes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB2057479A true GB2057479A (en) | 1981-04-01 |
Family
ID=26272211
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8012102A Withdrawn GB2057479A (en) | 1979-07-17 | 1980-04-11 | Reactive Dyes |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2057479A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT389306B (en) * | 1987-01-14 | 1989-11-27 | Sandoz Ag | Fibre-reactive monoazo-s-triazine derivative |
| EP0568876A1 (en) | 1992-05-04 | 1993-11-10 | Bayer Ag | Reactive dyes, their preparation and their use |
| US5268458A (en) * | 1989-12-29 | 1993-12-07 | Hoechst Aktiengesellschaft | Azo compounds, having a 1-sulfo-6-carboxy-2-naphthyl group as the diazo component and a halogen-substituted heterocyclic fiber-reactive group |
| GB2308376A (en) * | 1995-12-19 | 1997-06-25 | Zeneca Ltd | Monoazo dyes based on 2-[7-(2'-sulpho-phenylazo)-8-hydroxy-3,6-disulphonaphthylamino]-4,6-disubstituted-triazine skeleton for use in inks |
| US5772745A (en) * | 1995-12-19 | 1998-06-30 | Zeneca Limited | Monoazo compounds |
| USD728143S1 (en) | 2012-01-25 | 2015-04-28 | Hubbell Incorporated | Wall mounted light fixture having struts |
| USD751747S1 (en) | 2010-03-08 | 2016-03-15 | Hubbell Incorporated | Lighting fixture having struts |
-
1980
- 1980-04-11 GB GB8012102A patent/GB2057479A/en not_active Withdrawn
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT389306B (en) * | 1987-01-14 | 1989-11-27 | Sandoz Ag | Fibre-reactive monoazo-s-triazine derivative |
| US5268458A (en) * | 1989-12-29 | 1993-12-07 | Hoechst Aktiengesellschaft | Azo compounds, having a 1-sulfo-6-carboxy-2-naphthyl group as the diazo component and a halogen-substituted heterocyclic fiber-reactive group |
| EP0568876A1 (en) | 1992-05-04 | 1993-11-10 | Bayer Ag | Reactive dyes, their preparation and their use |
| GB2308376A (en) * | 1995-12-19 | 1997-06-25 | Zeneca Ltd | Monoazo dyes based on 2-[7-(2'-sulpho-phenylazo)-8-hydroxy-3,6-disulphonaphthylamino]-4,6-disubstituted-triazine skeleton for use in inks |
| US5772745A (en) * | 1995-12-19 | 1998-06-30 | Zeneca Limited | Monoazo compounds |
| GB2308376B (en) * | 1995-12-19 | 2000-03-29 | Zeneca Ltd | Monoazo dyes based on 2-[7-(2'-sulpho-phenylazo)-8-hydroxy-3,6-disulphonaphthylamino]-4,6-disubstituted-triazine skeleton for use in inks |
| USD751747S1 (en) | 2010-03-08 | 2016-03-15 | Hubbell Incorporated | Lighting fixture having struts |
| USD851800S1 (en) | 2010-03-08 | 2019-06-18 | Hubbell Incorporated | Lighting fixture having struts |
| USD952224S1 (en) | 2010-03-08 | 2022-05-17 | Hubbell Lighting, Inc. | Lighting fixture having struts |
| USD728143S1 (en) | 2012-01-25 | 2015-04-28 | Hubbell Incorporated | Wall mounted light fixture having struts |
| USD773716S1 (en) | 2012-01-25 | 2016-12-06 | Hubbell Incorporated | Wall mounted light fixture having struts |
| USD925096S1 (en) | 2012-01-25 | 2021-07-13 | Hubbell Incorporated | Wall mounted light fixture having struts |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |