 |
Claims  |
|
|
I claim:
1. In a process for transfer printing of acid-modified textile fiber
materials wherein a dyestuff is applied to a temporary carrier web and
subsequently transferred to the textile material by being pressed against
the textile and heated to cause the dyestuff to sublime and be adsorbed by
the textile material, the improvement which comprises employing a printing
ink consisting essentially of
(a) as a dyestuff intermediate a dyestuff base which can be sublimed at
160.degree.-240.degree. C, of the formula
##STR18##
wherein R.sub.1 and R.sub.2 represent an alkyl or conjointly with the C
atom by which they are linked form a carbocyclic ring;
R.sub.3 denotes hydrogen alkyl, cycloalkyl or aralkyl;
R.sub.4 denotes hydrogen, alkyl, cycloalkyl, aryl, aryl, aralkyl, alkoxy,
aryloxy, aralkoxy, alkylamino, dialkylamino, arylamino, aralkylamino,
acylamino, sulphonamido, carbonamido, alkoxycarbonyl, acyl, nitrile or
halogen;
R.sub.5 denotes hydrogen, alkyl, alkoxycarbonyl, or nitrile;
R.sub.6 and R.sub.7 denote hydrogen, alkyl, alkoxy, aralkoxy, acylamino,
dialkylamino or alkylmercapto; or
R.sub.6 and R.sub.7 conjointly form a heterocyclic structure; and
B represents CH, N, or C-alkyl;
(b) a practically anhydrous neutral organic solvent; and
(c) a neutral resin which is soluble in this solvent.
2. Process of claim 1 wherein
R.sub.1, r.sub.2 and R.sub.3 denote methyl,
R.sub.4 denotes H, methyl, methoxy or chlorine,
R.sub.5 denotes H or methyl and
R.sub.6 and R.sub.7 denote H, methyl, methoxy, ethoxy, methylmercapto,
dimethylamino, diethylamino or acetyl or conjointly form a thiazole or
dioxane radical. |
|
 |
|
 |
Claims |
|
|
|
Description |
|
|
The invention relates to new printing inks for the preparation of temporary
supports for transfer printing on acid-modified textile fibre materials.
These inks are characterised in that they contain at least
(A) A DYESTUFF BASE WHICH CAN BE SUBLIMED AT 160.degree.-240.degree. C, of
the formula
##STR3##
wherein R.sub.1 and R.sub.2 represent an alkyl radical or conjointly with
the C atom by which they are linked form a carbocyclic ring,
R.sub.3 denotes hydrogen or an alkyl, cycloalkyl or aralkyl radical,
R.sub.4 denotes hydrogen or a non-ionic substituent,
R.sub.5 denotes hydrogen or an alkyl, alkoxycarbonyl or nitrile group,
R.sub.6 and R.sub.7 denote hydrogen or identical or different non-ionic
substituents which can optionally conjointly form a heterocyclic structure
and
B represents --CH--, --N.dbd. or
##STR4##
(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 or printing
process which is characterised in that the dyestuffs are transferred by
the action of heat and optionally of pressure from a temporary support
printed with special printing inks onto the substrate which is to be
printed, that is to say, in general, that they sublime from the temporary
support onto the substrate (compare, for example, French Patent Nos.
1,223,330 and 1,334,829). Hitherto, readily sublimable disperse dyestuffs
have as a rule been employed as dyestuffs for this purpose, whilst
polyester fibre materials have preferably been employed as substrates.
The dyestuffs used in the inks according to the invention are, on the other
hand, preferentially suitable for printing of textile fibre materials
which can be dyed with basic dyestuffs.
The temporary supports are, as in the customary transfer process,
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
alkyl radicals R.sub.1, R.sub.2 and R.sub.5 above all represent alkyl
radicals with 1 to 4 C atoms, methyl being preferred.
Suitable alkyl radicals R.sub.3 are C.sub.1 -C.sub.4 -alkyl radicals which
are optionally substituted by OH, halogen, nitrile, C.sub.1 -C.sub.2
-alkoxy or C.sub.2 -C.sub.4 -alkoxycarbonyl, such as methyl, ethyl,
n-propyl, n-butyl, hydroxyethyl, chloroethyl, cyanoethyl, methoxyethyl and
ethoxyethyl, acetoxyethyl and others.
Suitable carbocyclic rings formed by R.sub.1 and R.sub.2 are cyclopentyl
and cyclohexyl rings.
Suitable cycloalkyl radicals R.sub.3 are cyclopentyl and cyclohexyl
radicals.
Suitable aralkyl radicals R.sub.3 are benzyl and phenylethyl radicals.
Suitable alkoxycarbonyl radicals R.sub.5 are methoxycarbonyl and
ethoxycarbonyl radicals.
Suitable non-ionic substituents R.sub.4, R.sub.6 and R.sub.7 are
non-dissociating substituents customary in dyestuff chemistry.
Preferred radicals R.sub.4 are alkyl, cycloalkyl, aryl, aralkyl, alkoxy,
aryloxy, aralkoxy, alkylamino, dialkylamino, arylamino, aralkylamino,
acylamino, sulphonamido, carbonamido, alkoxycarbonyl, acyl, nitrile and
halogen .
Preferred radicals R.sub.5 and R.sub.6 are alkyl, alkoxy, aralkoxy,
acylamino, dialkylamino or alkylmercapto.
The alkyl and alkoxy radicals mentioned above in any particular context
(thus, for example, also including alkylmercapto and alkoxycarbonyl) are
above all those with 1 to 4 C atoms.
By "acyl" there is to be understood C.sub.1-C.sub.4 -alkylcarbonyl,
arylcarbonyl and in the case of R.sub.4 also arylsulphonyl.
The aryl radicals mentioned in any particular context are above all to be
understood as phenyl and tolyl radicals. The preferred cycloalkyl and
aralkyl radicals have already been mentioned for R.sub.3.
Halogen is preferably F, Cl and Br.
Dyestuff bases to be used preferentially are those of the formula I
wherein
R.sub.1, r.sub.2 and R.sub.3 denote methyl,
R.sub.4 denotes H, methyl, methoxy or chlorine,
R.sub.5 denotes H or methyl and
R.sub.6 and R.sub.7 denote H, methyl, methoxy, ethoxy, methylmercapto,
dimethylamino, diethylamino or acetyl, or conjointly form a thiazole or
dioxane radical. Very particularly preferred dyestuff bases are those in
which
R.sub.6 " h and
R.sub.7 denotes methoxy, ethoxy or acetyl and is in the
p-position to the N atom.
The dyestuff bases to be used according to the invention are in many cases
known and are described, for example, in the following journals: Berichte,
57, 144 (1924) and 59, 2,413 (1926); J. org. Chem. (USSR) VIII, 2,409
(1972) and, as intermediate products, in the following patent literature:
German Patent Nos. 1,004,748, 1,205,638, 1,083,000, 1,050,475 and
1,050,476. Other suitable dyestuff bases of the formula I can be prepared
analogously.
The dyestuff intermediates to be used according to the invention can be
employed either in a pure, undiluted, pulverulent form (so-called uncut
ware), or in the form of preparations. A suitable method for producing
such preparations is especially that described in German
Offenlegungsschrift (German Published Specification) 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 general, the dyestuff is present in the printing inks according to the
invention 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 is again preferred.
To prepare the new printing inks it is in principle possible to employ, as
resins, the same types as are used in the preparation of transfer printing
inks based on disperse dyestuffs, provided the resins have a neutral
reaction, because of the sensitivity to acids and alkalis of the dyestuffs
to be used according to the invention. Suitable resins are, for example,
ketone resins, such as, say, Kunstharz AFS.sup.(R), and cellulose ethers,
such as, say, ethylcellulose.
To improve the sharpness of the contours of the prints produced according
to the invention it is possible, if desired, to coat the temporary
supports, 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) 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 Patent No. 549,179 and U.S. Pat. No.
2,893,816.
The dyestuff transfer takes place at temperatures of
160.degree.-240.degree. C, preferably 200.degree.-220.degree. C, for 15-60
seconds.
The heat transfer can be effected by direct contact with heating plates, by
hot air, by hot steam or by infrared radiation. The dyeings and prints
obtained on the materials used as substrates display good fastness
properties in use.
EXAMPLE 1
20 g of a compound of the formula
##STR5##
are ground in a pearl mill with 0-7.5 g of a cyclohexanoneformaldehyde
resin of softening point above 160.degree. C and 10-2.5 g of
ethylcellulose N.sub.4. 100 parts of a printing ink are prepared by
addition of toluene which contains 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 with 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 compound of the formula
##STR6##
are ground in a pearl mill with 0-7.5 g of a cyclohexanoneformaldehyde
resin of softening point above 160.degree. C and 10-2.5 g of
ethylcellulose N.sub.4. 100 parts of a printing ink are prepared by
addition of toluene which contains 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 with 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 3
20 g of the compound of the formula
##STR7##
are dissolved in 800 g of toluene which contains 10% of polywaxes. A paper
is impregnated with this solution and dried. If this paper is pressed
against a fabric of polyacrylonitrile fibres a yellow dyeing with good
fastness properties is obtained.
EXAMPLE 4
20 g of the compound of the formula
##STR8##
are converted to a printing ink as in Example 2. An aluminium foil is
impregnated with this printing ink by means of a spray gun. If this foil
is pressed against a fabric of polyacrylonitrile fibres for 15-40 seconds
at 180.degree. C, a clear yellow print is obtained. If a textile of
acid-modified polyamide is used, a yellow print is again obtained.
If instead of the dyestuff intermediates employed in Examples 1-4 the
carbinol bases indicated by formulae in the table which follows are used
to prepare printing inks, the temporary supports printed therewith give
transfer prints on acid-modified textile fibre materials, for example
polyacrylonitrile materials, which have the colour shades indicated in the
last column of the table which follows.
__________________________________________________________________________
Example
Formula Colour shade
__________________________________________________________________________
##STR9## yellow
6
##STR10## yellow
7
##STR11## yellow
8
##STR12## yellow
9
##STR13## yellow
10
##STR14## yellow
11
##STR15## orange
12
##STR16## red
13
##STR17## yellow
__________________________________________________________________________
* * * * *
|
|
|
|
|
|
|
Description |
|
