Manufacture of Mordant-dyeing Colouring Matters.
Year: 1893

page_text: Date of Application, 17th July, 1893
Complete Specification Left, 16th Apr., 1894-Accepted, 19th May,
1894
PROVISIONAL SPECIFICATION.
FÜR
[Communicated from abroad by THE ACTIEN GESELLSCHAFT
ANILIN FABRIKATION, of Berlin, in the Empire of Germany, Chemical
Manufacturers.]
Manufacture of Mordant-dyeing Colouring Matters.
I, CHARLES DENTON ABEL of No. 28 Southampton Buildings, Chancery
Lane in the County of London, Consulting Engineer and Chartered Patent
Agent do hereby declare the nature of this invention to be as follows:-
-
The invention relates to the production of azo-colours derived from a-amido-
3 naphthol (NH2: OH=1:2) and certain sulpho acids of the same.
My foreign correspondents have discovered that the presence of the amido and
hydroxyl group in ortho-position has a most important influence upon the properties
of the resulting dyes. As is well known, the colouring matters which contain the
following groups, namely: OH and OH, OH and COOH, OH and NO in ortho-
position are capable of forming lakes with metallic salts, and may, therefore, be
fixed on fibre by means of metallic mordants, as for instance, chromium salts.
Now my foreign correspondents have found that the same property belongs to
those dyes which are formed by combining diazo- or tetrazo-compounds with the
before mentioned amido-naphthol and the following sulpho acids of the same :
Amido-naphthol monosulpho-acids, NH₂ : OH : SO₂ = 1 : 2 : 6
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Witt in his publication (Berichte d. Deutschen. Chem. Gesellschaft 21. 3475 pp.)
has mentioned that these two sulpho acids form deeply coloured solutions with
certain diazo-compounds, but he states in his paper that none of these combination
products are capable of dyeing wool.
My foreign correspondents, on the contrary, have discovered that the combination
products of these amido naphthol sulpho acids, as well as of amido-naphthol, are
of high technical value for dyeing wool.
The wool can be dyed in an acid-bath with tints varying from yellow to violet.
If the wool is treated afterwards with a chromium salt, the tints turn from violet-
blue to black-blue. The same result is obtained by dyeing directly with addition
of chromium salt.
The colouring matters above mentioned are distinguished by their great fastness
against fulling and against the action of air and light.
The combination of the amido-naphthol and its aforesaid derivatives with
diazo- or tetrazo-compounds is effected in a neutral or slightly acid solution.
For instance; The colouring matters resulting in this manner from sulphanilic-
acid and amido-naphthol 1.2. dyes wool in an acid bath with a yellowish-red tint,
on addition of a chromium salt, black-violet.
The product obtained from para-nitro-diazobenzene and the amido-naphthol-
sulpho acid 1:2:6 or 1:2:7 yields an orange tint, when fixed on wool in an acid
dye bath whilst, by means of chromium salts, a deep violet-blue tint is produced.
By diazotising naphthionic acid and combining the diazo compound with the
amido-naphthol or the aforesaid sulpho acids, colouring matters are formed that
dye chromium-mordanted wool black-blue. They may be fixed on wool in an
acidulated dye-bath with a bluish-red tint.

page_text: Tetrazo-di-tolyl combined with two molecules of the before mentioned sulpho
acids yields bluish-black colours.
ABEL & IMRAY,
Agents for the Applicant.
Manufacture of Mordant-dyeing Colouring Matters.
I, CHARLES DENTON ABEL, of No. 28, Southampton Buildings, Chancery
Lane, in the County of London, Consulting Engineer and Chartered Patent Agent,
do hereby declare the nature of this invention and in what manner the same is
to be performed, to be particularly described and ascertained in and by the following
statement :-
The invention relates to the production of azo-colours derived from a-amido-
B-naphthol (NH₂: OH = 1 : 2) and certain sulpho acids of the same.
My foreign correspondents have discovered that the presence of the amido and
hydroxyl group in ortho-position has a most important influence upon the properties
of the resulting dyes. As is well known, the colouring matters which contain the
following groups, namely: OH and OH, OH and COOH, OH and NO in ortho-
position are capable of forming lakes with metallic salts, and may, therefore, be
fixed on fibre by means of metallic mordants, as for instance, chromium salts.
Now my foreign correspondents have found that the same property belongs to
those dyes which are formed by combining diazo- or tetrazo-compounds with the
before mentioned amido-naphthol and the following sulpho acids of the same:
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""
"
وو
Witt in his publication (Berichte d. Deutschen. Chem. Gesellschaft 21.3475 pp.)
has mentioned that these two sulpho acids form deeply coloured solutions with
certain diazo-compounds, but he states in his paper that none of these combination
products are capable of dyeing wool.
My foreign correspondents, on the contrary, have discovered that the combination
products of these amido naphthol sulpho acids, as well as of amido-naphthol, are of
high technical value for dyeing wool.
The wool can be dyed in an acid-bath with tints varying from yellow to violet.
If the wool is treated afterwards with a chromium salt, the tints turn from violet-
blue to black-blue. The same result is obtained by dyeing directly with addition
of chromium salt.
The colouring matters above mentioned are distinguished by their great fastness
against fulling and against the action of air and light.
The combination of the amido-naphthol and its aforesaid derivatives with
diazo- or tetrazo-compounds is preferably effected in a neutral or slightly acid
solution.
The following are examples which may serve to illustrate in what manner the
invention may be carried out practically.
Example I. 9 kilos. sulphanilic acid are diazotised in the well known manner;
the paradiazobenzene sulpho acid is combined with 8 kilos. 1 : 2 amido-naphthol,
previously dissolved in dilute acetic acid. The colouring matter produced separates
almost entirely in the form of a crystalline precipitate of black-green lustre ; it is
filtered off, pressed and dried. It dyes wool mordanted with chromium a black
violet shade.
If for the sulphanilic acid other sulphonic acids of amines or amidoazo bodies are
substituted, similar colouring matters are obtained; for example the colouring

page_text: matter prepared with a diazonaphthalensulphonic acid yields a blackish violet blue,.
that prepared with amidoazobenzene sulphonic acid yields a blackish-blue shade on:
mordanted wool.
Example II. 21 kilos. para-nitraniline are diazotised in the well known manner,.
and the free mineral acid is afterwards neutralized by the addition of acetate; the
solution of the diazo-compound is added to a well cooled solution of 41 kilos.
1:26 amidonaphthol sulphonate of sodium; the colouring matter separates as a
brown-violet powder; it produces on wool mordanted with chromium a deep violet-
.blue shade.
For the para nitraniline, other amines may be substituted and also amidoazo bodies
may be used; moreover, in all these cases for the 1:26 amidonaphthol sulpho
acid may be substituted the isomerie 1 :2: 7 amidonaphthol sulpho acid. Generally,
the colouring matters obtained in this way produce shades on wool mordanted with
chromium in which the blackish tint prevails.
Example III. 10.6 kilos. tolidine are converted into tetrazo ditolyl; after
neutralisation of the free. mineral acid by means of acetate, the solution of the
tetrazo compound is added to a solution of 26 kilos. 1:2:6 amidonaphthol
sulphonate of sodium; the colouring matter separates in the form of a dark blue
precipitate, which is filtered off and preferably employed in the form of a paste.
dyes wool mordanted with chromium a blueish-black shade; with a similar shade
it dyes cotton, mordanted with chromium; it may also be fixed on unmordanted
cotton.
It
With a similar result, for the tolidine may be substituted analogous paradiamines,
for instance benzidine and the like.
Example IV. 10-6 kilos. tolidine are converted into tetrazoditolyl-salt and
combined with 11-2 kilos. of a naphthol-a monosulpho acid (Nev.-Winth) to form an
intermediate product, which is afterwards combined with 13 kilos. 1:26 amido-
naphtholsulphonate of sodium in a weakly acetic-acid solution; the product
separates almost entirely in the form of a dark precipitate, it is filtered off and
preferably employed as a paste. It dyes wool mordanted with chromium violet
black and produces on chromium-mordanted cotton gray-violet shades.
For the a naphthol a monosulpho acid in the preceding example may be
substituted other components; if for instance salicylic acid is used, a product is
obtained, which dyes cotton gray brown, and wool mordanted with chromium dark
olive-brown.
Products of similar properties are obtained if, instead of the 1:2:6 acid the
isomeric 1:27 amidonaphtholsulpho acid is employed in the processes illustrated by
the Examples III and IV. If 1:2 amidonaphthol is used for the production of
tetrazo dye stuffs, either the para-diamine or, in case that mixed tetrazo-dyes are to
be produced, the other component used must contain such a number of sulpho and
carboxyl-groups as to render the resulting colouring matter sufficiently soluble in
water.
Example V. For instance, by combining tetrazostilbendisulphonic acid with two
molecules of 1:2 amidonaphthol in presence of a slight excess of acetic
acid, a product is obtained, dyeing wool mordanted with chromium a black violet-
blue shade.
Example VI. By combining tetrazoditolyl with one molecular proportion of
3 naphtholdisulpho acid R and one molecular proportion of 1:2 ainidonaphthol (the
latter combination being effected in presence of acetic acid) a product is obtained
which produces on wool, mordanted with chromium a Bordeaux shade.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed, I declare that what
I claim is :-
1. The herein described manufacture of azo-colouring matters derived from
1:2:6 and 1:2:7 amidonaphtholsulpho acids, by combining with these acids
certain diazo-compounds of amines, amidoazo bodies or the nitro-derivatives,

page_text: sulpho or carbo acids of these substances, other than the diazo compounds above
referred to as having been employed by Witt.
2. The herein described manufacture of tetrazo colouring matters derived from
1:2:6 and 1:2:7 amidonaphtholsulpho acids by combining one molecular
proportion of tetrazotized paradiamine or derivatives thereof with two molecular
proportions of each of the two acids, or with one molecular proportion of one
of the said acids and one molecular proportion of an amine, phenol amidophenol,
or a sulpho or carbo acid thereof other than the tetrazo derivatives employed by
Witt as above referred to.
3. The herein described manufacture of azo colouring matters derived from
1:2 amidonaphthol, by combining the diazo compounds of amines, amidoazo bodies
or their sulpho or carbo acids with the said amidonaphthol.
4. The manufacture of tetrazo-colouring matters derived from 1:2 amido-
naphthol by combining one molecular proportion of a tetrazotised sulpho or carbo
acid of a paradiamine with two molecular proportions of the 1:2 amidonaphthol.
5. The manufacture of mixed tetrazo colouring matters derived from 1: 2 amido-
naphthol by combining one molecular proportion of a tetrazotised para diamine or
a derivative thereof with one molecular proportion of 1:2 amidonaphthol and one
molecular proportion of an amine, phenol or amidophenol or a sulpho or carbo acid
thereof.
6. The colouring matters produced as set forth in the preceding claims.
ABEL & IMRAY,
Agents for the Applicant.