IMPROVEMENTS IN THE MANUFACTURE OF COLORING MATTER, AND IN THE PROAL THE APPLICATION THEREOF TO DYEING AND PRINTING
Year: 1865

page_text: LETTERS PATENT to Alexandre Schultz; of No. 52, Rue de l'Abbaye,
Montmartre, near Paris, in the Empire of France, for the Invention of
"IMPROVEMENTS IN THE MANUFACTURE OF COLORING MATTER, AND IN THE
PROVISIONAL SPECIFICATION left by the said Alexandre Schultz at the
Office of the Commissioners of Patents, with his Petition, on the
22nd September 1865.
I, ALEXANDRE SCHULTZ, of No. 52, Rue de l'Abbaye, Montmartre, near
Paris, in the Empire of France, do hereby declare the nature of the said
Invention for "IMPROVEMENTS IN THE MANUFACTURE OF COLORING MATTER, AND IN
THE APPLICATION THEREOF TO DYEING AND PRINTING," to be as follows:-
This Invention has for its object the production of a new "grenat " or
chocolate coloring matter, and the application of the same to dyeing 'and
printing. The new coloring matter is produced by the action of hyponitric
acid on aniline red. I take aniline red, or salt of rosaniline, such as are
known as
fuchsine," and also by other names, and I dissolve the same in
alcohol or other solvent, and add ammonia, after which I pass into the
solution nitrous vapours obtained from nitric acid (sp. gr. 25° "Beaumé)

page_text: by the action thereon of metallic copper, or hyponitric acid may be otherwise
obtained. I usually employ the following proportions:-I dissolve 32 lbs. of
fuschine in a mixture of 200 lbs. of alcohol and 160 lbs. of water; I heat
until the solution is complete, and then add 80 lbs. of the liquid ammonia of
I then pass hyponitric acid gas through the mixture until all or
nearly all the fuchsine is precipitated. It is important not to carry the action
of the hyponitric acid further. I then filter the liquid, and so obtain the new
grenat or chocolate coloring matter in a solid state. It may be dried, and sent
into the market in the form of powder.
commerce.
By dissolving this coloring matter in alcohol a solution is obtained with
which different shades of red may be dyed and printed. When nitric or other
acid is added to the alcoholic solution the color obtained in dyeing and printing.
is grenat or chocolate.
For dyeing silk and wool with the new coloring matter the following
process is convenient :-I dissolve one part of the dye in three parts of nitric
acid, or in five parts of acetic acid, and one part of hydrochloric acid. The
solution is 'made in the cold. Other acids or mixtures of acids and other
solvents may, however, be employed. I add to the above solution 20 parts of
water, and boil it. 1 filter and then add water to reduce the dye bath to the
required strength.
In printing on cotton the following process is applicable: -I dissolve
one ounce of the coloring matter in 3 oz. of nitric acid; I then take 10 oz. of
water and 2 oz. of white starch, and dissolve the starch in the water with the
aid of heat; I then add oz. of chlorate of potash. When this mixture is
cold I add to it 4 oz. of the solution of coloring matter, of which the compo-
sition is given above, and it is ready for printing. After the fabric has been
printed it is hung up for 12 hours, and afterwards passed through ammoniacal
gas, or the pieces of fabric may be left another 12 hours, and then washed or
steamed. If the whites are not satisfactory they may be cleared by passing
the pieces through chloride of lime, or they may be soaped. These processes
of employing and preparing the coloring matter may be considerably varied;
for example, in preparing the color .sulphuric acid which has been saturated
with hyponitric acid by passing the gas into it may be employed; as may also
a number of other acids and substances containing hyponitric acid in solution;
in this case I obtain the color in a liquid, form by dissolving fuchsine in the
acid or solution, but the color thus prepared will not keep so well, and the
process is less advantageous. The color can also conveniently be obtained
direct upon a cotton fabric by printing it with fuchsine dissolved in dilute

page_text: nitric acid, and thickened with gum senegal. The. fabric. thus printed is
dried and then passed through the vapours of hyponitric acid, which changes
it to a dark yellowish brown; afterwards the fabric. is passed. through
ammoniacal gas, and then, on again. exposing it to the air, & beautiful grenat
or chocolate color is: developed, which. is combined perfectly with the fibre:;;
it will stand well exposure to the air, and will bear soaping in hot water. In
short, the colors produced by this new coloring matter are more solid tlian
any of those produced up, to the present time from. fuchsine, and it fixes)
itself upon cotton. without any mordant, a result which has not been
obtained up to the present. time with any of the coloring matters: derived:
from fuchsine.
SPECIFICATION in pursuance of the conditions of the Letters Patent, filed.
by the said Alexandre, Schultz in the Great Seal Patent Office on the
20th March 1866.
TO ALL TO WHOM THESE PRESENTS SHALL COME,. I, ALEXANDRE
SCHULTZ, of No. 52, Rue de l'Abbaye, Montmartre, near Paris, in the Empire
of France, send greeting..
.
WHEREAS Her most, Excellent Majesty Queen Victoria, by Her Letters.
Patent, bearing date, the Twenty-second day of September, in the year of oun
Lord One thousand eight hundred and sixty-five, in the twenty-ninth-year, of
Her reign, did, for Herself, Her heirs and successors, give and grant unto me;
the said Alexandre: Schultz, Her: special licence that I, the said Alexandre
Schultz, my executors, administrators,, and assigns,, or such others as I,
the said. Alexandre Schultz,, my executors, administrators, and assigns,,should
at any time agree with, and no others, from time to; time and at all..times
thereafter during the term therein expressed, should. and lawfully might
make, use, exercise, and vend, within, the United Kingdom of Great. Britain:
and Ireland, the Channel Islands, and. Isle of Man, an Invention fon
"IMPROVEMENTS IN THE MANUFACTURE OF COLORING MATTER, AND INC. THE
APPLICATION THEREOF TO DYEING AND PRINTING," upon the condition (amongst
others) that I, the said Alexandre Schultz, my executors or administrators, by
an instrument, in writing under my, on their, or one of their hands audi seals,
should particularly describe and ascertain the nature of the said Invention,
and in what manner the same was to be performed, and cause, the same to

page_text: be filed in the Great Seal Patent Office within six calendar months next and
immediately after the date of the said Letters Patent.
NOW KNOW YE, that I, the said Alexandre Schultz, do hereby declare
the nature of the said Invention, and in what manner the same is to be
performed, to be particularly described and ascertained in and by the following
statement thereof, that is to say:-
This Invention has for its object the production of a new grenat or chocolate
coloring matter, and the application of the same to dyeing and printing.
The new coloring matter is produced by the action of hyponitric acid on
aniline red. I prefer to proceed as follows:-I take aniline red, a salt of
rosaniline such as are known as fuchsine, and also by other names, and I add
ammonia or any other suitable alkali, after which I pass into the mixture
nitrous vapours which may be obtained from nitric acid (specific gravity 40°
Beaumé) by the action thereon of starch, or hyponitric acid may be obtained
by the action of nitric acid on copper or otherwise. I usually employ the
following proportions:-I mix 32 lbs. of fuchsine with 80 lbs. of liquid
ammonia of commerce (sp. gr. 0·96), I then pass hyponitric acid gas through
the mixture until the whole mixture assumes a brown appearance, and all or
nearly all the fuchsine is transformed into the chocolate color. It is im-
portant not to carry the action of the hyponitric acid further. I then filter
the liquid, and so obtain the chocolate or grenat coloring matter in a solid
state. It may be dried and sent into the market in the form of powder. I
prepare also the new chocolate color in a liquid form by dissolving fuschine
in nitro-sulphuric acid which has been prepared by saturating sulphuric
acid of (sp. gr. 66° Beaumé) with hyponitric acid by passing the gas into it.
The following proportions are suitable:-In 140 parts by weight of
nitro-sulphuric acid I dissolve 40 parts of fuchsine, and then add 200 parts
of water; I stir and add little by little 80 parts of powdered chalk, and
filter in order to obtain a clear liquid.
For printing on wool and mixed fabrics the color may be prepared
in the following manner :-I thicken 120 parts of the nitro-sulphuric solution
of fuchsine of the strength given above (without the application of heat)
with 50 parts of powdered gum senegal, and then add 10 parts of chlorate of
potash.
For printing on cotton, the following preparation is suitable :-I thicken
120 parts of nitro-sulphuric solution of fuchsine of the strength above given
with 50 parts of powdered gum senegal, and add 2 parts of red prussiate of
potash in powder.

page_text: After printing the fabrics are hung up to dry for 12 hours, then they are
passed, after ageing, through ammoniacal gas, steamed and washed; or they
are well washed without steaming.
Or, if grenat color in powder is employed, then in printing on cotton, the follow-
ing process is applicable:-I dissolve one oz. of the coloring matter in powder
in 3 oz. of nitric acid (sp. gr. 40° Beaumé) or other acid; I then take 10 oz.
of water and 2 oz. of white starch, and dissolve the starch in the water with the
aid of heat; I then add of an oz. of chlorate of potash, or the same quantity
of nitrite of potash. When this mixture is cold I add to it 4 oz. of the
solution of coloring matter, of which the composition is given above, and it is,
ready for printing. After the fabric has been printed it is hung up for 12
hours, and afterwards passed through ammoniacal gas, and the pieces or fabric
may be left another 12 hours, and then steamed and washed, or washed
without steaming. This color for cotton can also be prepared by dissolving in
the acid solution of grenat the proportion given above of chlorate or nitrite of
potash in lieu of adding it to the solution of starch.
For the printing of wool and mixed fabrics, the following preparation is
applicable-25 parts of grenat color in powder I dissolve without heat
in a mixture of 125 parts of acetic acid, and 25 parts of hydrochloric acid.
To prepare the color for printing I thicken 250 parts of water with 250
parts of gum senegal, which I dissolve, and when the solution is hot I add
25 parts of chlorate of potash. After cooling, I add 175 parts of solution
of grenat colour of the strength above given. After printing the fabric is
steamed and washed without passing it through ammoniacal gas.
For dyeing cotton, wool, and silk, I prepare in the following manner a
grenat coloring matter soluble in water:-To 160 parts of fuchsine I -add
40 parts of caustic soda dissolved in 100 parts of water. The mixture is
allowed to stand for 12 hours, and I then add 20 parts of nitrite of potash
dissolved in 100 parts of water; I then boil and add 400 parts of water,
boil up once, and filter and evaporate to dryness in a water bath.
In this way a grenat coloring matter is obtained suitable for dyeing. Other
bodies acting in the same way as nitrite of potash can be employed in
preparing a grenat color for dyeing, such, for example, as the hypochlorite of
lime, chlorate of potash, chromate of potash, and others having an oxidizing
.action. Wool and silk can be dyed in the ordinary manner without
mordanting. For dyeing cotton I mordant the fabric or the fibre in, the
following manner :-
!.
1°. I immerse it for five minutes in a solution of sulphate of copper,

page_text: .
containing one part of the salt to 2,000 parts of water, the excess of this
solution is pressed out of the fabric.without washing.
2°. The fabric is immersed for a quarter of an hour in a tepid solution of
catechu bark or tannin, taking 6 parts of catechu or tannin to the 100 parts
of water, the fabric is taken out and pressed.
3º. The fabric is immersed for 5 minutes in a hot solution of chromate of
potash of sp. gr. of 1° Beaumé.
The fabric is then well washed, and it is dyed hot by putting the grenat
color into the water and heating it. To obtain upon cotton a deep grenat (or
chocolate) color, I immerse the cotton fabric or fibre in a weak solution of
sulphate of iron, and then, having pressed the fabric to expel the excess of the
solution, I again immerse it in a very weak solution of tannin, the fabric is
then well washed and is dyed hot with grenat color, prepared for dyeing as
already described, and dissolved in water. The application of catechu gives
in dyeing with the new coloring matter a very beautiful and fast grenat color.
The color can also conveniently be obtained direct upon a cotton fabric by
printing it with fuchsine dissolved in dilute nitric acid mixed with alcohol
and thickened with gum. The proportions I prefer to employ are the
following I dissolve 5 parts of fuchsine in a mixture of 25 parts of alcohol
and 50 parts of water, I bring up to the boiling, add 5 parts of nitric acid
and boil again, and then I add to the above solution gum water or starch
dissolved in water in the proportion required for the shade I want to obtain;
the fabric thus printed dried and then passed through the vapours of
byponitric acid which changes it to a dark yellowish brown, afterwards the
fabric is passed through ammoniacal gas, and then on again exposing it to the
air a beautiful chocolate color is developed, which is combined perfectly with
the fibre; it will stand well exposure to the air and will bear soaping in hot
water. In short, the colors produced by this new coloring matter are faster
than any of those produced up to the present time from fuchsine, a result
which has not been obtained up to the present time with any of the coloring
matters derived from fuchsine.
What I claim is the production of grenat or chocolate coloring matter by
acting on aniline red with hyponitric acid.
I also claim the producing the said color by printing or dyeing the fabric or
material with aniline red and then treating it with hyponitric acid.
I also claim, when printing or dyeing with the said color, the use in con-
junction therewith of chlorate of potash or other equivalent oxidizing re-agent
as described.

page_text: I also claim, when printing with the said color, the use of ammonical gas
for the developement and fixation upon the fabric of the coloring matter as
described.
In witness whereof, I, the said Alexandre Schultz, have hereunto set my
hand and seal, this Ninth day of March, in the year of our Lord
One thousand eight hundred and sixty-six.
ALEXANDRE SCHULTZ. (L.S:)