Note: Descriptions are shown in the official language in which they were submitted.
' BASF Aktienge~ellschaft 940541 O.Z. 0050/45402
2163387
~ye preparations
The present invention relates to novel dye preparations
5 containing at least one red reactive dye, at least one blue
reactive dye and also polyethyleneimine having an average
molecular weight of from 1000 to 10,000,000, to their use for
preparing recording fluids for the inkjet process and also to
recording fluids for the inkjet process containing these dye
10 preparations.
The inkjet printing process is usually carried out with aqueous
inks, which are sprayed as small droplets directly onto the
substrate. There is a continuous form of the process, in which
15 the ink is pressed at a uniform rate through a nozzle and the jet
is directed onto the paper, or into an ink collector, by an
electric field depending on the pattern to be printed, and there
is an interrupted inkjet or drop-on-demand process, in which the
ink is expelled only where a colored dot is to appear, the latter
20 form of the process employing a piezoelectric crystal or a heated
hollow needle (bubble or thermal jet process) to exert pressure
on the ink system and so eject an ink droplet. These techniques
are described in Text. Chem. Color 19 (1987), 23-29, and 21
(1989), 27-32.
The inkjet process generally utilizes water-soluble dyes. A
problem in this connection is the inadequate water fastness of
paper printed with water-soluble dyes. Especially magenta-colored
inkjet prints have hitherto shown the disadvantage of inadequate
30 water fastness.
It is an object of the present invention to provide novel dye
preparations which shall be advantageously suitable for preparing
recording fluids (inks) for the inkjet process. The resulting
35 inks shall on application to paper by the inkjet process or by
some other m;n;m~l add-on spray technique produce prints of high
water fastness and high water spotting fastness.
We have found that this object is achieved by the dye
40 preparations mentioned at the outset.
Suitable red or blue reactive dyes generally have from 1 to 4
fiber-reactive radicals of the aliphatic or heterocyclic series
and from 1 to 6 carboxyl and/or sulfonic acid groups.
BASF Aktienge~ell~chaft 940541 O.Z. 0050/45402
2163387
Such dyes are known per se and have been described in the
literature in large numbers. The dyes can belong to a very wide
range of classes, for example the class of the monoazo, disazo or
polyazo dyes, the metal complex azo dyes, such as 1:1 copper, 1:2
5 chromium or 1:2 cobalt complex monoazo or disazo dyes, the
anthraquinone dyes, the copper or cobalt phthalocyanine dyes, the
copper formazan dyes or the azomethine, nitroaryl, dioxazine,
triphendioxazine, phenazine or stilbene dyes.
10 Azo and anthraquinone dyes are particularly suitable.
Among the azo dyes, it is mono- or disazo dyes - metallized or
unmetallized - which may be singled out.
15 Important azo dyes include for example those whose diazo
component is derived from an aniline or from an aminonaphthalene.
Important azo dyes further include for example those whose
coupling component is derived from an aniline, naphthalene,
20 pyrazolone, aminopyrazole, diaminopyridine, pyridone or
acylacetarylide.
Exemplary are metal-free or metallized (metal complexes) azo dyes
of the phenyl-azo-naphthalene, phenyl-azo-l-phenylpyrazol-5-one,
25 phenyl-azo-benzene, naphthyl-azo-benzene,
phenyl-azo-aminonaphthalene, naphthyl-azo-naphthalene,
naphthyl-azo-l-phenylpyrazol-5-one, phenyl-azo-pyridone,
phenyl-azo-aminopyridine, naphthyl-azo-pyridone,
naphthyl-azo-aminopyridine or stilbyl-azo-benzene series, of
30 which dyes of the phenyl-azo-naphthalene series may be singled
out.
Important anthraquinone dyes include for example those of the
class of the l,4-diamino-2-hydroxysulfonylanthraquinones.
Fiber-reactive radicals are groups capable of reacting with the
hydroxyl groups of cellulose with the formation of covalent
chemical bonds. The fiber-reactive radical can be attached to the
dye radical directly or by a bridge member; preferably it is
40 attached directly, via an optionally monoalkylated amino group or
via an aliphatic radical.
Heterocyclic hooks include for example halogen-substituted
radicals of l,3,5-triazine, quinoxaline, phthalazine, pyrimidine
45 or pyridazone, and 2-alkylsulfonylbenzothiazolyl.
- BASF Aktienge~ell~chaft 940541 O.Z. 0050/45402
- 21633~7 3
Exemplary are the following heterocyclic radicals:
Cl Cl Cl
5Nl:l N~ N~
N~ CO-N- N~ CO-N- N~--S02-~-
Cl ;,~ Cl ~ Cl X
10Cl F F
N~lN NJ~N N~lN
Cl~ N- FJ~N- CH3~N-
15Cl ;,~ Cl ;,~ Cl ,,~
O2CH3 Cl X-N-
N--~N NJ~N NJ~N
20~ ClJ~ N- ClJ~Cl
CH3 Cl ;,~ CN X CN
Cl X-N- Cl
N~N N~N Cl~
Cl~ FJ~ F O~N~N
CO-~_
;~
Cl F F
Cl~ul Cl~ Ul Cl~Ul
O N' N IX o N' N O N' N X
C2H4-CO-N- C2H4-CO- N-
:~al Hal Hal
N--~N N~N N~N
Hal~N~ N~- U ~NJ~N~-
U3 X
BASF Aktiengesell~chaft 940541 O.Z. 0050/45402
- 2163387
CH3-SO2 ~ / ~ or C2Hs-sO
where
X is hydrogen or Cl- C4 - alkyl,
10 Hal is fluorine or chlorine,
Ul is hydrogen or nitro, and
U2 and U3 are independently of each other hydrogen, Cl-C6-alkyl,
which may be substituted by hydroxyl, halogen, cyano,
hydroxysulfonyl or a radical of the formula -SO2-Y, where Y
is vinyl or a radical of the formula C2H4-Q, where Q is a
group detachable under alkaline reaction conditions, and may
in each case be interrupted by 1 or 2 oxygen atoms in ether
function, imino or Cl-C4-alkylimino groups, or u2 and U3 are,
together with the nitrogen atom joining them together,
pyrrolidinyl, piperidinyl, morpholinyl, piperazinyl or
N-(Cl-C4-alkyl)piperazinyl, or else u2 ls a radical of the
formula
~,
where the rings A and K may each be hydroxysulfonyl-
monosubstituted or -disubstituted and benzofused and the ring K
may independently be monosubstituted or disubstituted by
chlorine, nitro, Cl-C4-alkyl, Cl- C4 - alkoxy, cyano, carboxyl,
35 acetylamino, hydroxysulfonylmethyl or a radical of the formula
CH2-SO2-Y, SO2-Y, NH-CO-Y or NU2-CO-NU2-Z-SO2-Y, where Y and u2 are
each as defined above and Z is C2-C6-alkylene, which may be
substituted by hydroxyl, chlorine, cyano, carboxyl,
Cl - C4 - alkoxycarbonyl, Cl- C4 - alkanoyloxy or sulfato and may in each
40 case be interrupted by 1 or 2 oxygen atoms in ether function or
imino or Cl- C4 - alkylimino groups.
Fiber-reactive radicals of the aliphatic series include for
example acryloyl, mono-, di- or trichloroacryloyl, mono-, di- or
45 tribromoacryloyl, -CO-CCl=CH-COOH, -CO-CH=CCl-COOH,
2-chloropropionyl, 1,2-dichloropropionyl, 1,2-dibromopropionyl,
3-phenylsulfonylpropionyl, 3-methylsulfonylpropionyl,
BASF AktiengeQellRchaft 940541 O.Z. 0050/45402
- 2163~87
2-sulfatoethylaminosulfonyl,
2-fluoro-2-chloro-3,3-difluorocyclobut-1-ylcarbonyl,
2,2,3,3-tetrafluorocyclobut-1-ylcarbonyl,
2,2,3,3-tetrafluorocyclobut-1-ylsulfonyl,
5 2-(2,2,3,3-tetrafluorocyclobut-1-yl)acryloyl, 1- or
2-alkyl- or -aryl-sulfonylacryloyl, such as 1- or
2-methylsulfonylacryloyl, or a radical of the formula SO2-Y, CONH -
W-SO2-Y or NHCONH-W-SO2-Y, where W is Cl-C4-alkylene or phenylene
and Y is in each case as defined above.
Q is a group which is detachable under alkaline reaction
conditions. Such groups include for example chlorine, bromine,
Cl - C4 - alkylsulfonyl, phenylsulfonyl, OS03H, SS03H, OP(O) (OH)2,
Cl - C4 - alkylsulfonyloxy, substituted or unsubstituted
15 phenylsulfonyloxy, Cl- C4 - alkanoyloxy, Cl- C4 - dialkylamino or a
radical of the formula
- N\- L2 An~, - N~ An~ 2 ~CONH2
where Ll, L2 and L3 are independently of one another Cl-Cg-alkyl
25 or benzyl and An~ is in each case an equivalent of an anion.
Suitable anions include for example fluoride, chloride, bromide,
iodide, mono-, di- or trichloroacetate, methanesulfonate,
benzenesulfonate and 2- or 4-methylbenzenesulfonate.
30 Preference is given to dye preparations containing at least one
red reactive dye of the series of the azo dyes and at least one
blue reactive dye of the series of the anthra~uinone dyes.
Particular preference is given to dye preparations containing, as
35 the red reactive dye, the azo dye of the formula I
N ~ N
~ ~
,S03H OH NH N N--C6H5 ( I ) .
CH~ N--N~S03H
~ BASF Aktienge~ell~chaft 940541 O.Z. 0050/45402
216~8~
Particular preference is further given to dye preparations
containing, as the blue reactive dye, the anthra~uinone dye of
the formula II
O ~H2
~ ~ ~ SO3H
O NH ~ Nl ~ N ~ NH ~ SO3H (II).
SO3H Cl
The dye preparations of the present invention further contain
polyethyleneimine having an average molecular weight of from 1000
to 10,000,000. Such polyethyleneimine is commercially available.
20 Polyethyleneimine is generally used in the form of an aqueous
solution from about 48 to 52% strength by weight, or else without
a solvent.
Preference is given to using polyethyleneimine having an average
25 molecular weight of from 1500 to 3000, in particular about 2000
(viscosity determination at 20 C in accordance with DIN 53019
(Brookfield): from 1000 to 2000 mPa-s), having an average
molecular weight of from 20,000 to 25,000 (viscosity
det~rmination at 20 C in accordance with DIN 53 019 (Brookfield):
30 from 100,000 to 250,000 mPa-s) or having an average molecular
weight of from 600,000 to 1,000,000 (viscosity determination at
20 C in accordance with DIN 53019 (Brookfield): from 18,000 to
40,000 mPa-s).
35 Preference is given to dye preparations containing from 80 to
96 parts by weight of at least one red reactive dye, from 3 to
8 parts by weight of at least one blue reactive dye and also from
1 to 30 parts by weight of polyethyleneimine.
40 Particular preference is given to dye preparations containing
from 84 to 94 parts by weight, in particular from 88 to 92 parts
by weight, of the dye of the formula I, from 3.5 to 6 parts by
weight, in particular from 4 to 5.5 parts by weight, of the dye
of the formula II and also from 2 to 20 parts by weight, in
45 particular from 3 to 15 parts by weight, of polyethyleneimine.
BASF Aktienge~ell~chaft 940541 O.Z. 0050/45402
21633~7
The dye preparations of the present invention can be obtained by
mixing the above-described components. They are advantageously
suitable for preparing recording fluids for the inkjet process.
5 The present invention accordingly further provides inkjet
recording fluids containing from 6 to 20 parts by weight,
preferably from 9 to 14 parts by weight, of the above-defined dye
preparation, from 5 to 20 parts by weight, preferably from 8 to
15 parts by weight, of a water-miscible diluent and also from 75
10 to 105 parts by weight, preferably from 80 to 100 parts by
weight, of water.
Water-miscible diluents are in particular organic diluents, for
example Cl-C4-alkanols, such as methanol, ethanol, propanol,
15 isopropanol, butanol, isobutanol, sec-butanol or tert-butanol,
carboxamides, such as N,N-dimethylformamide or
N,N-dimethylacetamide, lactams, such as N-methylpyrrolidone,
cyclic ureas, such as l,3-dimethyl-2-imidazolidinone, ketones or
ketoalcohols, such as acetone, methyl ethyl ketone or
20 2-methyl-2-hydroxypentan-4-one, ethers, such as tetrahydrofuran
or dioxane, mono-, oligo- or polyalkylene glycols or thioglycols
with C2-C6-alkylene units, such as ethylene glycol, 1,2- or
1,3-propylene glycol, 1,2- or 1,4-butylene glycol, 1,5-pentylene
glycol, l,6-hexylene glycol, diethylene glycol, triethylene
25 glycol, tetraethylene glycol, thiodiglycol, polyethylene glycol
or polypropylene glycol, other polyols, such as glycerol or
1,2,6-hexanetriol, Cl- C4 - alkyl ethers of polyhydric alcohols, in
particular of mono- or oligoglycols, such as the mono- or
dimethyl or mono- or diethyl ethers of ethylene glycol,
30 diethylene glycol, triethylene glycol or tetraethylene glycol, or
dimethyl sulfoxide.
Water-miscible diluents, which are preferred, are N-methylpyrro-
lidone, mono-, di- or trialkylene glycols with C2-C6-alkylene
35 units, in particular mono-, di- or triethylene glycol, or
dimethyl sulfoxide.
The novel recording fluids may further contain auxiliaries, for
example agents for influencing the viscosity, such as polyvinyl
40 chloride or cellulose derivatives, surfactants (nonionic, anionic
or cationic) or buffer systems.
The novel recording fluids containing the dye preparations of the
present invention print in magenta shades which are notable for a
45 high water fastness.
BASF Aktienge~ell~chaft 940541 O.Z. 0050/45402
2163~87 8
The Examples which follow illustrate the invention.
A) Preparation of dye preparations
Example 1
90.7 parts by weight of the dye of the formula I, 5.1 parts
by weight of the dye of the formula II and 4.2 parts by
weight of polyethyleneimine having an average molecular
weight of from 20,000 to 25,000 were mixed.
Example 2
83.6 parts by weight of the dye of the formula I, 4.7 parts
by weight of the dye of the formula II and 11.7 parts by
weight of polyethyleneimine having an average molecular
weight of about 2000 were mixed.
B) Preparation of recording fluids
Example 3
10 parts by weight of the dye preparation of Example 1,
10 parts by weight of N-methylpyrrolidone and 80 parts by
weight of water were mixed with stirring.
Example 4
10 parts by weight of the dye preparation of Example 2,
10 parts by weight of N-methylpyrrolidone and 80 parts by
weight of water were mixed with stirring.
Both cases result in a recording fluid which, on use in the
inkjet process, produces prints having good application
properties, in particular good water fastness.
