Improvements in the Production of White and Coloured Patterns on Aniline Black Grounds in Calico Printing.
Year: 1897

page_text: Complete Specification Left, 24th Feb., 1898-Accepted, 24th May, 1898
PROVISIONAL SPECIFICATION.
Improvements in the Production of White and Coloured Patterns
on Aniline Black Grounds in Calico Printing.
ERNEST BENTZ, of 5, Demesne Road, Alexandra Park, Manchester, in the County
of Lancaster, Technical Chemist, do hereby declare the nature of this invention to
be as follows:-
:-
This invention relates to the production in calico printing of white and coloured
patterns on aniline black grounds on fabrics composed of cotton, linen, and other
vegetable fibres, and it has for its object the production of such patterns in a better
and more economical manner than heretofore.
The invention consists in fixing upon the fabrics to be partially coloured aniline
black suitable resists or reserves, namely, the oxides, hydroxides or carbonates of
magnesium, cadmium, zinc or lead, or the carbonates of calcium, strontium or
barium, or the oxides or hydroxides of aluminium, or (stannic) tin, alone or in com-
bination or admixture together, if a white pattern is to be produced, or in admixture
with insoluble azo colouring matters formed on the fibre, if coloured patterns are to
be produced, and then padding with an aniline black padding mixture or printing
over in pattern an aniline black printing mixture, drying, ageing (to develope the
black in the parts not protected by the resists), and rinsing in water, soaping. or
chroming as usual.
and
beta-
Coloured patterns on aniline black grounds are produced according to this inven-
and
tion by padding the fabrics with alkaline solutions of alpha-naphthol or
diazotised solutions of
naphthol, drying the fabrics, printing them with
paranitraniline, metanitraniline, alphanaphthylamine, betanaphthylamine, amidoazo-
benzene, amidoazotoluene, benzidine, tolidine, nitrobenzidine, dianisidine, dipheneti-
dine, orthonitroparaphenetidine, paranitroorthotoluidine, and orthonitroparatoluidine,
suitably thickened for calico printing and admixed with one or more of the follow-
ing salts-Calcium chloride, chlorate, nitrate, nitrite, acetate, sulphocyanide or
lactate, barium chloride, chlorate, nitrite, nitrate, acetate, sulphocyanide or lactate,
strontium chloride, chlorate, nitrite, nitrate, acetate, sulphocyanide or lactate, zinc
sulphate, sulphocyanide, lactate, chloride, nitrate or acetate, cadmium sulphate,
chloride, nitrate acctate, lactate or sulphocyanide, magnesium sulphate, chloride,
nitrate, chlorate, acetate, lactate or sulphocyanide, lead nitrate or acetate, aluminium
sulphate, chloride, nitrate, lactate or sulphocyanide, stannic chloride or oxalate.
The printed fabrics are then dried and are next passed into suitable alkaline
solutions in order to fix upon the fabrics the oxides or carbonates of the metallic
elements the salts of which have been printed, for example, in the case of calcium,
strontium, and barium salts, the printed fabrics are passed into a solution of sodium
or potassium carbonate, in the case of magnesium salts, the printed fabrics are
preferably passed into a solution of caustic soda or caustic potash. The fabrics are
then well rinsed in water and are next dried and padded or printed with an aniline
black padding or printing mixture. The fabrics are next dried and the black is

page_text: developed in the parts of the fabrics where the metallic oxides or carbonates have
not been fixed by passing the fabrics through the steam aniline black ageing
machine, and then the fabrics are rinsed in water and soaped or chromed as usual.
White patterns are obtained by omitting the diazotised amines from the above-
mentioned printing mixtures and then proceeding as described, printing, for
instance, a concentrated suitably thickened solution of zinc chloride or calcium
chloride on calico prepared with an alkaline solution of beta-naphthol or alpha-
naphthol and passing the printed calico into a concentrated solution of sodium
carbonate, and then proceeding as herein before described, namely, washing,
padding or printing the black mixture, ageing, washing, soaping or chroming.
Coloured and white patterns may also be produced in conjunction with aniline
black by adding the compounds which serve to convert the metallic salts employed
in this process into suitable reserves for aniline black to the alkaline solutions of
alpha-naphthol and beta-naphthol employed for the preparation of the fabrics,
adding in this manner, for instance, sodium carbonate to the sodium beta-
naphtholate solution ordinarily used. The fabrics are in this case, after printing
and drying, rinsed in water, dried, padded or printed with an aniline black padding
or printing mixture, steamed for a short time, washed and soaped or chromed.
The following alkali and alkaline-earth compounds may be used in specific
instances for fixing the reserve compounds employed in this process to prevent the
* development of aniline black in the parts of the fabrics to be reserved, in addition
to the compounds herein before mentioned :-Sodium and potassium aluminate,
zincate, and stannate, ammonia, ammonium carbonate, calcium, strontium and
barium hydroxides.
A yellow pattern is produced when lead acetate or nitrate is printed without a
diazotised amine in admixture with it on fabrics prepared with alpha-naphthol and
beta-naphthol and the printed fabrics are passed into sodium carbonate or potassium
carbonate solution (or the sodium or potassium carbonate is added to the naphthol
preparation solution), then the fabrics are rinsed in water, dried, padded or printed
with aniline black and dried as usual, steamed for a short time, and chromed.
Coloured patterns may also be produced along with the white and coloured
patterns obtained as herein before described and specified by printing on the fabrics
prepared with alpha-naphthol and beta-naphthol basic colouring matters, capable
of withstanding the action of mild oxidising agents, for instance, rhodamine 6 G,
methylene blue, thioflavine T, and other colouring matters, with tannic acid and
acetic acid, and such salts as calcium chloride, zinc chloride, stannous chloride,
stannous acetate, calcium acetate and others, suitably thickened for printing, with
calcined starch, dextrin, or starch, for instance, and then passing the fabrics through
sodium or potassium carbonate solution, washing with water, and soaping.
Instead of aniline, analogous aromatic amido bases employed in calico printing
for the production of colours of similar nature to aniline black, may be used in the
above-described process, for instance, ortho-toluidine, para-toluidine, metaxylidine,
alphanaphthylamine, and other similar compounds. These bases may be employed
either singly or mixed together with one another or with aniline.
... 32 7 1
11003
Improvements in the Production of White and Coloured Patterns
on Aniline Black Grounds in Calico Printing.
I, ERNEST BENTZ, of 5, Demesne Road, Alexandra Park, Manchester, in the 5
County of Lancaster, Chemist, do hereby declare the nature of this invention

page_text: and in what manner the same is to be performed to be particularly described
and ascertained in and by the following statement:-
This invention relates to the production in calico printing of white and coloured
patterns on aniline black grounds on fabrics composed of cotton and it has for its
object the production of such patterns in a better and more economical manner
than heretofore.
The invention consists in fixing by precipitation upon the fabrics to be
partially coloured aniline black, suitable resists or reserves, such as, the oxides or
hydroxides, and carbonates of calcium, cadmium zinc or lead, the carbonates of
strontium or barium, the oxide or hydroxide of magnesium the hydroxide of
aluminium, and stannic tin or the silicates of calcium, strontium, barium,
magnesium, cadmium, zinc, and lead, borate and sulphite of calcium, and other
compounds, alone or in combination or admixture together if a white pattern is to
be produced, or in admixture with insoluble azo-colouring matters formed on the
fibre, if coloured patterns are to be produced, and then padding with an aniline
black padding mixture, or printing over in pattern an aniline black printing mixture,
drying, ageing or steaming (to develope the black in the parts not protected by
the resists), and rinsing in water, soaping or chroming as usual. When, however,
lead salts are employed to form the resists the fabrics, after developing the aniline
blacks upon them, are soaped and not chromed, unless it be desired to produce
upon them yellow resist patterns along with patterns of other colours.
Coloured patterns on aniline black grounds are produced according to this
invention by padding the fabrics in the usual manner with alkaline solutions of
beta-naphthol, drying the fabrics and printing them with diazotised solutions of
para-nitraniline, meta-nitraniline, alpha-naphthylamine, beta-naphthylamine,
amidoazobenzine, amidoazotoluene, dianisidine, ortho-nitro-para-phenetidine, para-
nitro-ortho-toluidine, and ortho-nitro-para-toluidine, suitably thickened for calico
printing, and admixed with suitable soluble salts of the above mentioned metallic
elements such as calcium chloride, calcium nitrate, calcium acetate, magnesium
chloride magnesium nitrate, magnesium acetate. The printed fabrics are dried
and passed into suitable alkaline solutions in order to remove from the unprinted
parts the unchanged sodium beta-naphtholate and to fix upon the fabrics the
oxides or hydroxides, carbonates or silicates or other suitable salts of the metallic
elements the salts of which have been printed; for example, in the case of calcium
strontium and barium salts, the printed fabrics are passed through a solution of
potassium carbonate or of sodium carbonate, or of sodium or potassium silicate, or
of sodium or potassium stannate, and in the case of calcium salts, sodium
or potassium borate or sodium or potassium sulphite; in the case of magnesium
salts the printed fabrics are passed through a solution of caustic soda or of caustic
potash, or of sodium or potassium silicate, zincate, aluminate or stannate. The
fabrics are then rinsed in water and are next dried and padded or printed with an
aniline black padding or printing mixture. After this, the fabrics are dried and
the aniline black is developed in the parts of the fabrics where the metallic oxides
or hydroxides or carbonates or other compounds have not been fixed, by passing
the fabrics through an ageing machine or steaming, according to the nature of the
mixture employed for the production of the aniline black, and then chroming or
soaping the fabrics as usual.
Coloured and white patterns are obtained by omitting for the white parts the
diazotised amines from the above mentioned printing mixtures and then proceeding
as described, printing for instance on calico prepared in the usual manner with an
alkaline solution of beta-naphthol (4 or 5 oz. of beta-naphthol per gallon) a
printing mixture for the coloured parts consisting of a suitably thickened
concentrated solution of magnesium acetate and a diazotised amine, along with a
suitably thickened concentrated solution of magnesium acetate alone for the white
parts and passing the printed calico through a solution of caustic soda, and then
proceeding as hereinbefore described, namely, washing, drying, padding, or

page_text: printing the mixture for amline black, drying, ageing or steaming, chroming, or
soaping.
The following are examples ofsuitable white and coloured printing mixtures.
1. For the production of a white resist pattern:
--
1 gallon of calcium chloride solution at a density of 44 degrees Twaddell.
1 quart of calcium acetate solution at 30° Twaddell, and 1 lb. of wheaten
starch.
This is heated until thick enough for calico printing.
2. For the production of a red resist pattern:-
(a) 2 gallons of the above mixture of calcium chloride, calcium acetate and
starch are first heated and then well cooled, and to them is added a
Bolution of diazotised paranitraniline prepared for example by adding 1lb.
of hydrochloric acid at a density of 32 degrees Twaddell to a mixture of
2 lb. of the nitrosamine red paste of commerce and lb. of ice, and allow-
ing the mixture to stand until the ice has melted.
(6) Example of a para-nitraniline red printing mixture, prepared directly from
para-nitraniline :-
:-
2 gallons of the above, thickened and well-cooled mixture of calcium chloride
and calcium acetate are taken and to them there is added a solution or
paste obtained by mixing together 10 oz. of finely ground para-nitraniline
5 oz. of sodium nitrite and 5 oz. of cold water, and adding the mixture
to a mixture of 16 oz. of hydrochloric acid at a density of 32 degrees
Twaddell and 5 oz. of ice.
3. Meta-nitraniline and ortho-nitro-para-toluidine, and para-nitro-ortho-toluidine
orange printing mixtures are prepared similarly to the last above example of a
paranitraniline red printing mixture, finely ground, meta-nitraniline, ortho-nitro-
para-toluidine and para-nitro-ortho-toluidine being substituted for the para-
nitraniline, weight for weight, and the rest of the materials being taken as in that
example.
4. An amidoazobenzene red printing mixture may be prepared in a manner similar
to that described for the preparation of the paranitraniline red printing mixture (b)
but with 10 oz. of finely ground amidoazobenzene 4 oz. of sodium nitrite and 12 oz.
of hydrochloric acid, at 32 degrees Twaddell to one gallon of the above thickened
mixture of calcium chloride and calcium acetate.
5. An amidoazotoluene red-brown printing mixture may be prepared in a similar
manner to example 2 (b), but with 10 oz. of finely ground amidoazotoluene, 3 oz.
of sodium nitrite, and 11 oz. of hydrochloric acid, at 32 degrees Twaddell
to 1 gallon of the above thickened mixture of calcium chloride and calcium
acetate.
6. An ortho-nitro-para-phenetidine pink printing mixture may be prepared in a
similar manner but with the following proportions.
4 oz. of finely ground ortho-nitro-para-phenetidine, 2 oz. of sodium nitrite and
12 oz. of hydrochloric acid, at 32 degrees Twaddell to 1 gallon of the
above thickened mixture of calcium chloride and calcium acetate.
7. An alphanaphthylamine claret printing mixture may be prepared as follows:-
To 1 gallon of the above thickened solution of calcium chloride and calcium acetate
there is added a solution which is prepared by mixing 1 lb. 10 oz. of a 36 per cent.
paste of alpha-naphthylamine hydrochloride with 6 oz. of hydrochloric acid
at 32 degrees Twaddell and 1 lb. of ice, and adding 4 oz. of sodium nitrite dissolved
in 4 oz. of cold water.
8. A beta-naphthylamine red printing mixture may be prepared by substituting
1 lb. 10 oz. of a 36 per cent. paste of beta-naphthylamine hydrochloride for the
same quantity of alpha-naphthylamine hydrochloride given in the last
example (7).
A suitable fixing bath for the above white and coloured resist printing mixtures
is composed of 20 gallons of water and 10 lb. of sodium carbonate and is employed
at a temperature of 120° Fahrenheit. Also suitable fixing baths of caustic soda,

page_text: caustic potash, soda and potassium silicate, zincate and aluminate are prepared by
adding 1 gallon of solutions of these at a density of 70 degrees Twaddell to
20 gallons of water, at the ordinary temperature.
A suitable fixing bath of sodium stannate is obtained by dissolving 5 lb. of
sodium stannate in 20 gallons of water. This also is employed at the ordinary
temperature.
Suitable fixing baths of sodium borate (borax) and sodium sulphite are obtained
by dissolving 20 lb. of these salts in 20 gallons of water. They may be employed
at the ordinary temperature.
The mixture for aniline black which is employed is preferably one prepared from
aniline hydrochloride, an alkali ferrocyanide and an alkali chlorate, as used at the
present time. Its preparation and application are well understood by those engaged
in calico printing.
Coloured and white patterns may also be produced in calico printing, according
to this invention, by adding in some cases the compounds which serve to convert
the metallic salts employed in this process into suitable reserves for aniline black,
to the alkaline solution of beta-naphthol employed in the preparation of the fabrics,
adding in this manner, for instance, 1 lb. of sodium carbonate to one gallon of
the sodium beta-naphtholate solution commonly employed. The fabrics are in this
case, after printing and drying, rinsed in water, dried, padded or printed with an
aniline black padding or printing mixture, dried, aged or steamed to develope the
black in the unprinted parts of the fabric, chromed or soaped, and dried.
Instead of aniline, analogous aromatic amido bases employed in calico printing
for the production of colours of similar nature to aniline black, may be used in the
above described process, for instance ortho-toluidine, metaxylidine, alpho-
naphthylamine, and other similar compounds. These bases may be employed either
singly or mixed with one another or with aniline.
The colours obtained according to this invention from beta-naphthol and the
diazo compounds of para-nitraniline, amidoazobenzene, beta-naphthylamine and
ortho-nitro-para-phenetidine are red, from meta-nitraniline, ortho-nitro-para-
toluidine, para-nitro-ortho-toluidine, orange, from alpha-naphthylamine claret,
from dianisidine purple, from amidoazotoluene red-brown.
my said
Having now particularly described and ascertained the nature of
invention and in what manner the same is to be performed I declare that what
I claim is :-
1. The production of coloured patterns on aniline black grounds in calico printing
by fixing by precipitation upon the fabrics suitable resists or reserves in admixture
with insoluble azo-colouring matters formed on the fibre to produce the coloured
patterns, then padding with an aniline black padding mixture, or printing over in
pattern an aniline black printing mixture and then drying the fabrics and developing
the black and rinsing soaping or chroming or otherwise completing the treatment
of the fabrics substantially as herein before described.
2. The production of coloured and white patterns on aniline black grounds in
calico printing by fixing by precipitation upon the fabrics suitable resists or
reserves, alone to produce the white parts of the pattern, and in admixture with
insoluble azo-colouring matters formed on the fabric where the coloured parts of the
pattern are required, then padding with an aniline black padding mixture, or
printing over in pattern an aniline black printing mixture, and then drying the
fabrics and developing the black and rinsing soaping or chroming or otherwise
completing the treatment of the fabrics substantially as herein before described.
Dated this 23rd day of February 1898.
GEO. DAVIES & SON,
Agents for the Applicant, 4, St. Ann's Square, Manchester.