Improvements in the Process for Printing, Transferring and Fixing Lithographic Colours and the like, with an Oily or Resinous Base, especially on to Stuffs,
Year: 1899

page_text: Date of Application, 4th Sept., 1899
Complete Specification. Left, 10th May, 1900-Accepted, 1st Sept., 1900
PROVISIONAL SPECIFICATION.
Improvements in the Process for Printing, Transferring and Fixing
Lithographic Colours and the like, with an Oily or Resinous Base,
especially on to Stuffs,
I, JEAN DIEDERICIIS, of Quai des Brotteaux, Lyons, in the Republic of France,
do hereby declare the nature of this invention to be as follows:-
This invention relates to improvements in the process by means of which
printing, transferring and fixing are effected with oily or lithographic inks or
varnishes in one or more colours, as well on stuffs as on paper, and to the refining
of such colours, in order to obtain as a final technical or commercial result,
impressions superior to those obtained hitherto.
The transfer of these chromolithographic or zincographic impressions from
paper to the stuffs has not been successfully effected hitherto in so far as the
colours should combine tinctorially with the stuffs.
By careful study and numerous experiments, I have ascertained the cause of
this want of success and have succeeded in avoiding all the existing disad-
vantages, by means of the following course of procedure.
1. Altering the nature of the colours and the manner of employing them.
2. Modifying the treatment and preparation of the transferring paper as well
as of the stuffs.
3. Effecting changes in the work to be carried out, or altering the means
employed in transferring the impressions from the paper to the stuffs.
4. By employing heat in effecting the transfer.
NATURE OF THE COLOURS AND MANNER OF EMPLOYING THEM.
All the colours tried hitherto, but without success, are tannates and fatty
acid salts, artificial colours of which rosaniline is the type.
Attempts have also been made, but with no greater success, with artificial
colours which are insoluble or not easily soluble in water, but soluble in ordinary
alcohol, or methyllic alcohol, or in acetic acid moans hitherto employed in
impregnating the tissue.
The tannin of these tannates was fixed to a large extent on the tissue where
it gradually tarnished under atmospheric action and spoiled the shades.
The fatty acid salts of these colours produce effects which are too pale, and
irregular tones.
The colours insoluble in water, but soluble in the substances mentioned above,
produce very inferior shades.
It was necessary to avoid the tarnishing of the tannin colours, and I have
discovered the means by combining the tannin with a metal, preferably tin and
antimony, metals which I employ for mordanting the stuffs, especially before
impregnation with the transferring liquid.
I effect these mordanting operations by means employed amongst dyers; for
example, with stannate of soda at about 7° B. or with a solution of antimoniate
of potash.

page_text: I have also found that additions of glycerine, of lactic acid, to this hot gummy
water are useful.
The stuff being spread out on a table, which it is desirable to cover suitably
as an ordinary stuff-printing table, I have proved that the ordinary steeping
produces a better effect. by printing the transferring liquid on the tissue with a
plate which should preferably be covered with linen cloth or felt; this is a
mode of impregnating with the transferring liquid.
I have also found that the introduction of glycerine and adraganth gum into
the material employed in the previous treatment or finishing of the tissues
facilitates the transfer.
plate which should preferably be covered with linen cloth or felt; this is a
mode of impregnating with the transferring liquid.
I have also found that the introduction of glycerine and adraganth gum into
the material employed in the previous treatment or finishing of the tissues
facilitates the transfer.
very good results are obtained with the following compound :
700 grammes of ordinary acetic acid.
300
15
وو
"
"
"
5 to 20
"
alcohol 90/95°.
glycerine.
adraganth gum.
"
The addition of glycerine and adraganth gum, whatever may be the pro-
portions of the added substances, ensures a new technical effect.
I have discovered that the addition of glycol, especially of propyllic glycol,
acetines, lactic acid, acid acetates having an alkaline base, chloride of aluminium,
facilitate the transferring, and enable a dry or less moist tissue to be employed.
These are improvements in the material employed as preparation for the
transfer.
TRANSFER TO THE STUFFS OF IMPRESSIONS MADE ON THE PAPER.
I apply the right side of the paper to the stuffs prepared in the manner just
mentioned, and proceed to effect transfer by simple pressure, as done hitherto
but without success, whilst such means are successful with my process owing to
the combined effect of my different improvements.
I have found that by interposing a leaden plate between the stuff and the
table, and putting another leaden plate on the wrong side of the papers the
effect of the pressure is more complète and more regular, and in such case, the
pressure may be less.
The plates may be of lead or any other elastic material or malleable metal.
Respecting the temperature at which it is suitable to act.
I have discovered that heat considerably facilitates the transfer and enables
the pressure to be very considerably diminished. It also enables more than one
transfer to be made with the same printed paper.
I principally heat the wrong side of the paper after the latter has been placed
on the stuff, and apply the heat either with a smoothing iron or with a heated
cylinder which I roll over the paper, or in any other manner.
The important point is the application of heat by means of any heating
apparatus whatever, with the object of facilitating the transfers now in question
and to avoid excessive pressure.
I would observe that in applying heat leaden or other plates as referred to
previously I obtain better results with the same pressure.
FINISHING.
The operations just described having been effected, then according to the
colours employed, the purity of tone desired, the desired strength, etc., I
expose to the action of vapour, wash, soap or not, the stuffs on which I have
made transfers.
"
When I have transferred tannin colours to the non-mardanted stuffs, I effect
the fixing, (preferably after the vaporising) by means of emetic or other salts
of antimony or tin, as is practised, but under other circumstances by dyers and
cotton printers.
I have conceived a new means of fixing the colours, insoluble in water, which

page_text: I transfer to this tissue. For this purpose, I expose these tissues, furnished with
their colours to the action of vapours capable of dissolving the colours, for
example, vapours of alcohol, of acetic acid, of acetines, or mixtures of several
of these vapours, mixed or not mixed with aqueous steam.
I apply these vapours preferably in a heated state.
The improvements described are equally applicable to the production on paper
of chromo-lithographs; the latter not having the dauby and inartistic appearance
observable in chromolithographics as produced at present.
With this object I print with coloured lithographic inks as referred to for
effecting transfers on to tissues; and I have perceived that, in applying to the
papers the mordants and the mordanting operations employed for cotton and
other filaments, superior technical results are obtained. This paper is adapted
to combine tinctorially with a large number of tinctorial substances, for example,
alizarine, purpurine, and colours derived therefrom, cochineal, vegetable colouring
matters.
I steep the paper, in sheets, in a solution of alkaline stannate of 5° to 20° B.
for example until it is well moistened. I drain or squeeze the paper, avoiding
any creases, I then immerse it in sulphuric acid of 10 to 15° B. for example;
when the acid has entirely reacted, which takes place in five or ten minutes, I
withdraw the sheets and wash them until they become neutralised I then dry
them, preferably at the ordinary temperature.
If the paper is continuous, perform these operations in tanks with roller
guides or in the dipping apparatus employed by calico printers.
I have proved that it is useful, for certain colours (alizarine and its deriva-
tions, cochineal, etc.,) to replace the stannate by alkaline alumniate of 3° to 8° B.
and the sulphuric acid by a solution of a salt of ammonia of 8° to 14° B.
I also employ, according to requirements, the other mordants used in dyeing
and printing on calico.
When the colour, does not dye the paper or the stuff even if mordant, (rosaniline.
for example) I make use of tannates, and of these mordant papers and tissues,
or again I complete the metallic mordant by the aid of Turkish red oil and I
am thus able to fix nearly all the tinctorial matters.
In many cases, in that of artificial colours such as carbons dyed with rosaniline,
gum, starches, especially proteic substances a simple "badigeoning" (stone-
colour painting) of the paper, before impression, with a solution of albumen, of
25 to 125 grammes per litre, for example, followed by coagulation by aqueous
steam, or by passing through boiling water or by formicaldehyde.
The albumen may be replaced by any other coagulate proteic substance.
After printing on this paper I vaporise, wash, soap and re-wash as mentioned
for the tissues, with more care, as the paper is not so strong.
Moreover I soap more circumspectly so as not to impair the shades.
When I have transferred an impression from the ordinary paper to this
"proteic" paper, I finish the latter in the manner just indicated.
It will thus be seen that I am able to obtain on paper, either directly or by
transfer, lithographic impressions in one or more colours, as well as the fixing
and refining of these colours.
Dated this 1st day of September 1899.
WHEATLEY & MACKENZIE,
40, Chancery Lane, London, W.C., Agents.

page_text: COMPLETE SPECIFICATION.
Improvements in the Process for Printing, Transferring and Fixing
Lithographic Colours and the like, with an Oily or Resinous Base,
especially on to Stuffs.
I, JEAN DIEDERICHS, of Quai des Brotteaux, Lyons, in the Republic of France,
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:―
This invention relates to improvements in the process by means of which
printing, transferring and fixing are effected with oily or lithographic inks or
varnishes in one or more colours, as well on stuffs as on paper, and to the refining
of such colours, in order to obtain as a final technical or commercial result,
impressions superior to those obtained hitherto.
The transfer of these chromolithographic or zincographic impressions from
paper to the stuffs has not been successfully effected hitherto in so far as the
colours should combine tinctorially with the stuffs.
By careful study and numerous experiments I have ascertained the cause of
this want of success and have succeeded in avoiding all the existing disad-
vantages, by means of the following course of procedure:-
1. Altering the nature of the colours and the manner of employing them.
2. Modifying the treatment and preparation of the transferring paper as well
as of the stuffs.
3. Effecting changes in the work to be carried out, or altering the means
employed in transferring the impressions from the paper to the stuffs.
4. By employing heat in effecting the transfer.
NATURE OF THE COLOURS AND MANNER OF EMPLOYING THEM.
All the colours tried hitherto, but without success, are tannates and fatty
acid salts of artificial colours of which rosaniline is the type.
Attempts have also been made, but with no greater success, with artificial
colours which are insoluble or not easily soluble in water, but soluble in ordinary
alcohol or in methyllic alcohol, or in acetic acid, means hitherto employed in
impregnating the tissue.
The tannin of these tannates was fixed to a large extent on the tissue where
it gradually tarnished under atmospheric action and spoiled the shades.
The fatty acid salts of these colours produce effects which are too pale, and
irregular tones.
The colours insoluble in water, but soluble in the substances mentioned above, *
produce very inferior shades.
It was necessary to avoid the tarnishing of the tannin colours, and I have
discovered the means by combining the tannin with a metal, preferably tin and
antimony, metals which I employ for mordanting the stuffs, especially before
impregnating with the transferring liquid.
I effect these mordanting operations by means employed amongst dyers; for
example, with stannate of soda at about 7° B. or with a solution of antimoniate
of potash.
I also bring about the desired effect by introducing the mordant after the
transferring operation, and then either before or after the washing; in this case,"
I prefer acid mordants such as the solutions of chloride of tin or chloride of
antimony, antimonic tartrates or alkaline stannates, of acetate, or of sub-sulphate.
of alumina.
The means consist in the introduction of metals capable, when a tannin colour

page_text: is employed, of producing an insoluble and inalterable composition of metal,
tannin and colouring matter.
I have discovered the means of dispensing with tannin by dyeing and super-
saturating, preferably carbon (especially animal carbon) with the colour to be
employed, for example, with rosaniline or one of its salts, with sulphurised
indigo (carmine of indigo) or any other kind of colouring matter, provided that it is
capable of being fixed on the carbon and of printing the fibre of the stuff or of
the paper; after which I dry this carbon and wash it as required, then braying
it with the varnish or the lithographic ink.
I have also discovered that good results may be obtained by colouring
"proteid" substances (gelatines, albumens, peptones, for example) carbohydrates
(starches and their derivatives, gums) with the colouring materials which they
are capable of transferring to the tissues.
Amongst the various means employed for colouring these substances I prefer
that which consists in placing them in contact with solutions of colouring
matters (salts of rosaniline, carmine of indigo, for example).
If starches be employed I act in the same way or at the boiling point in
order to obtain a coloured starch paste.
I then dry these products, bray them and incorporate them in the varnish.
I have also found that certain compounds of aluminium, of iron, and of chrome,
dyed with artificial colours (rosaniline for example) especially the phosphates,
arsenites, arsenates, benzoates, readily transfer their colours to the fibres after
being dried, brayed with the varnish and printed on paper.
TREATMENT OF TRANSFERRING PAPERS.
Chromo-lithographed paper transmits its colour to stuffs with difficulty and
always irregularly, in spite of the liquids with which the latter are impregnated
and the great pressure employed.
I have discovered the remedy for these disadvantages; which consists in apply-
ing to the printed side, and in the form of spray or vapour, liquids capable of
being absorbed by the impression to be transferred. The transfer, is thus
effected easily and regularly.
When I effect this impregnation with steam I expose the printed paper to.
cold or more or less heated vapours of hydrocarbons which will be
retained by the varnish; or acids (acetic, formic) which will be retained
by the colouring material or alcohols, glycols, acetones, acetines which will
be retained at the same time by the varnish and the colour.
The transfer to the tissue should be effected before the liquids evaporate.
When the said liquids which become fixed on the colouring material are
employed, the tissue may be less strongly impregnated with fixing liquid.
These impregnations may be effected on the right side as well as on the wrong
side and on both sides and with a cylinder made of elastic material (gelatine
for example, or india-rubber).
TREATMENT OF STUFFS.
I have proved that by previously impregnating the tissue with a very weak
solution of thickening material, at the rate, for example, of 25 grammes of gum
per litre) and effecting this impregnation in employing heat at the boiling point
the tissue takes the colours better from the paper. After this impregnation, I
preferably dry on cylinders by means of heat.
I have also found that additions of glycerine, of lactic acid to this hot gumming
water are useful.
The stuff being spread out on a table, which it is desired to cover suitably
as an ordinary stuff printing table, I have proved that the ordinary steeping
produces a better effect, by printing and transferring liquid on the tissue with a
plate which should preferably be covered with linen cloth or felt; this is a
mode of impregnating with the transferring liquid:

page_text: I have also found that the introduction of glycerine and tragacanth gum into
the material employed in the previous treatment or finishing of the tissues
facilitates the transfer.
Very good results are obtained with the following compound ·
15
5 to 20
"
glycerine.
"
tragacanth gum.
The addition of glycerine and tragacanth gum, whatever may be the pro-
portions of the added substances, ensures a new technical effect.
I have discovered that the addition of glycol, especially of propyllic glycol,
acetines, lactic acid, acid acetates having an alkaline base, chloride of aluminium,
facilitate the transferring, and enable a dry or less moist tissue to be employed.
These are improvements in the material employed as preparation for the
transfer.
TRANSFER TO THE STUFFS OF IMPRESSIONS MADE ON THE PAPER.
I apply the right side of the paper to the stuffs prepared in the manner just
mentioned, and proceed to effect transfer by simple pressure, as done hitherto
but without success, whilst such means are successful with my process owing to
the combined effect of my different improvements.
I have found that by interposing a leaden plate between the stuff and the
table, and putting another leaden plate on the wrong side of the papers the
effect of the pressure is more complete and more regular, and in such case, the
pressure may be less.
The plates may be of lead or any other elastic material or malleable metal.
Respecting the temperature at which it is suitable to act.
I have discovered that heat considerably facilitates the transfer and enables
the pressure to be very considerably diminished. It also enables more than one
transfer to be made with the same printed paper.
:.
I principally heat the wrong side of the paper after the latter has been placed
on the stuff, and apply the heat either with a smoothing iron or with a heated
cylinder which I roll over the paper, or in any other manner.
The important point is the application of heat by means of any heating
apparatus whatever, with the object of facilitating the transfers now in question
and to avoid excessive pressure.
I would observe that in applying heat and using leaden or other plates as
referred to previously I obtain better results with the same pressure.
FINISHING.
The operations just described having been effected then according to the
colours employed, the purity of tone desired, the desired strength etc., I
expose to the action of vapour, wash, soap or not, the stuffs on which I have
made transfers.
When I have transferred tannin colours to the nonmordanted stuffs, I effect
the fixing, (preferably after the vaporising) by means of "emetic " or other salts
of antimony or tin, as is practised, but under other circumstances by dyers and
cotton printers.
I have conceived a new means of fixing the colours, insoluble in water, which
I transfer to this tissue. For this purpose, I expose these tissues, furnished with
their colours to the action of vapours capable of dissolving the colours, for
example, vapours of alcohol, of acetic acid, of acetines, or mixtures of several
of these vapours, mixed or not mixed with aqueous steam.
are
I apply these vapours preferably in a heated state.
The whole of the preceding shows that the chief features of my invention

page_text: 1. Metallisation of tannin transferred to tissues and to papers or other sub-
stances, for the purpose of preserving the tannin from the tarnishing action of
atmospheric agencies.
2. The replacing of the tannates by dyed or coloured carbons, proteic, matters
or their derivatives, gummy or amylaceous substances.
3. The employment with the same object of varnishes which readily transfer
the whole or a part of their colouring matter, for example, lacs having a base of
benzoate of alumina.
4. The application to the papers or tissues of suitable liquids in a state of spray
or vapour, for the purpose of facilitating the transfers, without confusing the
design.
5. The slight previous gumming of the tissue.
6. The application to the tissues of transferring preparations by means of
plates.
7. The employment of tragacanth gum in the material employed as preparative
or dressing.
8. The addition to the transferring preparative, of glycol, acetines, lactic acid,
acetates, acid formiates and lactates having a base of ammonia, potash or soda,
of lactates and chlorides of aluminum.
9. The employment of leaden or other plates for facilitating the transfers.
10. The employment of heat in the transferring operations.
11. The vaporising operation applied after the transfer, to the tissues or papers,
when the vapours employed with this object are capable of dissolving the colours
which are insoluble in water or in aqueous steam, and thus effecting the fixing.
12. The employment of my means in direct lithochromic impression printings.
13. The combination of my means with one or more already known means.
The improvements described are equally applicable to the production on paper
of chromo-lithographs; the latter not having the dauby and inartistic appearance
observable in chromolithographics as produced at present.
With this object I print with coloured lithographic inks as referred to for
effecting transfers on to tissues; and I have perceived that, in applying to the
papers the mordants and the mordanting operations employed for cotton and
other filaments, superior technical results are obtained. This paper is adapted
to combine tinctorially with a large number of tinctorial substances, for example,
alizarine purpurine and colours derived therefrom, cochineal, vegetable colouring
matters.
I steep the paper, in sheets, in a solution of alkaline stannate of 5 to 20° B.
for example until it is well moistened. I drain or squeeze the paper, avoiding
any creases; I then immerse it in sulphuric acid of 10 to 15° B. for example;
when the acid has entirely reacted, which takes place in five or ten minutes, I
withdraw the sheets and wash them until they become neutralised; I then dry
them, preferably at the ordinary temperature.
If the paper is continuous, I perform these operations in tanks with roller
guides or in the dipping apparatus employed by calico printers.
I have proved that it is useful, for certain colours (alizarine and its deriva-
tives, cochineal, etc.), to replace the stannate by alkaline aluminate of 30 to 8° B.
and the sulphuric acid by a solution of a salt of ammonia of 8° to 14° B.
I also employ, according to requirements, the other mordants used in dyeing
and printing on calico.
When the colour, rosaniline for example, does not dye the paper or the stuff
even if it has been mordanted, I make use of tannates, or again I assist the
metallic mordant by the aid of Turkish red oil and I am thus able to fix nearly
all the tinctorial matters.
In many cases when artificial colours are employed a simple coating of the
paper effected before printing with a solution of albumen, of 25 to 125 grammes
per litre is sufficient if followed by coagulation by steam, or by passing through
boiling water, or by formicaldehyde,

page_text: The albumen may be replaced by any other coagulable proteid substance.
After printing on this paper I vaporise, wash, soap and re-wash as mentioned
for the tissues with more care, as the paper is not so strong.
Moreover I soap more circumspectly, so as not to impair the shades.
When I have transferred an impression from the ordinary paper to this
proteic" paper, I finish the latter in the manner just indicated.
It will thus be seen that I am able to obtain on paper, either directly or by
transfer, lithographic impressions in one or more colours, as well as the fixing
and refining of these colours.
Having now particularly described and ascertained the nature of my said
invention and in what manner the same is to be performed, I declare that what
I claim is:-
2. In a
1. In a printing process in which the design is transferred directly from one
material on to another by pressure the process consisting in heating the carrier
of the design during the transfer to facilitate the transference to the material.
printing process in which the design is transferred directly from one
material on to another by pressure the process consisting in mordanting the
material to be printed with a metallic solution, in printing the design on
carrier material, in heating the carrier with a liquid or spray that is absorbed by
the transfer ink, in applying a transfer dressing to the material to be printed, in
heating the design during the transfer and in applying a fixing vapour to the
printed material.
a
3. The improved process for printing transferring and fixing lithographic
colours substantially as described.
Dated this 9th day of May 1900.
WHEATLEY & MACKENZIE,
40, Chancery Lane, London, W.C., Agents.