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Description  |
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The invention relates to new printing inks for the production of auxiliary
carriers for transfer printing on acid-modified textile fibre materials.
These inks are characterised in that they contain at least
(a) as a dyestuff intermediate, a carbinol base of cationic dyestuffs,
which can be sublimed at 160.degree.-240.degree. C, of the formula
##STR2##
wherein A, B and D represent an aryl or heteryl radical,
B can also denote hydrogen or can, conjointly with A, form the remaining
members of a heterocyclic ring system,
E represents a direct bond or a >N-alkyl group,
L represents a methine group which is optionally substituted by alkyl,
nitrile or alkoxycarbonyl or represents a N atom and
n denotes the numbers 0 or 1,
(b) a practically anhydrous neutral organic solvent and
(c) a neutral resin which is soluble in this solvent.
By "transfer printing" there is understood a recent dyeing and printing
process which is characterised in that the dyestuffs are transferred by
the action of heat and optionally of pressure from an auxiliary carrier,
printed with special printing inks, onto the substrate which is to be
printed, that is to say are in general transferred by sublimation.
(Compare, for example, French Pat. Nos. 1,223,330 and 1,334,829).
Hitherto, as a rule, readily sublimable disperse dyestuffs have been
employed for this purpose, and polyester fibre materials have preferably
been employed as substrates.
The dyestuffs used in the inks according to the invention, on the other
hand, are preferentially suitable for printing of textile fibre materials
which can be dyed with basic dyestuffs.
As in the customary transfer process, the auxiliary carriers used are
preferably paper, but also cellophane, cellulose textiles, metal foils and
the like.
In the dyestuffs of the formula I required for the new printing inks, the
aryl radicals A, B and D represent naphthyl radicals and preferably phenyl
radicals of which at least one carriers an amino, alkylamino,
dialkylamino, arylamino, arylalkylamino, alkoxy or aralkoxy substituent in
the 4-position to the central C atom. In addition, these radicals can
contain further non-ionic substituents customary in dyestuff chemistry,
such as nitro, halogen, alkyl, cycloalkyl, hydroxyl, alkoxy, aralkoxy,
cycloalkoxy, aryloxy, acyloxy, acyl, alkoxycarbonyl, amidocarbonyl,
nitrile, amino, alkylamino, dialkylamino, acylamino, mercapto,
alkylmercapto and arylmercapto groups, with "acyl" in general being
intended to mean alkylcarbonyl or arylcarbonyl.
Suitable heteryl radicals A, B and D are radicals of the following
heterocyclic compounds: indole, indoline, thiazole, benzthiazole,
imidazole, benzimidazole, 1,2,4-triazole, indazole, pyrazole, pyridine,
quinoline, pyrimidine, quinoxaline, pyrane, benzo(b)-pyrane and
benz(cd)-indole.
These radicals can also be substituted further in the usual manner by
non-ionic substituents such as, for example, alkyl, cycloalkyl, aryl,
halogen and alkoxy.
Suitable heterocyclic structures which A and B can form conjointly with the
central C atom in compounds of the formula I are:
##STR3##
wherein Q is a fused arylene radical and
V.sub.1, v.sub.2, v.sub.3, w.sub.1, w.sub.2 and W.sub.3 are substiuents
customary for these types of dyestuff, such as, for example,
H, alkyl, halogen and others.
By the alkyl radicals mentioned above in any context there are to be
understood saturated and unsaturated alkyl radicals which preferably
contain 1-4 C atoms and can optionally be substituted, preferably
monosubstituted, by halogen, OH, CN, alkoxy, phenyl and the like. As
examples there may be mentioned: methyl, ethyl, propyl, butyl, vinyl,
allyl and cyanoethyl. By the aryl radicals mentioned above in any context
there are above all to be understood, unless otherwise defined, phenyl
radicals which can be substituted, preferably monosubstituted
bisubstituted or trisubstituted, by halogen, C.sub.1 -C.sub.4 -alkyl or
C.sub.1 -C.sub.4 -alkoxy.
The abovementioned cycloalkyl radicals are preferably cyclopentyl and
cyclohexyl radicals which can be substituted, for example by halogen or
C.sub.1 -C.sub.4 -alkyl.
The alkoxy radicals mentioned above in any context preferably have 1-4 C
atoms.
The dyestuff intermediates to be used according to the invention are known
or are easily obtainable according to known processes.
They are either synthesised directly (compare, for example, A 354,201) or
are liberated from the corresponding dyestuff salts in a known manner, for
example by the action of sodium hydroxide solution.
The dyestuff salts, in turn, are also largely known. Suitable dyestuff
salts for the preparation of the compounds to be used according to the
invention are
(1) diarylmethane and triarylmethane dyestuffs, such as are described in
Colour Index (for example C.I. Basic Blue 1, C.I. Basic Blue 5 C.I. Basic
Green 4) or in the more recent patent literature (for example German
Offenlegungsschriften (German Published Specifications) Nos. 1,811,337,
1,811,338, 1,811,651, and 1,811,652).
(2) Indolylarylmethane dyestuffs, such as are described, for example, in
German Offenlegungsschrift (German Published Specification) No. 1,569,742.
(3) Cyanine dyestuffs, such as are described, say, in the Colour Index, for
example C.I. Basic Violet 16 and C.I. Basic Orange 22.
(4) Azacyanine dyestuffs, such as are described, say, in German Pat. Nos.
1,083,000, 1,150,475 and 1,150,476 as well as 1,163,775.
(5) Cyanine dyestuffs which are derived from naphtholactam derivatives,
such as, for example, those of German Pat. Nos. 1,170,569, 1,184,882,
1,190,126, 1,190,126b, 1,287,004 and 1,225,325.
(6) Benzo-(b)-pyrane dyestuffs such as are described, say, in Helv. 34,
1772 (1951) and Teintex No. 8-9, 459 (1972).
Particularly suitable dyestuff intermediates are those of the formulae
##STR4##
wherein Z.sub.1 and Z.sub.2 denote hydrogen or C.sub.1 -C.sub.4 -alkyl,
Y.sub.1 denotes amino, C.sub.1 -C.sub.4 -alkylamino, C.sub.2 -C.sub.4
-dialkylamino or C.sub.4 -C.sub.4 -alkoxy,
Y.sub.2 denotes Y.sub.1 or H and
Y.sub.3 and Y.sub.4 denote H, methyl and/or chlorine.
(Those with Y.sub.1 = OCH.sub.3 ; Y.sub.4 = H and Y.sub.3 = Cl or CH.sub.3
are very particularly preferred.)
##STR5##
wherein T.sub.1 denotes methyl, ethyl, n-propyl, n-butyl or cyanoethyl,
T.sub.2 denotes methyl or ethyl,
T.sub.3 denotes T.sub.2 or H and
T.sub.4 denotes H, Br or Cl.
##STR6##
wherein T.sub.1 and T.sub.4 have the meaning mentioned and
T.sub.5 denotes H or CN,
T.sub.6 denotes H, CH.sub.3, OCH.sub.3, NO.sub.2, Cl, COOCH.sub.3 or
COOC.sub.2 H.sub.5 and
m denotes 1 or 2.
##STR7##
wherein T.sub.6 and m have the meaning mentioned and
U.sub.1 represents C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy or
C.sub.2 -C.sub.5 -alkylcarbonylamino.
The dyestuff intermediates to be used according to the invention can be
employed both in the pure, undiluted, pulverulent form (so-called uncut
material) and also in the form of a preparation. A suitable method for
producing a preparation is in particular the process described in German
Offenlegungsschrift (German Published Specification) No. 1,469,724, in
which the dyestuff is kneaded with a resin which does not soften below
120.degree. C, a non-ionic dispersing agent and optionally an antioxidant,
and the resulting granules are ground.
In the printing inks according to the invention, the dyestuff is generally
in the form of a solution.
Suitable solvents are neutral solvents, that is to say solvents which do
not react chemically with the dyestuff intermediates, namely: hydrocarbons
such as benzene, toluene and xylene; chlorinated hydrocarbons such as
chlorobenzene, ethylene chloride, trichloroethylene and
tetrachloroethylene; alcohols such as methanol, ethanol, isopropanol,
butanol and benzyl alcohol, ketones such as methyl ethyl ketone and
cyclohexanone, and various ethers and esters. They are used in the pure
form or as mixtures. Preferred solvents are the hydrocarbons mentioned,
and amongst these toluene, in turn, is preferred.
To prepare the new printing inks it is possible in principle to employ, as
resins, the same types as are used for the preparation of transfer
printing inks based on disperse dyestuffs, provided the resins react
neutral, because of the sensitivity to acid and alkali of the dyestuffs to
be used according to the invention. Examples of suitable resins are ketone
resins, such as, say, Kunstharz AFS.RTM. and cellulose ethers, such as,
say ethylcellulose.
To improve the sharpness of contour of the prints produced according to the
invention it is possible optionally to coat the auxiliary carriers,
printed with the new printing inks, with a colourless layer of binder or
resin, in accordance with the instructions of German Offenlegungsschrift
(German Published Specification) No. 2,110,910.
Suitable substrates which take up the dyestuff during the transfer printing
process are--as already mentioned--usual materials which can be dyed with
basic dyestuffs, for example materials of polyacrylonitrile, of copolymers
of acrylonitrile with other vinyl compounds, such as vinyl chloride,
vinylidene chloride, vinyl fluoride, vinyl acetate, vinylpyridine,
vinylimidazole, vinyl alcohol, acrylic and methacrylic acid esters and
amides and asymmetrical dicyanoethylene, and of acid-modified synthetic
materials, especially of acid-modified aromatic polyesters and
acid-modified polyamide fibres. Acid-modified aromatic polyesters are, for
example, polycondensation products of sulphoterephthalic acid and ethylene
glycol, that is to say polyethylene glycol terephthalates containing
sulphonic acid groups (type DACRON 64 of E. I. DuPont de Nemours and
Company), as are described in Belgian Pat. No. 549,179 and U.S. Pat. No.
2,893,816.
The dyestuff transfer is effected at temperatures of 160.degree. to
240.degree. C, preferably 200.degree. to 220.degree. C, over the course of
15 to 60 seconds.
The heat transfer can be effected by direct contact with heating plates, or
by hot air, hot steam or infrared radiation. Dyeings and prints which
display good fastness properties in use are obtained on the materials used
as substrates.
EXAMPLE 1
20 g of a carbinol base of the formula
##STR8##
are ground with 0-7.5 g of a cyclohexanone-formaldehyde resin of softening
point above 160.degree. C and 10-2.5 g of ethylcellulose N.sub.4 in a
pearl mill. 100 Parts of a printing ink are prepared by addition of
toluene containing 10% of polywaxes. A paper is impregnated with this
printing ink, using a spray gun. If this paper is pressed against a
textile of polyacrylonitrile fibres for 15-30 seconds at 180.degree. C, a
yellow print having good fastness properties is obtained. If a textile of
acid-modified polyester fibres (Dacron 64) is used, a strong yellow dyeing
is again obtained.
EXAMPLE 2
20 g of the carbinol base of the formula
##STR9##
are dissolved in 800 g of toluene containing 10% of polywaxes. A paper is
impregnated with this solution and dried. If this paper is pressed against
a fabric of polyacrylontrile fibres, a red dyeing with good fastness
properties is obtained.
EXAMPLE 3
20 g of the carbinol base of the formula
##STR10##
are converted to a printing ink as in Example 2. An aluminium foil is
impregnated with this printing ink, using a spray gun. If this foil is
pressed against a fabric of polyacrylonitrile fibres for 15-40 seconds at
180.degree. C, a clear blue print is obtained. If a textile of
acid-modified polyamide is used, a blue print is again obtained.
If, instead of the dyestuff intermediates employed in Examples 1-3, the
carbinol bases indicated by formulae in the table which follows are used
to prepare printing inks, an auxiliary carrier printed therewith gives
transfer prints of the colour shades indicated in the last column on
acid-modified textile fibre materials, for example of polyacrylonitrile.
__________________________________________________________________________
Example
Formula Colour shade
__________________________________________________________________________
4
##STR11## green
5
##STR12## blue
6
##STR13## blue
7
##STR14## blue
8
##STR15## reddish-tinged blue
9
##STR16## reddish-tinged blue
10
##STR17## reddish-tinged blue
11
##STR18## blue
12
##STR19## blue
13
##STR20## red
14
##STR21## bluish-tinged red
15
##STR22## bluish-tinged red
16
##STR23## red
17
##STR24## orange
18
##STR25## golden yellow
19
##STR26## violet
20
##STR27## blue
21
##STR28## blue
22
##STR29## orange
23
##STR30## red
24
##STR31## red
25
##STR32## orange
26
##STR33## orange
27
##STR34## orange
__________________________________________________________________________
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