Note: Descriptions are shown in the official language in which they were submitted.
~057905
The invention relates to a method of preparing printing
inks or pastes which are suitable for transfer printing and to the print-
ing inks or pastes so prepared.
It is known that dyestuff preparations for transfer print-
ing, by which is meant the thermal transfer of sublimable dyestuffs
from a carrier material to textile sheet materials, can be produced by
a process in which a dyestuff suitable for the transfer printing process,
together with about 25 to 50% of a suitable carrier, e.g. a cellulose
derivative, and of a dispersing agent, is ground down by wet grinding
or kneading, e.g. dispersion kneading, to obtain a particle size of about
0.01 to 2,u, with, however, the particle size mentioned rendering necessary
the presence of fairly large proportions of protective colloids in order
to avoid an agglomeration of the fine dyestuff particles in the printing
ink.
It has now been found that, surprisingly, it is also possi-
ble to employ dyestuff preparations consisting of pure dyestuff (the term
"dyestuff" is to be understood, here and in the following, as denoting
also the optical brighteners.
q~
C - 2 -
. . .
-- .
lOS~
since from the point of view of application and of the objective - modification
of the coloristic appearance of a substrate - there exists no fundamental dif-
ference), optionally together with small amounts of diluting agents and/or wet-
ting agents, for the preparation of printing pastes for transfer printing, pro-
vided that the particle size of the dyestuff has been reduced by a suitable
grinding operation to < 15 ~. The invention relates therefore to dyestuff pre-
parations, usable in the transfer printing process, which are free from carriers
and binders.
According to one aspect of the invention, therefore, there is pro-
vided a method of preparing a printing ink or paste which is suitable for trans-
fer printing, which method comprises dispersing in water or an organic liquid
suitable for use in a printing ink or paste a dyestuff or a dyestuff prepara-
tion containing at least 95% by weight of dyestuff and up to 5% by weight of
a diluting or wetting agent, based on the weight of the preparation, the dye-
stuff having a particle size less than 15 ~ and the volatility of the dyestuff
being such that at atmospheric pressure and at a temperature of from 160 to
220C. at least 60% by weight of the dyestuff is vapourised in less than 60
seconds.
According to another aspect of the invention there is provided a
printing ink or paste which is suitable for transfer printing which comprises a
dyestuff or a dyestuff preparation containing at least 95% by weight of dyestuff
and up to 5% of a diluting or wetting agent, based on the weight of the prepara-
tion, the dyestuff having a particle size less than 15 ~ and the volatility of
the dyestuff being such that at atmospheric pressure and at a temperature of
from 160 to 220C at least 60% by weight of the dyestuff is vapourised in less
than 60 seconds.
Suitable dyestuffs and optical brighteners for the process of the
invention are all those which are suitable for the transfer printing process
i.e. those which at atmospheric pressure are converted at between 150 and 220C
~-sj ~ ''"'.
.
~OS7905
into the vapour state, which are stable on heating, and which can be trans-
ferred undecomposed.
The products concerned are, for example, salts of cationic dye-
stuffs with acids having a pKs-value of > 3, which advantageously are trans-
ferable undecomposed up to 190C.
In the case of these cationic dyestuffs, they are quite generally
chromophoric systems of which the cationic character is due to a carbonium,
ammonium, oxonium or sulphonium grouping. Examples of such chromophoric systems
- 3a -
, ~ .
, - ~
.
. , .
1~3S790~
are: methine~ azomethine, hydrazone, azine, oxazine~ thiazine
diazine, acridine, xanthene, polyarylmethane, such as
diphenylmethane or triphenylmethane, and coumarin dyestuffs;
also arylazo~ phthalocyanine and anthraquinone dyestuffs
having an external ammonium group, for example, a cyclo-
ammonium or alkylammonium group. The cationic optical
brighteners concerned are, in particular, those from the
methine, azomethine, benzimidazole, coumarin, naphthalimide
or pyrazoline series.
The cationic dyestuffs mentioned are used in the form
of their salts with acids of which the p~ -value is greater
than 3. Suitable acids of which the pK -value is greater
than 3 are both inorganic and organic acids.
Suitable also are, for example: metal complex dyestuffs
such as are described in the British Patent No. 1,320,819,
reactive dyestuffs as described in the British Patent
No. 1,254,021 and vat dyestuffs as described in German
Offenlegungsschrift 1,635,382.
Preferably used, however, are disperse dyestuffs and
optical brighteners without water-solubilising groups. These
can belong to the most varied classes, for example, to the
azo or anthraquinone series; likewise suitable however are
quinophthalone dyestuffs, nitro dyestuffs, azomethine dyestuffs
styryl dyestuffs and so forth. It is advantageous to use such
dyestuffs which are converted under atmospheric pressure
at a temperature of between 160 and 220C, by sublimation
or evaporation, to the extent of at least 60% in less
than 60 seconds into the vapour phase. Such dyestuffs
which may be mentioned are, for example, the monoazo
dyestuffs of the formula
OH
N ~
CO-Y X
wherein X and Y each represent an alkyl radical having
1 to 4 carbon atoms
- OH
\C - N
H3 C~13 .
and
NO
1 2 ~CO - CH
~ N = N - CH 3
H3C \CO - NH
-- 5 --
. . ..
1~)57905
and above all the quinophthalone dyestuff of the formula
C
. OH
and the anthraquinone dyestuffs of the formulae
O ~H-X
O ~H-X
(X = alkyl having 1 to 4 carbon atoms~,
~o~3
O NH2
O - OR
NH2
(R = alkyl having 3 to 4 carbon atoms)
.. . . . , .......... , .. . . ., . : .
.. . ..
,-, ;,,
'
10575V5
O NilCII
NIICH3
O NH
OCH3
O NH2
O NH
)J~
. o ~1 - z
(Z = cyclohexyl or phenyl),
and also the brominated or chlor-nated 1,5-diamino-4,8-
dihydroxyanthraquinones.
Among the optical brighteners without water-solubilising
groups, there may be mentioned, for example, those from the
series of benzazoles (derivatives of mono-/bis-benzoxazole
or benzimidazole), v-triazoles (derivatives of triazolyl,
benztriazolyl or naphthtriazolyl), co~arins (e.g., derivatives
of 3-phenylcoumarin), distyrylbenzenes, distyrylbiphenyls,
1,3-diphenylpyrazolines, 4-alkoxy- and 4,5-dialkoxynaphthalimides,
derivatives of styryl and stilbenyl, as well as pyrene
derivatives.
10~'7~(~5
A further impor~ant factor is the choice of dyestuffs
in dyestuff combinations, for only dyestuffs which are alike,
or close together, wlth respect to their sublimation
temperature should be combined, such as, e.g., specific
disperse dyestuffs with specific cationic dyestuffs.
All these dyestuffs are known and can be produced by
kno~m methods.
According to the present invention, these dyestuffs
are-ground until they have a particle size within the range
of <15,u, especially ~ 5,u. This can be achieved, for
example, by dry grinding, advantageously in an air-jet mill.
A short wet grinding is however preferred in order, in
particular, to obtain a fineness of at least S ~ or less, but
not the very high degree of fineness of the known preparations.
lS This wet grinding operation may be performed in any suitable
mill, such as in a wet ball mill or in a "Dynomuhle". Wet
grinding can be carried out with an aqueous, aqueous/organic
or organic liquid medium. The presence of about 1 to 5%~
relative to the amount of dyestuff, of a customary dispersing
2~ agent, which has the function of a deflocculating agent and
which is intended to prevent agglomerating, is in general
advantageous. This dispersing agent should dissolve both in
water and in organic solvents. Whether a nonionic, anionactive
or cation-active dispersing agent is used, depends on the
-- 8 --
.
-
;
1~57~5type of dyestuff. For example, an anion-active dispersing
agent is used for disperse dyestuffs, and a cation-active
dispersing agent for cationic dyestuffs. The dyestuffs
are separated from the resulting dispersion, for example,
by means of a two-phase granulation, such as is described in
DT-OS 2,412,369. The employed dispersing agent remains behind
in the liquid phase, and is not present in the finished
granulate or present only to the extent of traces.
To these finely ground dyestuffs, there can be optionally
added dilutlng agents in an amount of from about 0.1 to 5%,
relative to tlle amount of dyestuff. These diluting agents are
used principally for the adjustment of the tinctorial
strength and to obtain constancy of shade. There can however
also be added wetting agents, which improve the wetting of
the dyestuffs.
There are obtained in all cases dyestuff preparations
having a content of dyestuff exceeding 95%; however, those
preparations consisting of pure dyestuff, i.e. 100% dyestuff,
are preferred.
These carrier-free dyestuffs, optionally containing
diluting agents and/or wetting agents and ground down to
a particle size of ~15,u, are subsequently used, either in
the form of powders or in the form of granules produced
_ g _
1~5~
therefrcm in the known manner, together with a thickener,
with water alone or in a mixture of water and organic
solvents, such as ethyl alcohol, ethylene glycol, toluene
or white spirit, or free from water in pure organic solvents,
for the preparation of printing pastes or printing inks;
these are then used for the printing of carrier materials
which, in their turn, are employed in the transfer
printing process.
The thickener required for the preparation of printing
pastes and printing inks should be stable up to 230C, and
should act as thickening agent for the printing mixture,
and, at least temporarily, as a binder of the dyestuff on
the carrier to be printed. Suitable thickeners are synthetic,
semi-synthetic and natural resins, these being polymerisation
products and also polycondensation and polyaddition products.
There can be used in principle all the resins and thickeners
commonly employed in the industries producing paints and
varnishes and printing inks and pastes. The thickeners should
not melt at the transfer temperature, should not react
chemically in air or with themselves (e.g., cross-linking),
should have little or no affinity for the dyestuffs used,
merely retaining these on the printed area of the inert carrier
without modifying them, and should remain behind completely
on the carrier after the thermal transfer process. The
- 10 -
.
.
r. , . ~
.
~7~ ~ S
thickenrs preferred are those which are soluble in organic
solvents, and which rapidly dry, for example in a warm
stream of air, and form a fine film on the carrier. Suitable
water-soluble thickeners which may be mentioned are: alginate,
tragacanth, carubin ~from locust bean flour) dextrin,
mucilage etherified or esterified to a greater or lesser
degree, hydroxyethylcellulose or carboxymethylcellulose,
water-soluble polyacrylamides and polyacrylates and, in
particular, polyvinyl alcohol; and suitable thickeners
soluble in organic solvents are: cellulose esters, such
as nitrocellulose, cellulose acetate or cellulose butyrate,
and especially cellulose ethers, such as methyl, ethyl,
propyl~ isopropyl, benzy], hydroxypropyl or cyanoethyl
cellulose, as well as mixtures thereof.
For the improvement of the ready-for-use property of
these printing pastes, optional constituents may be added,
such as softening agents, swelling agents, high-boiling
1~ ~etr~ JecQ//n
solvents, such as Tetrali~ or Dcltali~, ionic or nonionic,
surface-active compounds, such as, for example, the condensation
product of 1 mole of octylphenol with 8 to 10 moles of
ethylene oxide. These printing pastes (solutions, dispersions,
emulsions) are produced by processes known per se, wherein the
dyestuffs as defined are, e.g. dissolved or dispersed in water
andJor solvent or solvent mixture, or are produced in situ,
- 11 -
579(~5
advantageously in the presence of a thickener which is
stable up to 230GC.
The carrier materials printed with such printing pastes
are ~nown, and consist advantageously of a flexible sheet
S material that is preferably dimensionally stable, such as a
strip, band or sheet, preferably having a smooth surface.
These carrier materials must be s~able to heat, and they
are made of the most varied types of materials, particularly
non-textile materials, such as, for example, metal, such as
an aluminium or steel sheet; or they consist of a con~inuous
strip of stainless steel, plastics or paper, preferably of a
clean, non-lacquered cellulose parchment paper, which is
optionally coated with a film of vinyl resin, ethylcellulose,
polyurethane resill or Teflon.
The optionally filtered printing pastes or printing inks
are applied to the carrier material, in places or over the
whole surface, by, for example, spraying, coating or,
advantageously, printing. There can also be applied to the
carrier material a multi-coloured pattern, or the carrier
material can be printed with a ground shade and thereafter
successively with identical or different designs. After
application of the printing paste to the carrier material,
this is dried, e.g., with the aid of a warm flow of air or
by infra-red irradiation.
- 12 -
~5'~ ~5
The carrier materials can be printed also on both
sides, whereby it is possible to select different colours
and/or designs for the two sides. In order to avoid the
use of a printing machine, the printing pastes can be
sprayed onto the carrier materials by means, for example,
of a spray gun. Particularly interesting effects are obtained
when simultaneously more than one shade is printed or
sprayed on the carrier material. Specific designs can be
obtained, e.g., by the use of stencils, or artis~ic designs
can be applied by brush. If the carrier material is printed,
then the most diverse printing processes may be employed,
such as high-pressure processes (letter~press prirlting,
flexographic printing), gravure printing (e.g., roller printing),
screen printing (e.g., rotary printing or film printing)
or electrostatic printing processes.
The carrier-free dyestuff preparations of the invention
are weak with regard to the tinctorial strength on the
carrier material, but they develop after the performance
of the transfer operation to produce a good tinctorial
strength and yield.
The transfer is effected in the usual malmer by the
action of heat. For this purpose, the treated carrier materials
are brought into contact with the materials to be printed,
especially textile materials, and are held at about 120 to Y
V~
210C until the defined dyestuffs applied to the c~rrier
material have been transferred to ~he textile material.
As a rule, 5 to 60 seconds are sufficient to achieve this.
The action of heat can be applied by various known
methods, for example, by passage over a hot hea~ing cylinder,
by passage through a tunnel-shaped heating zone, or by
means of a heated roller, a~vantageously together with
a pressure-exerting, heated or unheated counter roller, or
by means of a hot calender, or with the aid of a heated
plate, optionally under vacuum, which devices are preheated
to the required temperature by steam, oil, infra-red
irradiation ~r microwaves, or which are located in a
preheated heating chamber.
After completion of the heat treatment, the printed
material is separated from .he carrier. This material requires
no aftertreatment, neither a steam treatment to fix the
dyestuff, nor a washing to improve the fastness properties.
For printing with the transfer process, all s~nthetic
fibres are basically suitable, provided ~hat their thermo-
stability with respect to the process is sufficient. Suitablematerials in practice are polyester, polyacrylonitrile and
polyamide fibres, cellulose-2 1/2- and -triacetate fibres,
and mixtures of these with each other, or mixtures of
cellulose fibres-or albumen fibres.
- 14 -
~ ! ,.,.~ .:
.,.' '''' ~ , , .
. . ' ' ,, " , . ' ' , ~
' , ' ' " ~ ' ' ~ ~, ' ' ' '
~0579(~5
The use according to the invention of the solid dyestuff
preparations preferably consisting of 100% dyestuff compared with that
of known carrier-containing dyestuff preparations having a dyestuff con-
tent of about 50 to 75%, which are already in use commercially, has the
following outstanding advantages:
a) An appreciably greater universal possibility of application in the
various printing processes. The carrier-free preparations can be dis-
persed in the respective applied medium by means of ordinary commercial
intensive stirrers. The dyestuff preparations at present known for trans-
fer printing are, on the other hand, not universally applicable, but are
designed only for the production of a specific printing-paste composition.
b~ They render possible an increase in concentration or a correction
of printing pastes already prepared, without noticeably raising their
viscosity. This property of the preparations produced according to the
invention can in practice be of great advantage, in that unused stocks of
printing pastes can be incorporated.
c) Lower dyestuff losses in the transfer process. In the case of print-
ing on more highly absorbent carrier materials, for example, on porous
paper, the dyestuff that is more coarsely
- , ~ . : ' : ' , : : , -
.. , . . : ,,
- '"
~ 7~ V S
dispersed compared with the known preparations is deposited
preferably only on the surface. It cannot therefore be
carried by the solvent of the printing paste into the pores
of the carrier layer to the extent that the hitherto
customary, very finely dispersed preparations are carried
into the pores. By virtue of this fact, there can be obtained
in the case of thermal transferring higher colour yields
on the fabric.
d) Possibility of the production of printing pastes having an
extremely high content of dyestuff, in consequence of the
absence in the preparation of polymer carriers which raise the
viscosity.
e) As a result of the absence of additives increasing viscosity,
such as are constituted, e.g., by the carrier materials or
binders normally contained in transfer preparations, it is
possible, since no increase in viscosity occurs, to allow the
operating speed to increase to double the hither~o usual
operating speed, a factor which results in an increase of the
production of printed carriers with the same machine.
With the dyestuff preparations usable according to the
invention, there are obtained in the transfer printing process
very finely detailed designs and patterns having fine
indentations, which can be reproduced sharply outlined in
practically any shade of colour. An overlapping of the colours
- 16 -
.. ..
' '; -. . '. ' ' : ~ .. . . .
.
:- ' .. . .
'
1~57gV~
at the edges of the designs does not occur. Besides
patterned printings, also plain printings are possible,
and thes2 are particularly suitable for the covering
of materials which dye streakily.
S These carrier-free dyestuff preparations have a
preferred use for, in particular, the production of dark
shades, such as nigger brown, dark blue and black, and also
for the treatment of carpet materials, since they ensure
a high deposition of colour.
The following examples illustrate the invention, without
its scope being limited by them. Where not otherwise stated,
the term 'parts' denotes parts by weight.
. . . ~ , , .:
., ~ .
., - , , , :: ~ ,
,: , ''' :, , ,,,:
, -~;
~sy~os
A. Production of the dyestuff preparations
Example 1
1000 parts of the dyestuff of the formula
' ~
are ground in an air-jet mill under normal pressure
conditions (5-6 atmospheres) until an upper limit of the
particle-size distribution of 10 to 15 ,u maxim~. is attained.
There is obtained a dyestuff preparation (powder) which
consists of 100% dyestuff.
Example 2
1000 parts of the dyestuff according to Example 1 are
ground together with 20 parts of cellulose ethyl ether
(Ethocel E 7) in an air-jet mill under normal pressure
conditions until an upper limit of the particle-size distribution
of about 10 to 15 ~ is attained:
There is obtained a dyestuff preparation (powder) which
contains 98% of dyestuff.
Example 3
1000 parts of the dyestuff according to Example 1 are
- 18 -
~Je ~r~
. .
.
.
~ 0~79 0 5
ground together with 10 parts of sodium-isopropylnaphthalene-
sulphonate (Aerosol OS) in an air-jet mill, under normal
pressure conditions, until an upper limit of the particle-size
distribution of about 10 to 15,u is attained.
There is obtained a dyestuff preparation (powder) which
contains 99% of dyestuff.
- Example 4
1000 parts of the dyestuff according to Example 1 is
ground together with a m xture of 20 parts of cellulose
ethyl ether (Ethocel E 7) and 10 parts of sodium-isopropyl- t
naphthalenesulphonate (Aerosol OS) in an air-jet mill, under
normal pressure conditions, until an upper limit of the
particle-size distribution of about 10 to 15 ~u is attained.
There is obtained a dyestuff preparation (powder) which
contains 97% of dyestuff.
Example 5
If, instead of the dyestuff according to Examples 1 to 4,
identical amounts of the dyestuff of the formula
OH
are used under otherwise the same grinding conditions, then
- 19 -
3~ fr~ ~a~ '
.: , , ~ . : ~. .
:. . ::: .. , : - -
. : . - : .
'' ' ' ' " ' . ~ , ' : .
'
'~ - . .
~57~
there are obtained a dyestuff having an upper limit of
the particle-size distribution of about 10 to 15,u, and
preparations (powders) having a content of dyestuff of
between 97 and 100%.
Example 6
If, instead of the dyestuff according to Examples 1 to 4,
identical amounts of the dyestuff of t:he formula
are used under otherwise the same grinding conditions, then
there are obtained a dyestuff having an upper limit of the
particle-size distribution of about 10 to 15~u, and
preparations (powders) having a dyestuff content of between
97 and 100%.
Example 7
If, instead of the dyestuff according to Example 1,
identical amounts of the optical brightener of the formula
~ ~ CH = CH-
- 20 -
; ,~
', ' ' ~ '
'
1~7S~0S
are used, under otherwise tlle same grinding conditions,
then there is obtained an optical brightener having an
upper limit of the particle-size distribution of about lO,u.
There is thus obtained a preparation (powder) consisting
of 100% of opcical brightener.
t
Example 8
10 parts of a dyestuff preparation obtained according
to Examples 1 to 6 are added to 20 parts of water, whereupon
6 parts by volume of ethyl ace~ate are added with vigorous
shaking. After 10 minutes' shaking, there are obtained
spherical granules of 0.2 to 1 mm diameter, which are
separated from the two-phase system by means of a sieve
and then dried.
There are obtained free flowing, non-dusty dyestuff
preparations readily dispersible in a printing paste, which
preparations have a dyes~uff content of between 97 and 100%
and which are in the form of mechanically stable granules.
Example 9
30 parts of the dyestuff of the formula
O NH2
,o~
O OH
- 21 -
.' ,' . '~ ~ ' . ..
. . . . . .
, ~
' .
~ (~579(~5
are ground, in a continuous stirrer ball mill, with 70 parts
of water and 1 part of hydroxypropylcellulose until the
particle size is smaller than 15 microns, essentially
about 1 to 5 microns.
There are added, with stirring, 21 parts of isobutyl
alcohol to the grinding suspension, and the dyestuff is
caused to agglomerate. After a short time, there are obtained
spherical granules of 0.2 to 1 mm diameter, which are
separated from the suspension by a sieve, and subsequently
dried. The resulting dyestuff preparation is a granulate
consisting of practically 100% of dyestuff with slight
traces of hydroxypropylcellulose. The granulate obtained
is non-dusty and mechanically stable. When introduced into
a printing ink, it wets very readily, and can be dispersed
with a dispersing device into the separate particles which
have a particle size of below S microns.
Example 10
30 parts of the dyestuff of the formula
O ~H
~¢~
are ground, ir~ a continuous stirrer ball mill, with 80 parts
- 22 -
,
'
of watcr and 1 part of hydroxypropylcellulose until the
particle size is below 15 microns~ essentially about 1 to 5
microns. There are then added, with stirring, 23 parts of
ethyl acetate to the grinding suspension, and the dyestuff
S is brought into the agglomerated state. After a short time,
there are obtained spherical granules of 0.2 to 1 mm diameter,
which are separated from the suspension by means of a sieve,
and subsequently dried. The dyestuff preparation thus
obtained is a granulate consisting of practically 100% of
dyestuff with slight traces of hydroxypropylcellulose. It
wets very rapidly in a printing ink, and can be readily
dispersed by a normal dispersing stirrer into its separate
particles.
Example 11
An aqueous dyestuff press cake containing 30 parts of
the dyestuff of the formula
~/C~
,
OH
is ground in a 'Permill' with 100 parts of water until the
particle size is smaller than 15 microns, essentially about
1 to 10 microns. There are added, with stirring, 20 parts
of ethyl acetate to ~he grinding suspensi~n (after separation
- 23 -
"~ f~ e t~
- ,
..,~
.- ' ' "~ .
. . .
.
~79~15
of the glass beads used for grinding), and the dyestuff
is caused to agglomerate. There are obtained after a short
time spherical granules of 0.2 to 1 mm diameter, which are
separated from the suspension by means of a sieve, and
then dried. The dyestuff preparation thus obtained consists
of granules of pure (lOOa/o) dyestuff.
- 24 -
s
... .
.. .:
905
B App] ication o, the dyestuEf preparations accordin~ to A
for the preparation of printin~ pastes for the transfer-
pr;ntin~; process.
Example 12
20 parts of a dyestuff preparation obtained according
to Examples 1 to 8 are dispersed by means of a stirrer,
within 5 minutes, in a solution of 8 parts of ethylcellulose
in 72 parts of a mixture of methyl ethyl ketone and ethanol
(1:1). The aggregated dyestuff particles wet very rapidly
and disperse spontaneously into the primary particles. The
result is a printing paste, for gravure printing, having a
viscosity of 22 seconds (Ford cup 4), which printing paste
is suitable for the printing of paper for the transfer
printing process.
Example 13
10 parts of a dyestuff preparation obtained according to
i5 Examples 1 to 8 are dispersed within 5 minutes, by means of
a stirrer, in a solution of 22 parts of Versamid 930 (Schering),
1 part of AC Polyethylene 6A (Allied Chemical), 1 part of
Stabiliser XE-35 (Schering) and 0.1 part of silicone oil
SISS 200-350 (Soc. Ind. des Silicones) in 69.9 parts of a
solvent mixture isopropanol/benzine (1:1). The result is
an agglomerate free printing paste having a viscosity of
- 25 -
,
, '
.
- - " . ~ : . ~
. . , ,~, ,
,, , :,, ,
.:
.
- `
~s~ s
34 seconds (Ford cup 4), which can be printed perfectly
satisfactorily by flexographic printing on paper; this
paper can then be used in the transfer printing process
by placing the paper with a piece of tufted carpet made
from polyester fibres for 30 seconds in a press heated to
210C, and subsequently removing the paper. There is obtained
on the carpet an extremely clear and strong printing.
Example 14
A completely disaggregated dispersion having a viscosity
of 32 seconds (Ford cup 4), which is very suitable or
flexographic printing on paper, is obtained after 5 minutes
by the stirring in each case of 15 parts of the air-jet-ground
dyestuff preparations produced according to Examples 1 to 8
A into a solution of 3 parts of Cibamin M 86 (Ciba-Geigy) and
9 parts of Mowital B30M (Hoechst) in 73 parts of 96% denatured
alcohol by means of an Ultra-Turrax stirrer. The printing
paste can, by an increasing of its concentration with the
sa~e finely dispersed dyestuff preparations, be adjusted to
have a content of 30% and more, without any appreciable
change in viscosity.
Example 15
8 parts of a dyestuff preparation obtained according to
Examples 9 to 11 are dispersed by means of a Homorex stirrer,
within 10 minutes, in a solution of 8 parts of ethylcellulose
- 26 -
~ra~ ~4~`k
- .
`~
~57~(~5
in 84 parts of ethanol. The result is a printing paste
having a viscosity of 21 seconds (Ford cup 4), which is
suitable for the printing of paper for the transfer printing
process.
Example 16
23 parts of a dyestuff preparation obtained according
to Examples 9 to 11 are dispersed by means of an Ultra
Turax stirrer, within 4 minutes, in a solution of 2 parts
of ethylcellulose in 75 parts of ethanol. The dyestuff
preparations wet very well, and rapidly disperse into the
primary particles. There results a printing paste having
a viscosity of 21 seconds (Ford cup 4), which is suitable
for the printing of paper for the transfer printing process.
Example 17
S parts of the crystalline dyestuff of the formula
O NH-CH
O NH-CH3
and 5 parts of the crystalline dyestuff of the formula
O ~
H
- 27 -
. . . . -
- : ' . ~ '' -
'"'
. . . ' . ' ' ' .
1~)575~05
are ground, jointly in a glass-bead mill or sand mlll,
in denatured ethanol in the presence of 4 parts of ethyl-
cellulose until the particle size is reduced to about 2~u
and smaller. After removal of the grinding elements, there
is obtained a violet printing paste which i5 excellently
suitable for printing on transfer papers (viscosity Ford 4:
21 seconds).
This violet printing paste can, by the mere stirring-in,
by means of a turbine impeller, of 2 parts of an air-jet-
ground dyestuff of the formula
~ C~c~ '. ,
and 2.3 parts of the air-jet-ground dyestuff of the formula
b ~IH ~
be processed into a black printing paste, the viscosity of
which still remains very good in the optimum range of a
gravure-printing paste (viscosity difference only 1.5 seconds,
i.e. Ford 4: 22.5 seconds).
If, on the other hand, the same pure-pigment amounts of
the same two dyestuffs in the form of 50V/o ethylcellulose-
- 28 -
-
~V~7~ 5
dyestuff preparations are stirred into the viole~ printing
paste, then the viscosity of the resulting black printing in~
increases to above 50 seconds. A printing paste of such a
high viscosity is however unusable in rotary gravure (intaglio)
printing on paper.
Example 18
150 parts of a cationic dyestuff (ground by means of
an air-jet mill) of the formula
- Cl13 -
~----C - C113 \UCH
are stirred, with a planetary mixer, with 130 parts of
Printing Ink Solvent 2325 (Shell) containing 20 parts of
cobalt-linoleate in the dissolved state, for 30 minutes at
room temperature. There results a completely disaggregated
dyestuff dispersion in paste form, which can be mixed together
with 650 parts of a linseed oil varnish (350 P) containing
1S Pentalyn 833 (Hercules resin)~and 50 parts of polyethylene
wax to form a lithographic printing paste.
A paper printed therewith by the offset process produces
by transfer to an Orlon fabric, after 30 seconds contact time
in a BASF press at 195 to 200C, an intensely yellow-coloured
- 29 -
t~a~/e ~k
:. , ,: .: ' , - : ,
- .
'
. ~ . :
., , ~ ! .
~ 7~U5
printing.
If, instead of the cationic dyestuff, there are used
identical amounts of the cationic optical brightener
of the formula
3 C~3 ] C~l30503 Q
CH3
the procedure otherwise being the same, then a well optically
brightened Orlon fabric is obtained.
Example 19
20 parts of a dyestuff preparation obtained according
to Examples 1 to 8 are introduced, by means of a high-speed
stirrer, into 980 parts of a 2.5% aqueous solution of
sodium alginate, and the whole is stirred for 5 minutes.
There is obtained a printing paste which, by means of
screen printing, ca-n be printed on paper (simply sized paper,
65 g/m ), which can then be used in the transfer printing
process.
Example 20
20 parts of a dyestuff preparation obtained according
to Examples 1 to 8 are introduced into 980 parts of oil-in-
water emulsion. There results a printing paste which can
- 30 -
....
~ 7~
be printed on paper by means of screen printing, which
paper can then be employed in the transfer printing process.
The oil-in-water emulsion is prepared as follows:
15 parts of a carob bean flour ether and 5 parts of
a suitable emuLsifier are dissolved in 480 parts of water.
By means of a high speed stirrer, 500 parts of a high-boiling
benzine-mixture (boiling point 120 ~ 200C) are stirred into
this solution to form an emulsion.
Example 21
20 parts of a dyestuff preparation according to Examples
1 to 8 are stirred, by means of a high-speed stirrer, into
980 parts of a water-in-oil emulsion. A printing paste
is obtained, which can be printed by screen printing on
paper, which can then be used in the transfer printing
process.
The water-in-oil emulsion is prepared as follows:
15 parts of a suitable emulsifier is dissolved in 100
parts of a high-boiling benzine mixture. Into this solution
there are then stirred, by means of a high-speed stirrer,
885 parts of a 2.5% aqueous solution of sodium alginate.
.. ....
:" :'
, ' ~
