CA1134817A - Azo compounds - Google Patents
Azo compoundsInfo
- Publication number
- CA1134817A CA1134817A CA000344770A CA344770A CA1134817A CA 1134817 A CA1134817 A CA 1134817A CA 000344770 A CA000344770 A CA 000344770A CA 344770 A CA344770 A CA 344770A CA 1134817 A CA1134817 A CA 1134817A
- Authority
- CA
- Canada
- Prior art keywords
- azo compound
- formula
- alkyl
- group
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- 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
- C09B44/00—Azo dyes containing onium groups
- C09B44/02—Azo dyes containing onium groups containing ammonium groups not directly attached to an azo group
-
- 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
- C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
- C09B62/443—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being alternatively specified
- C09B62/447—Azo dyes
- C09B62/45—Monoazo dyes
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/28—Colorants ; Pigments or opacifying agents
Abstract
ABSTRACT OF THE DISCLOSURE
The invention describes novel basic azo compounds of the formula (I) wherein X is one or more of the radicals (CH2,NR,CO(CH2)nA) and/or (SO2NH(CH2)nA), R is hydrogen or an alkyl group of 1 to 4 carbon atoms, A
is a non-quaternised or quaternised basic radical, n is 1 to 4, is 1 to 4, M is hydrogen or any cation, p is 0 to 2, with the proviso that the value of m is as great or greater than p, and wherein the benzene radicals 8 optionally contain one or more identical or different substituents, selected from alkyl groups of 1 to 4 carbon atoms, halogen, alkoxy groups having 1 to 4 carbon atoms, NO2, OH, SO2NH2, SO2NH-alkyl C1-C4, SO2N(alkyl C1-C4)2, benzthiazol, SO2-heterocyclic with an N-atom linked to SO2, unsubstituted phenyl, and phenyl substituted by halogen and alkyl C1-C4, and the benzene radicals D optionally contain one or one identical or different substituents namely halogen, alkyl C1-C4 and alkoxy C1-C4. Methods of obtaining the novel compounds and their use as dyes, in particular for colouring and printing natural and regenerated cellulosic fabrics without the addition of salt, and also described.
The invention describes novel basic azo compounds of the formula (I) wherein X is one or more of the radicals (CH2,NR,CO(CH2)nA) and/or (SO2NH(CH2)nA), R is hydrogen or an alkyl group of 1 to 4 carbon atoms, A
is a non-quaternised or quaternised basic radical, n is 1 to 4, is 1 to 4, M is hydrogen or any cation, p is 0 to 2, with the proviso that the value of m is as great or greater than p, and wherein the benzene radicals 8 optionally contain one or more identical or different substituents, selected from alkyl groups of 1 to 4 carbon atoms, halogen, alkoxy groups having 1 to 4 carbon atoms, NO2, OH, SO2NH2, SO2NH-alkyl C1-C4, SO2N(alkyl C1-C4)2, benzthiazol, SO2-heterocyclic with an N-atom linked to SO2, unsubstituted phenyl, and phenyl substituted by halogen and alkyl C1-C4, and the benzene radicals D optionally contain one or one identical or different substituents namely halogen, alkyl C1-C4 and alkoxy C1-C4. Methods of obtaining the novel compounds and their use as dyes, in particular for colouring and printing natural and regenerated cellulosic fabrics without the addition of salt, and also described.
Description
1~3~iP7 The present invention relates to novel basic azo compounds, pro-cesses for their production, and their use as dyes for colouring and printing textiles, paper and leather, as well as for the preparation of inks.
The novel basic azo compounds have the formula I
[~ ~ 5 ~ \ D ~ - N =~N ~ ~ / 1i3 ~
wherein X is one or more of the radicals (CH2.NR.CO(CH2)nA) and/or (SO2NH(CH2)nA), R is hydrogen or an alkyl group of 1 to 4 carbon atoms, A
is a non-quaternised or quaternised basic radical, n is 1 to 4, m is 1 to 4 M is hydrogen or any cation, p is 0 to 2, with the proviso that the value is m is as great or greater than p, and wherein the benzene radicals B
obtionally contain one or more identical or different substituents selected from alkyl groups of 1 to 4 carbon atoms, halogen, alkoxy groups having 1 to 4 carbon atoms, N02, OH, S02NH2, S02NH-alkyl Cl-C4, S02N(alkyl Cl-C4)2, benzthiazol, S02-heterocyclic with an N-atom linked to S02, unsubstituted phenyl, and phenyl substituted by halogen and alkyl Cl-C4, and the benzene radicals D optionally contain one or more identical or different substituents namely halogen, alkyl Cl-C4~and alkoxy Cl-C4.
R as an alkyl group of 1 to 4 carbon atoms is e.g. an unbranched or a brqched alkyl group, for example the methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl group. In preferred azo compounds, R is hydrogen.
As a non-quaternised or quaternised basic group, A has e.g. the following values:
a) as a basic group, e.g. the radical ~ T
~ T
~ - 1 -~ *
.: .
113~317 wherein Tl is hydrogen or a low molecular alkyl radical which i5 unsub-stituted or substituted by hydroxyl, or a cyclohexyl radical which is Imsubstituted or substituted by 1 to 3 methyl radicals, or is a phenyl radical, and T2 is a low molecular alkyl radical which is unsubstitu-ted or substituted by hydroxyl, or Tl and T2 together with the nitro-gen atom to which they are at~ached form a hydrogenated heterocyclic ring which may contain a further heteroatom, e.g. the morpholine ring:
b~ as a quaternised group, e.g. the radical of the formula Rl a ) (~ R2 ~ ~) . . . 2 wherein each of Rl and R2 independently is hydrogen, an alkyl radical of 1 to 4 carbon atoms which is unsubstituted or substituted e.g. by hydroxyl, such as the methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl radical, an unsubstituted or sub8tituted cycloalykl group, especially the cyclohexyl group which is unsubstitu-ted or substituted by one or more alkyl groups, in particular the C~3 group, or is an aryl radical, especially the phenyl radical; or R
and R2 together with the nitrogen atom to which they are attached form a heterocyclic ring, such as the pyrrolidine, piperidine, morpho-line or piperazine ring, b) - ~ - R
S
wherein each of R3 and R4 independently is hydrogen, an unsubstituted or substituted alkyl radical of 1 to 4 carbon atoms, such as the methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl radical, or the hydroxyethyl or aminoethyl radical; an unsubstituted or substituted cycloalkyl group, especially the cyclohexyl group, or an aryl radical, such as the phenyl radical, and R5 is an alkyl group .
1~3~817 of 1 to 4 carbon atoms; or R3 and R4 together with the nitrogen atom to which they are attached form a heterocyclic ring, in particular the pyrrolidine, piperidine, morpholine or piperazine ring; or R3, R4 and R5 together with the nitrogen atom to which they are attached form a heterocyclic ring which may contain a further heteroatom, such as ~, O or S, e.g. the pyridine ring which may be substituted by OH, NH2, COOH, CN or lower alkyl, or the ring of the formula HC~
The novel basic azo compounds have the formula I
[~ ~ 5 ~ \ D ~ - N =~N ~ ~ / 1i3 ~
wherein X is one or more of the radicals (CH2.NR.CO(CH2)nA) and/or (SO2NH(CH2)nA), R is hydrogen or an alkyl group of 1 to 4 carbon atoms, A
is a non-quaternised or quaternised basic radical, n is 1 to 4, m is 1 to 4 M is hydrogen or any cation, p is 0 to 2, with the proviso that the value is m is as great or greater than p, and wherein the benzene radicals B
obtionally contain one or more identical or different substituents selected from alkyl groups of 1 to 4 carbon atoms, halogen, alkoxy groups having 1 to 4 carbon atoms, N02, OH, S02NH2, S02NH-alkyl Cl-C4, S02N(alkyl Cl-C4)2, benzthiazol, S02-heterocyclic with an N-atom linked to S02, unsubstituted phenyl, and phenyl substituted by halogen and alkyl Cl-C4, and the benzene radicals D optionally contain one or more identical or different substituents namely halogen, alkyl Cl-C4~and alkoxy Cl-C4.
R as an alkyl group of 1 to 4 carbon atoms is e.g. an unbranched or a brqched alkyl group, for example the methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl group. In preferred azo compounds, R is hydrogen.
As a non-quaternised or quaternised basic group, A has e.g. the following values:
a) as a basic group, e.g. the radical ~ T
~ T
~ - 1 -~ *
.: .
113~317 wherein Tl is hydrogen or a low molecular alkyl radical which i5 unsub-stituted or substituted by hydroxyl, or a cyclohexyl radical which is Imsubstituted or substituted by 1 to 3 methyl radicals, or is a phenyl radical, and T2 is a low molecular alkyl radical which is unsubstitu-ted or substituted by hydroxyl, or Tl and T2 together with the nitro-gen atom to which they are at~ached form a hydrogenated heterocyclic ring which may contain a further heteroatom, e.g. the morpholine ring:
b~ as a quaternised group, e.g. the radical of the formula Rl a ) (~ R2 ~ ~) . . . 2 wherein each of Rl and R2 independently is hydrogen, an alkyl radical of 1 to 4 carbon atoms which is unsubstituted or substituted e.g. by hydroxyl, such as the methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl radical, an unsubstituted or sub8tituted cycloalykl group, especially the cyclohexyl group which is unsubstitu-ted or substituted by one or more alkyl groups, in particular the C~3 group, or is an aryl radical, especially the phenyl radical; or R
and R2 together with the nitrogen atom to which they are attached form a heterocyclic ring, such as the pyrrolidine, piperidine, morpho-line or piperazine ring, b) - ~ - R
S
wherein each of R3 and R4 independently is hydrogen, an unsubstituted or substituted alkyl radical of 1 to 4 carbon atoms, such as the methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl radical, or the hydroxyethyl or aminoethyl radical; an unsubstituted or substituted cycloalkyl group, especially the cyclohexyl group, or an aryl radical, such as the phenyl radical, and R5 is an alkyl group .
1~3~817 of 1 to 4 carbon atoms; or R3 and R4 together with the nitrogen atom to which they are attached form a heterocyclic ring, in particular the pyrrolidine, piperidine, morpholine or piperazine ring; or R3, R4 and R5 together with the nitrogen atom to which they are attached form a heterocyclic ring which may contain a further heteroatom, such as ~, O or S, e.g. the pyridine ring which may be substituted by OH, NH2, COOH, CN or lower alkyl, or the ring of the formula HC~
2 H2 c) -(~ - R2 ~ X ~) ... . . . . .
wherein Rl ant R2 have the meanings assigned to them under a) and R6 is an alkyl radical of l to 4 carbon atoms, ant wherein in all quater-nised basic radicals, X~i8 an anion.
In preferred azo compounds, A is a pyridine ring and X ~ is any anion.
Where A is a quaternised basic group, suitable anions are both inorganic and organic anions, e.g.: halogen, such as chloride, bromide or iodide, sulfate, methyl sulfate, aminosulfate, perchlorate, carbo-..
nate, bicarbonate, phosphate, phosphomolybdate, phosphotungstate,phosphotungstomolybdate, benzenesulfonate, naphthalenesulfonate, 4-chlorobenzenesulfonate, oxalate, maleate, acetate, propionate, lactate, succinate, chloroacetate, tartrate, methanesulfonate or benzoate ions, or complex anions, such as those of zinc chloride double salts. Preferred anions are the chloride, acetate, zinc chloride .
or methyl sulfate ions.
1~3g~1~
M as a cation is e.g. the Li, Na, K or NH4 ion; preferably it is the Na ion.
If the benzene radicals B are further substituted, they can contain one or more identical or different substituents, e.g. an alkyl group of 1 to 4 carbon atoms, halogen, such as fluorine, chlorine or bromine, a phenyl group which is unsubstituted or substituted e.g.
by halogen or alkyl; an alkoxy group, N02, OH, a S02NH2 group which is mono- or disubstituted (e.g. by alkyl) at the nitrogen atom, an S2 ~ ~ group in which the nitrogen atom, optionally together with a further heteroatom, e.g. an oxygen atom, forms part of a heterocyclic ring; or a heterocyclic group, especially the benzthiazole group.
In preferred azo compounds, the benzene radicals B are further substituted by an alkyl group of 1 to 2 carbon atoms, especially by the CH3 group, in particular in the para-position to the nitrogen atom.
If the benzene raticals D are further substitutet, these can also contain one or more itentical or different substituents, e.g.
halogen, such as fluorine, chlorine or bromine; alkyl or alkoxy groups, each containing 1 to 4 carbon atoms, e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl, or methoxy, ethoxy, propoxy or butoxy. In preferred azo compounds, the benzene radicals D
are not further substituted.
Particularly interesting azo compounds are those of the formula I, ~herein R is hydrogen, A is a quaternised basic radical, especially one of the formula . .. ..
- R
wherein R3, R4 and R5 together with the nitrogen atom to which they :, .
.
113~817 are attached are linked to a pyridine ring, and X ~ is any anion, n is 1 and m is 2, p is O, and wherein the benzene radical B is further substituted by an alkyl group of 1 to 2 carbon atoms, especially by l:he CH3 group, and the benzene radical D is not further substituted.
The azo compounds of the formula I are obtained in known manner. One possibility consists e.g. in a) introducing the group -CH27-CO-(CH2)n-halogen and/or -S02NH(CH2) -halogen wherein R and n are as defined for formula I, 1 to 4 times into an azo compound of ~he formula II
~ 3 ~ -\ D / \ , / ~ \.~ (II) ~, wherein B and D are as defined for formula I, then replacing the halogen atom by a basic group A or by a quaternised basic group A ~ X ~ wherein X ~ is any anion, and, if desired, converting the basic group A by quaternisation into a quaternised basic group, and if desired, subsequently introducing a SO3M group; or b) introducing the group -CH2-~-CO-(CH2)n-A and/or -S02NH(CH2)nA
R
wherein A is a basic group and R and n are as defined for formula I, 1 to 4 times into an azo compound of the formula II, and, if desired, subsequently quaternising the basic group A and then, if desired, introducing a SO3-M group.
The starting compounds of the formula II are ~nown (Helv. Chem.
Acta 1944, p. l ff) and can be obtained by known methods.
.. .
: : . :
: ~ .
.. : .
-': ' ' .
~13~817 Finally, a further variant for obtaining the compounds of theformula I consists in introducing the group -(CH2NR.CO.(CH2) A) and/or -S02NH(CH2) A 1 to 2 times into an amine of the formula I~ 5 ~ D ~--NH2 subsequently, if desired, sulfonating and diazotising and proceeding analogously in accordance with Helv. Chem. Acta 1944, p. 1 ff.
In this variant of the process, the introduction of a quaterni-sable basic group -CH2-N(R)-C0-(CH2)nA and~or -S02NH(CH2)nA, wherein R, A and n are as defined for formula I, is accomplished in known manner, e.g. by reacting the compound of the formula II with e.g.
N-methylolchloroacetamide in concentrated sulfuric acid or phosphoric acid, optionally in the presence of P205, at 0 to 50C, preferably at room temperature, and then, by amination, replacing the chlorine atom of N~methylolchloroacetamite by a basic or especially a cationic group A, or by replacing the chlorine atom of N-methylolchloroacetamite by a basic group A and then converting this basic group by quaterni-sation into a quaterniset group A.
The quaternisation is also carried out in known manner, e.g. in an inert solvent such as chlorobenzene, or, if tesired, in an aqueous suspension or without a solvent in an excess of the quaternising agent, at a temperature of about 20 to 120C, with a quaternising agent.
~ xamples of suitable quaternising agents are alkyl halides, such as methyl or ethyl chloride, methyl, ethyl or butyl bromide, or methyl or ethyl iodide, and especially alkyl sulfates, such as di-methyl, diethyl or dibutyl sulfate, or benzyl chloride, chloroacet- :
amide, acrylates, epoxide~, such as ethylene oxide, epichlorohydrin and alkyl esters of aromatic sulfonic acids, such as methyl-p-toluene-sulfonate, methylbenzene sulfonate, ant the propyl and butyl esters of . , .
-~3~817 benzenesulfonic acid.
Should it be desired that the azo compounds of the formula I containa -S03-M group, then this group can be introduced before or after the quaternisation reaction, e.g. by sulfonation with sulfuric acid.
The novel basic non-quaternised or quaternised azo compounds of the formula I are employed as dyes for dyeing and printing textiles, leather and paper and also for the preparation of inks.
Thus, this invention also provides for a process for colouring and printing textiles, paper and leather and for the preparation of inks, as well as for the mass colouration of synthetic linear polyamides and for the pro-duction of lacquers by using an azo compound of the invention or the azo compound obtained by the process of the invention as a dye.
Suitable textiles for dyeing and printing with these dyes are:
natural and regenerated cellulosic fabrics, especially cotton and viscose, on which fabrics brilliant yellow dyeings are obtained; natural polyamide material, such as wool and silk, and acid-modified polyamide material, as well as acrylic fibres, especially wet tow and modified polyester material which can be dyed with basic dyes. The azo compounds of the formula I have good affinity for these textiles, especially on cellulosic fabrics, a good degree of exhaustion, and the dyeings obtained have very good fastness proper-ties, in particular wetfastness properties, such as fastness to water, water/
alcohol, and especially light.
It is furthermore advantageous that the azo compounds of the formula I exhaust onto the cellulose material without subjecting the material to a pretreatment and without the further addition of salt to the dyebath.
The azo compounds of the formula I are yellow compounds. For their application it is further not necessary to add fixing agents to the bath.
`~3 . - 7 -113~81~
A further utility of the azo compounds of the formula I is for colouring paper of all kinds, especially of bleached, unsized and - 7a -`~
, ~ , .
. ~
~13~817 sized lignin-free paper. In particular, the lightfastness on paper is unexpectedly high to a degree which is not usually obtained with con-ventional yellow dyes for paper, thereby affording the possibility of using the dyes of the invention in the document sector. These compounds are most suitable for colouring unsized paper (tissues) on account of their very high standard affinity for this substrate.
The azo compounds of the invention exhaust very well onto these substrates, while the wastewaters remain virtually colourless even in the production of deep shades (up to 1~1 reference type strength).
This is a prime ecological advantage, especially in view of present wastewater legislation, and also whenever the process is carried out with wastewater recycling.
The dyeings are wetfast, i.e. they show no tentency to bleeding when coloured paper in the wet state is brought into contact with moist white paper. This is an especially tesirable property for tissues, with which it is to be expected that the colouret paper in the wet state (e.g. soaked with water, alcohol, surfactant solution etc.) will come into contact with other surfaces, such as textiles, paper and the like, which have to be protected against soiling.
The high affinity for paper and the high rate of exhaustion of the azo dyes of the formula I is most advantageous for the continous colouration of paper and thus makes possible a much broader use of this economic procesr, which has the following advantages:
a) a simpler and more rapid correction of the shade and therefore less loss of non-standard paper (broke) in comparison with the batchwise colouring of pulp;
b) a better constancy of shade; and c) when the dye is added shortly before the stock preparation in the dilute paper pulp, a thorough cleansing of the hollander, mixing chest etc.,after each batch is no longer necessary, while at the same time the operation is shortened and the process optimised.
~.. ~... ._ _.. ..... _. _ .. .. ~.. ... _ .. _ _. .. : .. . ______ ., _ _.. _~__.__. .. __ _. _.. _._. _._.. _ ...
, ,. ~
' : ., ~ '` - :~'' ~3~7 Further, the novel azo compounds are used for dyeing leather material by a very wide variety of application methods, such as spray-ing, brushing and immersing, and for the preparation of inks, especi-ally for ball-point pens.
Finally, the novel a7O compounds of the formula I are used for the mass colouration of synthetic linear polyamides, such as poly-hexamethylene-adipamide. The colouration of the polyamide chips is effected in particular from an aqueous bath in the presence of wetting or dispersing agents and optionally salts, and by subsequent melting and forming.
In view of the reducible properties of the fused polyamide melts and the high melt temperature (about 270-300C), the use of these dyes of the formula I consistutes a surprising enlargement of the stock of technical knowledge, The following Examples illu~trate the invention without implying any restriction to what is described therein. Parts and percentages are by weight.
Example 1: 48 pares of 4,4'-bis(6-methyl-2-benzthiazole)azobenzene I (obtained according to the particulars of Helv. Chem. Acta 1944, 27,1) and 28 parts of N-methylolchloroacetamide are added at 0-50C to 500 parts of 98~ sulfuric acid. The reaction mixture is then stirred for 15 hours at room temperature. The solution is poured on ice, whereupon the reac1ion product precipitates. The precipitate is collected by filtration, washed neutral with water and dried, affor-ding 55 parts of the compound of the formula `:
., .., . ..: .. .. .
r T 11 ~ . .-N~N~ S il t S/ ~ 2N~COC82Cl.
113~B17 30 parts of this compound are heated for 1 hour to 100C in 250 parts of pyridine. The precipitated dye of the formula r .~ s~ ~ ca31 C1~3 is isolated by filtration and dried. It colours paper and cotton in bright yellow shades of very good fastness properties and has excellent build-up.
Similar dycs with equally good properties are obtained by using -picoline or y-picoline, or a mixture of both, instead of pyridine.
Example 2: A mixture of 48 parts of 4,4'-bis(6-methyl-2-benzthiazole)-azobenzene and 40 parts of N-methylolchloroacetamide are added at 0-5C to 500 parts of monohydrate. The reaction mixture iB stirred for 15 hours at 50C ant then pouret on ice. The precipitatet reaction product is then filtered with suction, washéd neutral with water and dried, afforting 68 parts of the compounds of the formula ~ t i~ --N-N-- ~-- f ~
~ 2N~COC~2C~ 2 30 parts of this compound are reacted with 250 parts of pyridine as described in Example 1. The resultant dye of the formula N N ~
. .
.
li3~L131 7 exhausts very well on paper and cotton and the bright yellow dyeings obtained have excellent wetfastness properties and very good light-fastness.
The above procedure is repeated, substituting 200parts of o-di-chlorobenzene and 15 parts of triethylenediamine for the 250 parts of pyridine. The product is the cationic compound of the formula - t il ~ N-N--; ~- - ~ 2Cl~
L /1~ 2~C~2 which colours paper and cotton in bright yellow shades and exhausts well.
I Example 3: 25.4 parts of the compound of the formula ~03H
C~ ~ / \6/ \ ~ \ fi S03H_ are stirred in 80 parts of chlorosulfonic acid for 6 hours at 90C.
The reaction mixture is then poured on ice and the precipitate is filtered with suction and washed weakly acid with 2% NaCl solution.
The moist sulfochloride is added at 0-5C to a mixture of 16.4 parts of 3-dimethylamino-l-propylamine, 120 parts of ice and 16 parts of sodium acetate. The reaction mixture is stirred for 10 hours at 20-25C and the compound of the formula S02NHCH2cH2cH2~(cH3)2 il 5~ N~ - f l;
02NHCH2CH2cH2N(cH3)2 ~134817 is isolated by filtration.
Quaternisation is carried out by boiling this compound with 100 parts of ethylene chlorohydrin at 120C, affording the dye of the formula S02~HCH2CH2CH2~ 2C~20H]Cl ~ 2 ;z ~ ~ ; 2 3 .. .. . . . .. . . . ...
which produces on paper a bright yellow colouration of good fastness to light and water.
Example 4: 50 psrts of chemically bleached beach sulfite are mixed with 50parts of bleached sulfite RKN 15 (degree of freeness 22 SR) aDd 2 p-rts of the dye of the formula C~3~ . / S~ C~3- 2C1~3 i i~ N=N~ ~ 2N~COC~2~ ~
, ,. . .. . _ , .. .
in water (pH 6, water hardness 10 dH,Ite~perature 20C, liquor ratio 1:40). After stirring for 15 minutes, paper sheets are prepared on a Frank sheet former. The paper is coloured in a very intense yellow shade. The wastewater is completely colourless. The de8ree of exhaus-tion is 100%.
The light- and wetfastness properties are excellent. The fast-ness to water determined in accordance with DIN 53 991/SNV 195 806 has e.g. the rating 4. The lightfastness determined in accordance with SNV 196 809 has the rating 6.
:
' ' :
113~817 _.~ample 5: The procedure of Example 4 is repeated, but using 2 parts oE the known dye of the formula
wherein Rl ant R2 have the meanings assigned to them under a) and R6 is an alkyl radical of l to 4 carbon atoms, ant wherein in all quater-nised basic radicals, X~i8 an anion.
In preferred azo compounds, A is a pyridine ring and X ~ is any anion.
Where A is a quaternised basic group, suitable anions are both inorganic and organic anions, e.g.: halogen, such as chloride, bromide or iodide, sulfate, methyl sulfate, aminosulfate, perchlorate, carbo-..
nate, bicarbonate, phosphate, phosphomolybdate, phosphotungstate,phosphotungstomolybdate, benzenesulfonate, naphthalenesulfonate, 4-chlorobenzenesulfonate, oxalate, maleate, acetate, propionate, lactate, succinate, chloroacetate, tartrate, methanesulfonate or benzoate ions, or complex anions, such as those of zinc chloride double salts. Preferred anions are the chloride, acetate, zinc chloride .
or methyl sulfate ions.
1~3g~1~
M as a cation is e.g. the Li, Na, K or NH4 ion; preferably it is the Na ion.
If the benzene radicals B are further substituted, they can contain one or more identical or different substituents, e.g. an alkyl group of 1 to 4 carbon atoms, halogen, such as fluorine, chlorine or bromine, a phenyl group which is unsubstituted or substituted e.g.
by halogen or alkyl; an alkoxy group, N02, OH, a S02NH2 group which is mono- or disubstituted (e.g. by alkyl) at the nitrogen atom, an S2 ~ ~ group in which the nitrogen atom, optionally together with a further heteroatom, e.g. an oxygen atom, forms part of a heterocyclic ring; or a heterocyclic group, especially the benzthiazole group.
In preferred azo compounds, the benzene radicals B are further substituted by an alkyl group of 1 to 2 carbon atoms, especially by the CH3 group, in particular in the para-position to the nitrogen atom.
If the benzene raticals D are further substitutet, these can also contain one or more itentical or different substituents, e.g.
halogen, such as fluorine, chlorine or bromine; alkyl or alkoxy groups, each containing 1 to 4 carbon atoms, e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl, or methoxy, ethoxy, propoxy or butoxy. In preferred azo compounds, the benzene radicals D
are not further substituted.
Particularly interesting azo compounds are those of the formula I, ~herein R is hydrogen, A is a quaternised basic radical, especially one of the formula . .. ..
- R
wherein R3, R4 and R5 together with the nitrogen atom to which they :, .
.
113~817 are attached are linked to a pyridine ring, and X ~ is any anion, n is 1 and m is 2, p is O, and wherein the benzene radical B is further substituted by an alkyl group of 1 to 2 carbon atoms, especially by l:he CH3 group, and the benzene radical D is not further substituted.
The azo compounds of the formula I are obtained in known manner. One possibility consists e.g. in a) introducing the group -CH27-CO-(CH2)n-halogen and/or -S02NH(CH2) -halogen wherein R and n are as defined for formula I, 1 to 4 times into an azo compound of ~he formula II
~ 3 ~ -\ D / \ , / ~ \.~ (II) ~, wherein B and D are as defined for formula I, then replacing the halogen atom by a basic group A or by a quaternised basic group A ~ X ~ wherein X ~ is any anion, and, if desired, converting the basic group A by quaternisation into a quaternised basic group, and if desired, subsequently introducing a SO3M group; or b) introducing the group -CH2-~-CO-(CH2)n-A and/or -S02NH(CH2)nA
R
wherein A is a basic group and R and n are as defined for formula I, 1 to 4 times into an azo compound of the formula II, and, if desired, subsequently quaternising the basic group A and then, if desired, introducing a SO3-M group.
The starting compounds of the formula II are ~nown (Helv. Chem.
Acta 1944, p. l ff) and can be obtained by known methods.
.. .
: : . :
: ~ .
.. : .
-': ' ' .
~13~817 Finally, a further variant for obtaining the compounds of theformula I consists in introducing the group -(CH2NR.CO.(CH2) A) and/or -S02NH(CH2) A 1 to 2 times into an amine of the formula I~ 5 ~ D ~--NH2 subsequently, if desired, sulfonating and diazotising and proceeding analogously in accordance with Helv. Chem. Acta 1944, p. 1 ff.
In this variant of the process, the introduction of a quaterni-sable basic group -CH2-N(R)-C0-(CH2)nA and~or -S02NH(CH2)nA, wherein R, A and n are as defined for formula I, is accomplished in known manner, e.g. by reacting the compound of the formula II with e.g.
N-methylolchloroacetamide in concentrated sulfuric acid or phosphoric acid, optionally in the presence of P205, at 0 to 50C, preferably at room temperature, and then, by amination, replacing the chlorine atom of N~methylolchloroacetamite by a basic or especially a cationic group A, or by replacing the chlorine atom of N-methylolchloroacetamite by a basic group A and then converting this basic group by quaterni-sation into a quaterniset group A.
The quaternisation is also carried out in known manner, e.g. in an inert solvent such as chlorobenzene, or, if tesired, in an aqueous suspension or without a solvent in an excess of the quaternising agent, at a temperature of about 20 to 120C, with a quaternising agent.
~ xamples of suitable quaternising agents are alkyl halides, such as methyl or ethyl chloride, methyl, ethyl or butyl bromide, or methyl or ethyl iodide, and especially alkyl sulfates, such as di-methyl, diethyl or dibutyl sulfate, or benzyl chloride, chloroacet- :
amide, acrylates, epoxide~, such as ethylene oxide, epichlorohydrin and alkyl esters of aromatic sulfonic acids, such as methyl-p-toluene-sulfonate, methylbenzene sulfonate, ant the propyl and butyl esters of . , .
-~3~817 benzenesulfonic acid.
Should it be desired that the azo compounds of the formula I containa -S03-M group, then this group can be introduced before or after the quaternisation reaction, e.g. by sulfonation with sulfuric acid.
The novel basic non-quaternised or quaternised azo compounds of the formula I are employed as dyes for dyeing and printing textiles, leather and paper and also for the preparation of inks.
Thus, this invention also provides for a process for colouring and printing textiles, paper and leather and for the preparation of inks, as well as for the mass colouration of synthetic linear polyamides and for the pro-duction of lacquers by using an azo compound of the invention or the azo compound obtained by the process of the invention as a dye.
Suitable textiles for dyeing and printing with these dyes are:
natural and regenerated cellulosic fabrics, especially cotton and viscose, on which fabrics brilliant yellow dyeings are obtained; natural polyamide material, such as wool and silk, and acid-modified polyamide material, as well as acrylic fibres, especially wet tow and modified polyester material which can be dyed with basic dyes. The azo compounds of the formula I have good affinity for these textiles, especially on cellulosic fabrics, a good degree of exhaustion, and the dyeings obtained have very good fastness proper-ties, in particular wetfastness properties, such as fastness to water, water/
alcohol, and especially light.
It is furthermore advantageous that the azo compounds of the formula I exhaust onto the cellulose material without subjecting the material to a pretreatment and without the further addition of salt to the dyebath.
The azo compounds of the formula I are yellow compounds. For their application it is further not necessary to add fixing agents to the bath.
`~3 . - 7 -113~81~
A further utility of the azo compounds of the formula I is for colouring paper of all kinds, especially of bleached, unsized and - 7a -`~
, ~ , .
. ~
~13~817 sized lignin-free paper. In particular, the lightfastness on paper is unexpectedly high to a degree which is not usually obtained with con-ventional yellow dyes for paper, thereby affording the possibility of using the dyes of the invention in the document sector. These compounds are most suitable for colouring unsized paper (tissues) on account of their very high standard affinity for this substrate.
The azo compounds of the invention exhaust very well onto these substrates, while the wastewaters remain virtually colourless even in the production of deep shades (up to 1~1 reference type strength).
This is a prime ecological advantage, especially in view of present wastewater legislation, and also whenever the process is carried out with wastewater recycling.
The dyeings are wetfast, i.e. they show no tentency to bleeding when coloured paper in the wet state is brought into contact with moist white paper. This is an especially tesirable property for tissues, with which it is to be expected that the colouret paper in the wet state (e.g. soaked with water, alcohol, surfactant solution etc.) will come into contact with other surfaces, such as textiles, paper and the like, which have to be protected against soiling.
The high affinity for paper and the high rate of exhaustion of the azo dyes of the formula I is most advantageous for the continous colouration of paper and thus makes possible a much broader use of this economic procesr, which has the following advantages:
a) a simpler and more rapid correction of the shade and therefore less loss of non-standard paper (broke) in comparison with the batchwise colouring of pulp;
b) a better constancy of shade; and c) when the dye is added shortly before the stock preparation in the dilute paper pulp, a thorough cleansing of the hollander, mixing chest etc.,after each batch is no longer necessary, while at the same time the operation is shortened and the process optimised.
~.. ~... ._ _.. ..... _. _ .. .. ~.. ... _ .. _ _. .. : .. . ______ ., _ _.. _~__.__. .. __ _. _.. _._. _._.. _ ...
, ,. ~
' : ., ~ '` - :~'' ~3~7 Further, the novel azo compounds are used for dyeing leather material by a very wide variety of application methods, such as spray-ing, brushing and immersing, and for the preparation of inks, especi-ally for ball-point pens.
Finally, the novel a7O compounds of the formula I are used for the mass colouration of synthetic linear polyamides, such as poly-hexamethylene-adipamide. The colouration of the polyamide chips is effected in particular from an aqueous bath in the presence of wetting or dispersing agents and optionally salts, and by subsequent melting and forming.
In view of the reducible properties of the fused polyamide melts and the high melt temperature (about 270-300C), the use of these dyes of the formula I consistutes a surprising enlargement of the stock of technical knowledge, The following Examples illu~trate the invention without implying any restriction to what is described therein. Parts and percentages are by weight.
Example 1: 48 pares of 4,4'-bis(6-methyl-2-benzthiazole)azobenzene I (obtained according to the particulars of Helv. Chem. Acta 1944, 27,1) and 28 parts of N-methylolchloroacetamide are added at 0-50C to 500 parts of 98~ sulfuric acid. The reaction mixture is then stirred for 15 hours at room temperature. The solution is poured on ice, whereupon the reac1ion product precipitates. The precipitate is collected by filtration, washed neutral with water and dried, affor-ding 55 parts of the compound of the formula `:
., .., . ..: .. .. .
r T 11 ~ . .-N~N~ S il t S/ ~ 2N~COC82Cl.
113~B17 30 parts of this compound are heated for 1 hour to 100C in 250 parts of pyridine. The precipitated dye of the formula r .~ s~ ~ ca31 C1~3 is isolated by filtration and dried. It colours paper and cotton in bright yellow shades of very good fastness properties and has excellent build-up.
Similar dycs with equally good properties are obtained by using -picoline or y-picoline, or a mixture of both, instead of pyridine.
Example 2: A mixture of 48 parts of 4,4'-bis(6-methyl-2-benzthiazole)-azobenzene and 40 parts of N-methylolchloroacetamide are added at 0-5C to 500 parts of monohydrate. The reaction mixture iB stirred for 15 hours at 50C ant then pouret on ice. The precipitatet reaction product is then filtered with suction, washéd neutral with water and dried, afforting 68 parts of the compounds of the formula ~ t i~ --N-N-- ~-- f ~
~ 2N~COC~2C~ 2 30 parts of this compound are reacted with 250 parts of pyridine as described in Example 1. The resultant dye of the formula N N ~
. .
.
li3~L131 7 exhausts very well on paper and cotton and the bright yellow dyeings obtained have excellent wetfastness properties and very good light-fastness.
The above procedure is repeated, substituting 200parts of o-di-chlorobenzene and 15 parts of triethylenediamine for the 250 parts of pyridine. The product is the cationic compound of the formula - t il ~ N-N--; ~- - ~ 2Cl~
L /1~ 2~C~2 which colours paper and cotton in bright yellow shades and exhausts well.
I Example 3: 25.4 parts of the compound of the formula ~03H
C~ ~ / \6/ \ ~ \ fi S03H_ are stirred in 80 parts of chlorosulfonic acid for 6 hours at 90C.
The reaction mixture is then poured on ice and the precipitate is filtered with suction and washed weakly acid with 2% NaCl solution.
The moist sulfochloride is added at 0-5C to a mixture of 16.4 parts of 3-dimethylamino-l-propylamine, 120 parts of ice and 16 parts of sodium acetate. The reaction mixture is stirred for 10 hours at 20-25C and the compound of the formula S02NHCH2cH2cH2~(cH3)2 il 5~ N~ - f l;
02NHCH2CH2cH2N(cH3)2 ~134817 is isolated by filtration.
Quaternisation is carried out by boiling this compound with 100 parts of ethylene chlorohydrin at 120C, affording the dye of the formula S02~HCH2CH2CH2~ 2C~20H]Cl ~ 2 ;z ~ ~ ; 2 3 .. .. . . . .. . . . ...
which produces on paper a bright yellow colouration of good fastness to light and water.
Example 4: 50 psrts of chemically bleached beach sulfite are mixed with 50parts of bleached sulfite RKN 15 (degree of freeness 22 SR) aDd 2 p-rts of the dye of the formula C~3~ . / S~ C~3- 2C1~3 i i~ N=N~ ~ 2N~COC~2~ ~
, ,. . .. . _ , .. .
in water (pH 6, water hardness 10 dH,Ite~perature 20C, liquor ratio 1:40). After stirring for 15 minutes, paper sheets are prepared on a Frank sheet former. The paper is coloured in a very intense yellow shade. The wastewater is completely colourless. The de8ree of exhaus-tion is 100%.
The light- and wetfastness properties are excellent. The fast-ness to water determined in accordance with DIN 53 991/SNV 195 806 has e.g. the rating 4. The lightfastness determined in accordance with SNV 196 809 has the rating 6.
:
' ' :
113~817 _.~ample 5: The procedure of Example 4 is repeated, but using 2 parts oE the known dye of the formula
3\ ~-\ /S \ .,. .,. / S\ ~ ca~ ~ C~
i li ~ N-N~ i 11 \ t~
- _ _ c~2-~-Na~ 2Cl'' The paper is coloured in the same intense yellow shade as in Example 4.
! The degree of exhaustion, however, is only about 95%. The waterfast-ness rating is only 2.
Example 6: The procedure of Example 4 is repeated, but using 2 parts of the known dye of the formula , C~3~ S \ ~ /C~3-t il N~ --N~N--~ I ~ 3~)2 .
The paper is coloured in a similar, somewhat brighter yellow shade than in Example 4. The degree of exhaustion is only just 90%. The wastewater is intensely coloured. The waterfastness rating is below 2 Example 7: A paper web of bleached beach sulfite (22 SR) is pre-pared on a continously operating laboratory paper machine. Ten seconds before the stock preparation, an aqueous solution of the dye of the formula .. .. . .
~ C~3- 2Cl~
t 11 _-~ ~--N=N--~ ~-- 11 t f G~D-~
~ , , , ~ , is added continously to the dilute pulp with vigorous turbulence (0.5 colouration, liquor ratio 1:400, water hardness 10 dH, pH 6, tempe-~' ~
~13~8i7 rature 20C).
The paper web is coloured a level yellow shade of averageintensity and of very good wet- and lightfastness. The wastewater i9 completely colourless.
Example 8: 10 parts of cotton fabric (bleached mercerised cotton) are dyed in a labora~ory beam dyeing machine in 200 part of a liquor (water hardness 10 dH, pH 4, 3 circulations of the liquor per min-ute) which contains 0.05 part of the dye of the formula r~3~ . f~ B31 -- 2Cl~
~ --N5N--~ ! ! ~ ~3 3-~;
_ ~ ... ~ _ _ :a2NE~COCa2N~; ~
The temperature is raised in the course of 60 minutes to 20-100C, then kept constant for 15 minutes.
The tyebath i8 completely exhaustet ant the cotton fabric is tyet in an intense yellow shate. The tyeing i9 distinguished by very good lightfastness and very goot wetfastness which compares with that of a vat tyeing.
i li ~ N-N~ i 11 \ t~
- _ _ c~2-~-Na~ 2Cl'' The paper is coloured in the same intense yellow shade as in Example 4.
! The degree of exhaustion, however, is only about 95%. The waterfast-ness rating is only 2.
Example 6: The procedure of Example 4 is repeated, but using 2 parts of the known dye of the formula , C~3~ S \ ~ /C~3-t il N~ --N~N--~ I ~ 3~)2 .
The paper is coloured in a similar, somewhat brighter yellow shade than in Example 4. The degree of exhaustion is only just 90%. The wastewater is intensely coloured. The waterfastness rating is below 2 Example 7: A paper web of bleached beach sulfite (22 SR) is pre-pared on a continously operating laboratory paper machine. Ten seconds before the stock preparation, an aqueous solution of the dye of the formula .. .. . .
~ C~3- 2Cl~
t 11 _-~ ~--N=N--~ ~-- 11 t f G~D-~
~ , , , ~ , is added continously to the dilute pulp with vigorous turbulence (0.5 colouration, liquor ratio 1:400, water hardness 10 dH, pH 6, tempe-~' ~
~13~8i7 rature 20C).
The paper web is coloured a level yellow shade of averageintensity and of very good wet- and lightfastness. The wastewater i9 completely colourless.
Example 8: 10 parts of cotton fabric (bleached mercerised cotton) are dyed in a labora~ory beam dyeing machine in 200 part of a liquor (water hardness 10 dH, pH 4, 3 circulations of the liquor per min-ute) which contains 0.05 part of the dye of the formula r~3~ . f~ B31 -- 2Cl~
~ --N5N--~ ! ! ~ ~3 3-~;
_ ~ ... ~ _ _ :a2NE~COCa2N~; ~
The temperature is raised in the course of 60 minutes to 20-100C, then kept constant for 15 minutes.
The tyebath i8 completely exhaustet ant the cotton fabric is tyet in an intense yellow shate. The tyeing i9 distinguished by very good lightfastness and very goot wetfastness which compares with that of a vat tyeing.
Claims
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An azo compound of the formula I
(I) wherein X is one or more of the radicals (CH2.NR. CO(CH2)nA) and/or (SO2NH(CH2)nA), R is hydrogen or an alkyl group of 1 to 4 carbon atoms, A
is a non-quaternised or quaternised basic radical, n is 1 to 4, m is 1 to 4, M is hydrogen or any cation, p is O to 2, with the proviso that the value of m is as great or greater than p, and wherein the benzene radicals B
optionally contain one or more identical or different substituents, selected from alkyl groups of 1 to 4 carbon atoms, halogen, alkoxy groups having 1 to 4 carbon atoms, NO2, OH, SO2NH2, SO2NH-alkyl C1-C4, SO2N(alkyl C1-C4)2, benzthiazol, SO2-heterocyclic with an N-atom linked to SO2, unsubstituted phenyl, and phenyl substituted by halogen and alkyl C1-C4, and the benzene radicals D optionally contain one or more identical or different substituents namely halogen, alkyl C1-C4 and alkoxy C1-C4.
2. An azo compound of the formula I according to claim 1, wherein X is the radical (CH2.NR.CO(CH2)nA).
3. An azo compound of the formula I according to claims 1 and 2, wherein R is hydrogen.
4. An azo compound of the formula I according to claim 1, wherein A
is a quaternised basic radical.
5. An azo compound of the formula I according to claim 4, wherein A is one of the following quaternised basic radicals:
a) wherein each of R1 and R2 independently is hydrogen, an alkyl radical of 1 to 4 carbon atoms, unsubstituted or substituted by OH a cycloalkyl group, unsub-stituted or substituted by C1-C4 alkyl or an aryl radical; or R1 and R2 together with the nitrogen atom to which they are attached form a heter-ocyclic ring;
b) wherein each of R3 and R4 independently is hydrogen, an alkyl radical of 1 to 4 carbon atoms, unsubstituted or substituted by OH and NH2 cycloalkyl group or an aryl group, and R5 is an alkyl group of 1 to 4 carbon atoms, or R3 and R4 or R3, R4 and R5 together with the nitrogen atom to which they are attached form a heterocyclic ring;
wherein R1 and R2 are as defined above under a) and R6 is an alkyl radical of 1 to 4 carbon atoms, and wherein in all quaternised basic radicals, X?
is an anion.
6. An azo compound of the formula I according to claim 5, wherein A
is a pyridine ring and X? is any anion.
7. An azo compound of the formula I according to claim 1, wherein n is 1.
8. An azo compound of the formula I according to claim 1, wherein m is 2.
9. An azo compound of the formula I according to claim 1, wherein p is 0.
10. An azo compound of the formula I according to claim 1, wherein benzene radicals B are substituted by an alkyl group containing 1 to 2 carbon atoms.
11. An azo compound according to claim 1, wherein the benzene radicals D do not contain further substituents.
12. An azo compound of the formula I according to claim 1, wherein R
is hydrogen, A is a quaternised basic radical, n is 1, m is 2 and p is 0, and wherein the benzene radical B is substituted by an alkyl group containing 1 to 2 carbon atoms and the benzene radical D is not further substituted.
13. An azo compound according to claim 11, wherein A is a pyridine ring and X? is any anion.
14. An azo compound of the formula 15. A process for the production of an azo compound of the formula I
according to claim 1, which process comprises a) introducing the group -CH2-?-CO(CH2)n-halogen and/or -SO2NH(CH2)n-halogen wherein R and n are defined for formula I, 1 to 4 times into an azo compound of the formula II
(II) wherein B and D are as defined for formula I, then replacing the halogen atom by a basic group A or by a quaternised basic group A?] X?, wherein X? is any anion, and, if desired, converting the basic group A by quaternisation into a quaternised basic group, and if desired, subsequently introducing a SO 3M group, or b) introducing the group and/or -SO2NH(CH2)nA
wherein A is a basic group and R and n are as defined for formula I, 1 to 4 times into an azo compound of the formula II, and, if desired, subsequently quaternising the basic group A and then, if desired, introducing a SO3-M group.
16. A process for colouring and printing textiles, paper and leather and for the preparation of inks, as well as for the mass colouration of syn-thetic linear polyamides and for the production of lacquers by using an azo compound according to claim 1 or the azo compound obtained by the process claimed in claim 15 as a dye.
17. A process for cpolouring and printing natural regenerated cellulosic fabrics, without the addition of salt by using an azo compound according to claim 1 or the azo compound obtained by the process claimed in claim 15 as a dye.
18. A process for colouring and printing paper of all kinds by using an azo compound according to claim 1 or the azo compound obtained by the process claimed in claim 15.
19. A process for colouring and printing lignin-free, bleached paper (tissues) by using an azo compound according to claim 1 or the azo compound obtained by the process claimed in claim 15.
20. A process for colouring and printing natural polyamide material or modified polyamide which can be dyed by basic dyes by using an azo compound according to claim 1 or the azo compound obtained by the process claimed in claim 15 as a dye.
21. A process for colouring and printing acrylic fabrics by using an azo compound according to claim 1 or the azo compound obtained by the process claimed in claim 15.
22. A process for colouring and printing modified polyester material which can be dyed by basic dyes by using an azo compound according to claim 1 or the azo compound obtained by the process claimed in claim 15 as a dye.
23. A process for colouring and printing cotton and viscose without the addition of salt by using an azo compound according to claim 1 or the azo compound obtained by the process claimed in claim 15 as a dye.
24. A process for colouring and printing wool or silk by using an azo compound according to claim 1 or the azo compound obtained by the process claimed in claim 15 as a dye.
25. The material which is dyed or printed with an azo dye according to
claim 1.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1040/79-6 | 1979-02-02 | ||
| CH104079 | 1979-02-02 | ||
| CH6280 | 1980-01-07 | ||
| CH62/80-5 | 1980-01-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1134817A true CA1134817A (en) | 1982-11-02 |
Family
ID=25683400
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000344770A Expired CA1134817A (en) | 1979-02-02 | 1980-01-31 | Azo compounds |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0014677B1 (en) |
| BR (1) | BR8000640A (en) |
| CA (1) | CA1134817A (en) |
| DE (1) | DE3060981D1 (en) |
| ES (1) | ES8100670A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5212312A (en) * | 1980-12-23 | 1993-05-18 | Ciba-Geigy Ag | Vattable and non-vattable quinoid dyes |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3164935D1 (en) * | 1980-02-18 | 1984-08-30 | Basf Ag | Dyestuffs containing imidazolylethylene groups and their use |
| DE3030197A1 (en) * | 1980-08-09 | 1982-04-01 | Sandoz-Patent-GmbH, 7850 Lörrach | ORGANIC COMPOUNDS, THEIR PRODUCTION AND USE |
| JPS57164156A (en) * | 1981-01-23 | 1982-10-08 | Ciba Geigy Ag | Azo dye and manufacture |
| US4525583A (en) * | 1982-01-19 | 1985-06-25 | Ciba-Geigy Corporation | Quaternary ammonium substituted benzothiazolylphenyl azo pyrimidine dyes |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB576270A (en) * | 1944-05-08 | 1946-03-26 | Norman Hulton Haddock | New yellow azo dyestuffs |
| CH447422A (en) * | 1963-05-31 | 1967-11-30 | Sandoz Ag | Process for the production of dyes |
| FR1495232A (en) * | 1965-09-28 | 1967-09-15 | Allied Chem | New bis (benzothiazolyl) azobenzene dyes and their preparation process |
| DE2403736A1 (en) * | 1973-02-01 | 1974-08-08 | Sandoz Ag | SULPHONIC ACID GROUP-FREE BASIC AZO COMPOUNDS, THEIR PRODUCTION AND USE |
-
1980
- 1980-01-28 EP EP19800810023 patent/EP0014677B1/en not_active Expired
- 1980-01-28 DE DE8080810023T patent/DE3060981D1/en not_active Expired
- 1980-01-31 CA CA000344770A patent/CA1134817A/en not_active Expired
- 1980-02-01 ES ES488195A patent/ES8100670A1/en not_active Expired
- 1980-02-01 BR BR8000640A patent/BR8000640A/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5212312A (en) * | 1980-12-23 | 1993-05-18 | Ciba-Geigy Ag | Vattable and non-vattable quinoid dyes |
Also Published As
| Publication number | Publication date |
|---|---|
| BR8000640A (en) | 1980-10-21 |
| EP0014677B1 (en) | 1982-10-27 |
| EP0014677A3 (en) | 1980-10-15 |
| DE3060981D1 (en) | 1982-12-02 |
| ES488195A0 (en) | 1980-12-01 |
| ES8100670A1 (en) | 1980-12-01 |
| EP0014677A2 (en) | 1980-08-20 |
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