A New or Improved Dyeing Material and Method of Employing the same.
Year: 1888

page_text: Date of Application, 24th Nov., 1888
Complete Specification Left, 24th Aug., 1889-Accepted, 28th Sept., 1889
PROVISIONAL SPECIFICATION.
A New or Improved Dyeing Material and Method of Employing
the same.
I, CHARLES FRANÇOIS XAVIER NOROY, of 223 Faubourg St. Honoré, Paris, in the
Republic of France, Chemist, do hereby declare the nature of this invention to be as
follows:-
This invention relates to a new or improved material for dyeing, and in a method of
applying the said material to the dyeing of animal and vegetable fibrous or textile
materials and to the dyeing of skins of all kinds.
The aforesaid new or improved dyeing material is produced by the chemical
reaction of nitric acid upon fecula, starch, or flour (generally derived from lignine
and cellulose. It is neither soluble starch, as understood in chemistry, nor tartaric
acid, nor oxalic acid, as might be supposed; but is the product which is formed
between the first and last states of oxidation by nitric acid. It is in fact starch
diminished by a certain quantity of carbon and hydrogen and perhaps increased by a
certain quantity of nitrogen.
This product possesses the property of dissolving almost all the known metallic and
earthy oxides, such as those of iron, copper, zinc, chromium, nickel, antimony, tin,
arsenic, calcium, aluminium and so forth, and of preventing them from being
re-precipitated by the addition of an excess of the alkalies potash, soda, ammonia, or
carbonates of those bases. It is this property which enables me to effect the dyeing
in a more or less alkaline medium in which cotton and wool, and in general all
animul and vegetable textile materials, can be dyed.
Slight alkalinity (without causticity) is indispensable in the dyeing of cotton, and is
very favourable to the dyeing of wool, for without causing injury of any kind it
assures a very prompt penetration, into the material to be dyed, of the oxides which
serve for the production of black dye, and ultimately it accelerates the oxidation, by
the oxygen of the air, of the colouring materials combined with the said oxides.
The wool is in the best condition for being charged with the oxides or the lakes
for which it has the greatest affinity, whilst in the acid baths heretofore generally
employed, the affinity of the wool for the oxides is overcome by that for the acids.
Dyeing wool in acid baths requires a long time, a sustained heat, and repeated
manipulations. In my carbonated alkaline baths, wool is much more easily and
quickly treated; it requires comparatively no heat; the number of manipulations is
enormously decreased, and injury due to the acids is wholly avoided.
I will now proceed to describe the composition and method of preparing my dye
liquors or baths, and the method I employ for dyeing black on cotton and wool,
whether mixed or separate.
I employ two dye liquors or baths, the first containing the astringent colouring
matter such as logwood, Jamaica rosewood, turmeric, gall-nuts etcetera, with a salt
of copper such as sulphate, chloride, nitrate, or acetate for example, and also a certain
quantity of some suitable acid; and the second an alkaline bath composed of my
new or improved product, which I call "nitrated starch," earthy and metallic oxides,
and alkaline carbonates. These baths are composed and prepared as follows:-
First bath For producing blue black. I take 30 to 40 parts, by weight, of
dry extract of logwood, strengthened, if required, by a certain quantity of another
tannin, such as sumach, gall-nuts, or chesnuts, for example, and 1000 parts, by weight,
of warm water.
I dissolve the logwood, or its extract, in the warm water, and let the solution cool.
When the solution is tepid, or cold, I add thereto a cooled solution composed of 6 to 10
parts of sulphate, chloride, nitrate, acetate, etcetera, of copper, 20 to 30 parts of water,
5 to 7 parts of hydrochloric acid, and 10 to 15 parts of acetic acid. For deep black,

page_text: I use the same materials and the same proportions as for blue black, but with the
addition of from 4 to 6 parts of extract of Jamaica rosewood, or of turmeric, or other
- yellow astringent material.
All these proportions may be varied according to the strength of the bath and the
shade to be produced.
Second bath The "nitrated starch," used in the forination of the second bath, is
produced by the reaction of 2 parts of ordinary nitric acid of commerce on 1 part of
starch or fecula. These quantities may be varied slightly according to the strength
of the nitric acid; but with the ordinary nitric acid of commerce the above proportions
are suitable.
I place the starch, or the fecula, in a porcelain, or enamelled sheet iron, vessel, and
pour over it the nitric acid; I then slighily heat the mixture. As soon as the starch
is dissolved and the vapours are about to be disengaged abundantly, I remove the
vessel from the fire, and allow the reaction to proceed until no more vapour is given
off. The liquid thus obtained is what I call "nitrated starch."
In order to associate this liquid with the various oxides which compose the second
bath, I take the said oxides in the hydrated state, that is to say freshly precipitated
from their salts, and I introduce them into the "nitrated starch" liquid diluted with
one or two times its volume of water. I then neutralize with liquor ammonia of
commerce, or other alkali, or with an alkaline carbonate such as soda or potash for
example.
To complete the composition of the bath, I add the necessary quantity of water, and
from 5 to 6 parts, by weight, of carbonate of soda per 1000 parts of bath, in order
to assure a certain amount of alkalinity.
Instead of oxides, I may employ the salts themselves from which they are obtained.
In that case I take quantities of the salts corresponding to those of the oxides and
dissolve them in water; I add these solutions to that of the "nitrated starch;"
then neutralise with ammonia or carbonate of soda, taking care always to secure
alkalinity by using an excess of carbonate of soda or potash.
In the preparation of the two baths, I only employ heat for the solution of the
salts.
The composition of this second bath may be varied considerably, because being
intended to deposit the lakes upon the fibres and to fix them there, all the oxides, that
the "nitrated starch" holds in alkaline solution, assist separately or united in pro-
ducing the result.
These shades of black, produced from a logwood or other astringent base, may be
varied by adding to the first, or second, bath, or to both, yellow, green, or blue coal-
tar colours, or indigo in the various states in which it is employed in dyeing.
In performing the dyeing process I proceed as follows:-
I place the stuffs, yarn, hair, skins etcetera it is intended to dye, in the first or
acid bath, and leave them well immersed therein during one or two hours, according
to the surrounding temperature. I then remove them from the first bath and wring
them as dry as possible; then partly dry them in the open air, or in a stove, so
as to leave in them a little moisture. This is essential in order to avoid too great a
concentration of the acid which textile materials retain, and which would lead to
slight damage to the colouring matters not yet fixed.
When it is required to dye yarns or woven goods of great thickness, or that have
already been dyed and which are difficult to re-dye in black, it is advantageous to
raise the temperature slightly to from 40° to 60° centigrade. For light yarns and
woven goods, cotton, and wool in hair, a temperature of 10° to 20° centigrade should
not be exceeded.
Instead of a continuous immersion in the bath, of the articles to be dyed, they
may be subjected to successive immersions in the usual way by means of the apparatus
ordinarily employed for that purpose.
The articles taken from the first acid bath, wrung, and sufficiently dried, or even
drained only, are immersed in the second or alkaline bath. They there remain, or
are subjected to repeated immersions therein, for from three quarters of an hour to an

page_text: hour and a half, or more, according to their thickness or size; care should be taken
that the bath, either before or after the immersion of the articles in it, is distinctly
alkaline. The articles, on leaving the second bath, are wrung as on leaving the
first, but not so much; a notable quantity of liquid should be left in. I expose
them, after this light wringing, to the air for from one to three hours, or more,
according to the heat of the day and other circumstances. By this exposure, the
oxygen of the atmosphere produces a black colour, and as soon as this is attained, I
stop this oxidation, the enegy of which is attributable to the alkalinity of the liquid,
by washing in a large quantity of cold or tepid water until all discharge ceases.
Other washings may follow with water slightly soapy, or simply alkaline, if thought
necessary. After washing, it only remains to wring as completely as possible, and to
dry either in the open air, in a heated chamber or stove, or on heated cylinders. The
operation of dyeing, which, including exposure to the air, has only occupied a few
hours, and has required little or no heat except that necessary for the preparation
of the baths, is now complete. The astringent colouring matters have been deposited
on the articles in the first or acid bath; they have been fixed by the oxides in the
second or alkaline bath, and have attained a definite black colour solely by the
oxidizing action of atmospheric air without taking other oxygen from chromates,
chlorates, or other oxydizing agents accompanied by acids, which always produce
more or less injury of the fibres and even of the colour that they have taken part in
producing. If, however, it is desired to facilitate the oxidation, chromates, chlorates
etcetera, may be used in the second bath without fear of injurious effects, provided
the alkalinity of the bath is maintained.
'
30
COMPLETE SPECIFICATION.
A New or Improved Dyeing Material and Method of Employing
the same.
I, CHARLES FRANÇOIS XAVIER NOROY, of 223 Faubourg St. Honoré, Paris, in the
Republic of France, Chemist, 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, that is to say :-
This invention relates to a new or improved material for dyeing, and in a method or
applying the said material to the dyeing of animal and vegetable fibrous or textile
materials and to the dyeing of skins of all kinds.
The aforesaid new or improved dyeing material is produced by the chemical
reaction of nitric acid upon fecula, starch or flour or more generally upon lignine and
cellulose. It is neither soluble starch, as understood in chemistry, nor tartaric acid,
nor oxalic acid, as might be supposed; but is the product which is formed between
the first and last states of oxidation by nitric acid. It is in fact starch diminished by
a certain quantity of carbon and hydrogen and perhaps increased by a certain quantity
of nitrogen.
This product posses the property of dissolving almost all the known metallic and
earthy oxides such as those of iron, copper, zinc, chromium, nickel, antimony, tin,
arsenic, calcium, aluminium and so forth, and of preventing them from being
re-precipitated by the addition of an excess of the alkalies such as, for example,
potash, soda, ammonia, or carbonates of those bases. 1t is this property which
enables me to effect the dyeing in a more or less alkaline medium in which cotton
and wool, and in general all animal and vegetable textile materials can be dyed.
Slight alkalinity (without causticity) is indispensible in the dyeing of cotton, and
is very favourable to the dyeing of wool, for without causing injury of any kind it
assures a very prompt penetration into the material to be dyed of the oxides which
serve for the production of black dye and ultimately it accelerates the oxidation, by

page_text: Instead of oxides, I may employ the salts themselves from which they are obtained
In that case I take quantities of the salts corresponding to those of the oxides and
dissolve them in water; 1 add these solutions to that of the "nitrated or denatured
starch," then neutralise with ammonia or corbonate of soda taking care always to
secure alkalinity by using an excess of carbonate of soda or potash.
In the preparation of the two baths I only employ heat for the solution of the
salts.
The composition of this second bath may be varied considerably because, being
intended to deposit the lakes upon the fibres and to fix them there all the oxides that
the "nitrated or denatured starch" holds in alkaline solution assist separately or
united in producing the result. The following are a few examples of compositions
that may be employed
a. "Nitrated or denatured starch" 130 parts, sulphate of copper 24 parts, or
an equivalent quantity of oxide of copper, sulphate of alumina 40 parts, or an
equivalent quantity of alumina, arsenious acid 12 parts previously dissolved in a
solution containing 5 parts of potash, sufficient ammonia to neutralise, water 1000 parts,
and carbonate of soda 5 parts to alkalize.
b. "Nitrated or denatured starch" 72 parts, sulphate of alumina 24 parts, or an
equivalent quantity of alumina sulphate of iron 12 parts, or an equivalent quantity of
oxide of iron, a quantity of chloride of antimony containing four parts of antimony,
a sufficient quantity of ammonia to neutralise, water 1000 parts and carbonate of
soda for alkalizing 6 parts.
C.
"Nitrated or denatured starch" 120, sulphate of alumina 20 parts, or an
equivalent quantity of alumina, sulphate of magnesia 10 parts, or an equivalent
quantity of magnesia, sulphate of iron 20 parts, or an equivalent quantity of oxide of
iron, proto-chloride of tin 10 parts, a sufficient quantity of ammonia to neutralise,
water 1000, carbonate of soda for alkalizing 5 parts.
In the practice of my invention it is only necessary to choose the oxides or the salts
in the quantities which give the best shades and which the washing in water, carbonate
of soda and soap show to be the most resisting.
These shades of black produced from a logwood or other astringent tanniferous
base may be varied by adding to the first or second bath or to both, yellow,
green, or blue coal tar colours, or indigo in the various states in which it is employed
in dyeing..
For this purpose I place in the first or acid bath such colours as can co-exist with
the astringent materials and the acid; in the second bath such colours as can co-exist
with alkalinity. The proportions of these materials are best ascertained by trial for
each case.
In performing the dyeing process I proceed as follows:-
I place the stuffs, yarn, hair, skins etcetera it is intended to dye in the first or acid
bath and leave them well immersed therein during one or two hours, according to the
surrounding temperature; I then remove them from the first bath and wring them
as dry as possible; then partly dry them in the open air, or in a stove so as to leave
in them a little moisture. This is essential in order to avoid too great a concentration
of the acid which textile materials retain and which would lead to slight damage to
the colouring matters not yet fixed.
When it is required to dye yarns or woven goods of great thickness or that have
already been dyed and which are difficult to re-dye in black, it is advantageous to
raise the temperature slightly to from 40° to 60° centigrade. For light yarns and
woven goods, cotton, and wool on the skin, a temperature of 10° to 20° centigrade
should not be exceeded.
Instead of a continuous immersion in the bath, of the articles to be dyed, they
may be subjected to successive immersions in the usual way by means of the apparatus
ordinarily employed for that purpose.
The articles taken from the first or acid bath, wrung out and sufficiently dried, or
even drained only, are immersed in the second or alkaline bath. They there remain,

page_text: or are subjected to repeated immersions therein for from of an hour to an hour and
a half or more, according to their thickness or size, care should be taken that the
bath, either before or after the immersion of the articles in it is distinctly. alkaline.
A solution of carbonate of soda should be kept always at hand to enable the
alkalinity to be maintained after the immersion; the acid brought from the first bath
must not be allowed to destroy the alkalinity of the second.
It is only necessary to employ artificial heat under the same circumstances as
those mentioned in reference to the first bath; it is advisable only to apply heat
after a first immersion cold and at rest of 20 or 30 minutes duration. Time must be
left before heating for the colour to be fixed. It is never necessary to raise the
temperature beyond 50° or 60° cent. The articles on leaving the second bath are
wrung out as on leaving the first, but, not so much; a notable quantity of liquid
should be left in. expose them after this light wringing to the air for from one
to three hours or more according to the heat of the day and other circumstances. By
this exposure the oxygen of the atmosphere gradually produces a black colour and
as soon as this is attained I stop this oxidation (the energy of which is attributable
to the alkalinity of the liquia) by washing in a large quantity of cold or tepid
water until all discharge ceases. Other washings may follow with water slightly
soapy or simply alkaline if thought necessary. After washing it only remains to
wring as completely as possible and to dry either in the open air, in a heated
chamber or stove or on heated cylinders. The operation of dyeing which including
exposure to the air has thus only occupied a few hours and has required little or
no heat except that necessary for the preparation of the baths is now complete.
The astringent colouring matters have been deposited on the articles in the first
or acid bath; they have been fixed by the oxides in the second or alkaline bath
and have attained a definite black colour solely by the oxydizing action of atmo-
spheric air without taking other oxygen from chromates, chlorates, or other
oxydizing agents accompanied by acids, which always produce more or less injury
of the fibres and even of the colour that they have taken part in producing. If
however it is desired to facilitate the oxidation, chromates chlorates &c. may be used
in the second bath without fear of injurious effects, provided the alkalinity of the bath
is maintained.
This new method of dyeing may be practised not only on cotton and woollen
fibres, stuffs &c., which have not been dyed before, but also on all fibres, stuffs,
hair &c. which have already been dyed in various shades, and even in black, by
other processes. On all fibres or stuffs which have received what is called in dyeing
a foundation of indigo or any other more or less solid colouring matter.
Having now particularly described and ascertained the nature of my said inven-
tion and in what manner the same is to be performed, I declare that what I
claim is :-
First The application and use in the art of dyeing, of the product which I call
"nitrated or denatured starch" resulting from the oxidizing reaction of nitric
acid on starch or fecula or other forms of lignine or cellulose, as hereinbefore
described.
Second-The method of employing in the art of dyeing the aforesaid "nitrated or
denatured starch," such method consisting in the use of two baths the first of which
contains the tanniferous astringent materials usually employed in dyeing but to
which is added a salt of copper, with or without another salt, and with or without
coal-tar, or other colouring matters; and the second of which baths the base of which
is the aforesaid "nitrated or denatured starch," holds in alkaline solution one or
more of the oxides or salts which are not precipitated therein; the said second
bath being used with or without such colouring matters as can co-exist in the alkaline
medium, as herein before described.
Third-The application and use, in the art of dyeing in black, of a bath consisting
of an alkaline mixture in which arsenious acid is associated with oxide of copper

page_text: and alumina with or without the addition of any other oxide or oxides which
is, or are soluble in the aforesaid "nitrated or denatured starch," as hereinbefore
described.
Fourth-The application and use in the art of dyeing in black. of a bath consisting
of an alkaline mixture in which oxide of antimony is associated with oxide of iron
and alumina with or without the addition of any other oxide or oxides which is or
are soluble in the aforesaid "nitrated or denaturel starch," as hereinbefore described.
Fifth—The application and use, in the art of dyeing in black, of a bath consisting
of an alkaline mixture in which oxide of tin is associated with alumina, magnesia,
and oxide of iron with or without the addition of any other oxide or oxides which is
or are soluble in the aforesaid "nitrated or denatured starch," as hereinbefore
described.
Sixth The application and use in the art of dyeing of mixtures which by the aid
of the aforesaid "nitrated or denatured starch are enabled to retain metallic or
earthy oxides, or colouring matters, whether such such mixtures are alkaline, acid,
or neutral, substantially as hereinbefore described.
Dated this 24th da
O1 August 20
C. F. X. NOROY.
Per W. H. Beck,
115, Cannon Street, London, Agent.
C. F. X. NOROY.
Per W. H. Beck,
115, Cannon Street, London, Agent.