IMPROVEMENTS IN PRINTING AND DYEING TEXTILE FABRICS AND YARNS
Year: 1865

page_text: LETTERS PATENT to Alfred Paraf, of the City of Manchester, in the County
of Lancaster, Chemist, for the Invention of "IMPROVEMENTS IN PRINTING
AND DYEING TEXTILE FABRICS AND YARNS."
Sealed the 1st May 1866, and dated the 6th November 1865.
PROVISIONAL SPECIFICATION left by the said Alfred Paraf at the Office
of the Commissioners of Patents, with his Petition, on the 6th November
1865.
I, ALFRED PARAF, of the City of Manchester, in the County of Lancaster,
Chemist, do hereby declare the nature of the said Invention for "IMPROVE-
MENTS IN PRINTING AND DYEING TEXTILE FABRICS AND YARNS," to be as
follows:-
Instead of using chloric acid combined with potash I combine other bases
which form salts more soluble or less liable to crystallize, as soda, oxyde of
lead, barytes, strontian, lime, magnesia, or similar bases. As the chloric acid
of the chlorate ought to be set free to enable it to oxydize it will be easily
perceived that I can raise the base more easily of the chlorate of barytes,

page_text: lead, strontian, or line, than chlorate of potash, which does not give, as they
do, sulphates or other salts nearly insoluble. I have already applied a reaction
of the potash to facilitate the decomposition of the chlorate of potash, and thus
dispense with a great part of its defects. For that purpose, instead of decom-
posing by the usual acids, as oxalic, lactic, nitric, and similar acids, I decom-
pose by hydro-fluo-silicic acid, which gives me a salt of potash nearly insoluble,
sets the chloric acid free, and consequently acts more completely and naturally,
preventing the making of crystals. In consequence of the greater solubility
of the chlorate and more completely setting at liberty of the chloric acid I can
put a larger quantity in contact with the substances to be oxydized. I obtain
more complete oxydation for steam colors, such as, catechu and the aniline
black and similar colors, which are produced more advantageously. I can
add to a color containing chlorate of potash or other bases one or more
chlorates of different solubility to chlorate of potash; the result will always be
better than with chlorate of potash alone, and this advantage will, make part
of my present improvements. "In fact whatever plan shall be employed in
printing or dyeing, the chlorates most soluble or less liable to crystallize than
potash will always form a leading part of my Invention. It will be the same
thing if hydro-fluo-silicic acid is used to decompose the chlorate of potash.
When I impregnate a fibre or fabric with a chlorate; and put the said goods
to be printed or dyed in contact with the coloring matter which contains the
necessary substance to decompose the chlorate, as hydrochloric acid, if it be
chlorate of potash or barytes, hydro-fluo-silicic acid, sulphuric, and similar
acids; if it be chlorate of lime, barytes, strontian, or lead; in a word, an
acid or acid salt, or other salt or body which will decompose the chlorate,
I can press the oxydizing action of the chlorate by adding to the coloring
matter a salt of iron. I also find that the chlorites and hypochlorites
oxydize still more quickly and more completely than the chlorates; and I
reserve to myself the use of the chlorites and hypochlorites. As by the
decomposition of the chlorate it forms some chlorhydric acid, which in some
instances does harm by altering the fibre, I take all or a part of the chloric
acid in the state of chlorate of lead, or add some fluo silicate of lead, whereby
all or part of the chlorbydric acid is transformed into harmless chloride of lead.
In some cases, as the acid contained in the color produces chlorhydric acid of
the chlorate, that may be the acid used to decompose the chlorate, notwith-
standing other colors being printed at the same time, it produces some white
edges and the colors become more pale. This happens especially in printing
an acid color to the chlorate in a design of several colors, where some are
red, rose, violet, or chocolate, to be dyed in madder, or some buffs, orange,

page_text: chrome, and similar colors. In some cases, where the acid contained in the
color, either chlorhydric acid produced by decomposition of the chlorate, or the
acid used to decompose the chlorate, that acid injures other colors which are
printed at the same time. I have two methods of refixing on the fibre the
metallic oxyde which the acid will have dissolved:-First, by dunging in an
alkaline liquid silicate of soda or potash to a degree of concentration sufficient
to precipitate the mordant dissolved at 7° to 30° Twaddell ; secondly, by
exposing the fibre or material, after ageing and before dunging, to ammoniacal
vapour. Suppose all the animal matters do not take well, or even do not take
some colors at all, in which the chlorate acts an important part, and which
take well upon a vegetable matter, but not upon such substances as wool.or
silk, the addition even of copper to the color in the coloring trough in this
case will be of no use as the black will not be good. I surmount this diffi-
culty as follows:-I combine with the animal matter some metallic salts, as
copper or others, capable of assisting the decomposition of the chlorate, and
then the animal substance will take the black which the cotton has already
taken. Sometimes the solution of the salt of copper combines with the animal
matter in a cold state, as for light wool or silk, but for heavy wool, as goats'
wool, I often make it very hot, sometimes to ebullition, with a solution of salt
of copper. This operation being completed I wash to raise the part of the
salt of copper not combined with the animal matter. If the animal matter is
to be printed with the salt of aniline I dry it after washing, and then print
the same black as upon cotton. Drying or not in the dyeing process is im-
material. It is not to the aniline alone that this means is applicable for fixing
upon animal matter the chlorate preparations, which are not easily applied by
other means. This mode of preparing the animal matters constitutes a portion
of my Invention, whether any color to which it is to be applied immediately,
or the result shall be to give an animal matter proper or more capable of
taking a cotton chlorate color. I also use chloric acid or hypochloric acid
combined with aniline or its homologues for the production of black and grey
colors. I decompose sulphate, oxylate of aniline, or similar salts with chlorate
or hypochlorate of barytes, lead, lime, strontian, so as to produce, by double
decomposition chlorate of or bypochlorate of aniline or its homologues, printed
or dyed upon fabrics or yarns produces fast black or grey by ageing.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent, filed
by the said Alfred Paraf in the Great Seal Patent Office on the 5th
May 1866.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, ALFRED
PARAF, of the City of Manchester, in the County of Lancaster, Chemist, send
greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her Letters
Patent, bearing date the Sixth day of November, in the year of our 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 Alfred Paraf, Her special license that I, the said Alfred Paraf
my executors, administrators, and assigns, or such others as I, the said Alfred
Paraf, 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 for "IMPROVEMENTS IN PRINTING AND
DYEING TEXTILE FABRICS AND YARNS," upon the condition (amongst others) that
I, the said Alfred Paraf, my executors or administrators, by an instrument in
writing under my, or their, or one of their hands and 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 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 Alfred Paraf, do hereby declare the
nature of my said Invention, and in what manner the same is to be per-
formed, to be particularly described and ascertained in and by the following
statement (that is to say) :-
:-
Chloric acid has only hitherto been used in dyeing and printing in the state of
chlorate of potash, which was mixed with coloring matters to oxydize, or used
for padding cloth when complete fixing of iron and tin mordants was wanted;
the chlorate of potash being very insoluble it crystalized very easily either in
the color or upon the cloth, and so occasioned. a great many inconveniences,
which I overcome as follows:-Instead of using chloric acid combined with
potash I combine other bases which form salts more soluble or less liable to
crystalize, as soda, oxide of lead, barytes, strontian, lime, magnesia, or similar
bases. As the chloric acid of the chlorate ought to be set free to enable it to
oxydize, it will be easily perceived that I can liberate the base more easily

page_text: from the chlorate of barytes, lead, strontian, or lime than from chlorate of
potash by means of acids forming insoluble salts with the bases herein named.
I have already applied a re-action of the potash to facilitate the decomposition
of the chlorate of potash, and thus dispense with a great part of its defects.
For that purpose instead of decomposing by the usual acids as oxálic, tartaric,
nitric, and similar acids, I decompose by hydro-fluo-silicic acid, which gives me
a salt of potash nearly insoluble, sets the chloric acid free, and consequently
acts more completely and naturally, preventing the making of crystals. In
consequence of the greater solubility of the chlorate and more complete setting
at liberty of the chloric acid, I can put a larger quantity in contact with the
substances to be oxydized, I obtain more complete oxydation for steam colors,
such as catechu and the aniline blacks, and similar colors, which are produced
more advantageously. I obtain good results for aniline black by using the
following proportions, which I will call black liquor:-One part of chloride of
aniline, one part hydro-fluo-silicic acid at 6°, ten per cent. of protochloride of
iron dissolved in the aniline and acid. To save the greys the cloth is prepared
in a solution of chlorate of soda at 6° Twaddell, then print upon with the.
following color, two pounds aniline black liquor, three pounds of water, two
pounds white starch, two pounds gum dragon paste, one pound brown British
gum, seven ounces lampblack, boil well together, and cool down; age in a
cold room for one or two days, but if pressed for time the black can be
produced in a few hours by running one or twice through an ageing machine.
But if saving the greys is no object the cloth does not require any preparation,
and the soluble chlorate can be given in the color, and printed together
upon the cloth. I use the following proportions:-First, two pounds black
liquor, three pounds water, one pound of starch, all well boiled together;
second, six pounds chlorate of soda at 20° Twaddell, two pounds of starch, two
pounds of brown gum paste, two pounds of gum dragon. For the color I use
one part of the first mixture to one part of the second, and mix them cold.
I can add also to a color containing a small quantity of chlorate of potash
other chlorates of greater solubility than chlorate of potash, and the result
will in all cases be better than with chlorate of potash alone. When I
impregnate a fibre or pad fabrics in a soluble chlorate which I dye in or print
upon with a coloring matter to be oxydized, as, for instance, in the aniline
black when I want to secure the greys, I can hasten the oxydation by adding
to the coloring matter to be oxydized or in the aniline black color two or three
per cent. of a salt of oxide of iron, copper, chrome, or manganese. I also
use chloric acid combined with aniline or its homologues for the production
of black and grey colors. I decompose sulphate, oxalate of aniline, or similar

page_text: salts with chlorate of barytes, lead, lime, strontian, so as to produce by double
decomposition chlorate of aniline or its homologues, which printed or dyed
upon
fabrics or yarns produces fast blacks or greys by ageing, and in this case
I find also an advantage in adding to the aniline two or three per cent. of a
salt of iron, copper, chrome, or manganese. Animal matters do not take easily
colors formed by oxidation which are going very well upon vegetable matters.
And, for instance, an aniline black, containing copper or not, which gives
good results upon cotton or linen, will give no color at all upon wool or silk.
I surmount this difficulty by fixing in the fibre metallic oxides, such as copper,
alone or combined with chrome, and then the animal matter takes well aniline
black colors, which vegetable matters have already taken. I find an advantage
in preparing the animal matters which have to be dyed or printed upon with
aniline black colors in the following mixture:-One pound of sulphate of
copper, half a pound of chlorate of soda, half a pound of bichromate of potash,
and one gallon of water. Use one part of this liquor to two, parts of water.
Having now described the nature and particulars of my said Invention, and
the manner
in which the same is to be performed, I desire it to be understood
that I claim as oxidizing agents in dyeing and printing,
1
First, the use of oxygenous compounds of chlorine more soluble than those
combined with potash, as chlorates of soda, ammonia, barytes, strontian, lead,
lime, magnesia, alumina, zinc, nikel, copper, chrome, iron, manganese, and
potash, when decomposed by hydro-fluo-silicic acid.
Secondly, the preparation of the fibre or material to be dyed or printed with
a chlorate more soluble than potash for the production of steam colors, as
aniline black and its analogues.
Thirdly, the preparation of the fibre or material intended to receive mordants
of iron or tin with a chlorate more soluble than potash.
Fourthly, a soluble chlorate to replace in all colors or dye liquors the
chlorate of potash.
Fifthly, the chlorate of potash. and hydro-fluo-silicic acid mixed in the dye
liquid and the coloring matter, where till now a less active acid was used for
decomposing the chlorate of potash.
Sixthly, the addition of a salt of iron, copper, chrome, or manganese to the
coloring, matter or dye liquor intended to be printed or put in immediate
contact with the fibre or material previously prepared in chlorate of potash.
.Seventhly, the addition of a salt of iron, copper, chrome, or manganese to
the coloring matter or dye liquor intended to be printed or put in immediate
contact with the fibre or material previously prepared in a more soluble
chlorate..

page_text: Eighthly, the preparation of animal matters in salts of copper or copper and
chrome, in order to enable them to take aniline blacks and similar colors
either by dyeing or printing.
In witness whereof, I, the said Alfred Paraf, have hereunto set my
hand
and seal, this Fourth day of May, in the year of our Lord One thou-
sand eight hundred and sixty-six.
Signed, sealed, and delivered by the
within-named Alfred Paraf, in
the presence of
E. J. HUGHES,
Patent Agent,
Manchester.
ALFRED PARAF. (L.S.)