CA2163387A1

CA2163387A1 - Dye preparations

Info

Publication number: CA2163387A1
Application number: CA002163387A
Authority: CA
Inventors: Helmut Bellaire; Walter Kurtz
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1994-11-25
Filing date: 1995-11-21
Publication date: 1996-05-26
Also published as: EP0713903A1; BR9505512A; JPH08225754A; KR960017794A; DE4441960A1

Abstract

Dye preparations 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 are useful for preparing recording fluids for the inkjet process.

Description

' BASF Aktienge~ellschaft 940541 O.Z. 0050/45402 ~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 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

:~al Hal Hal N--~N N~N N~N
Hal~N~ N~- U ~NJ~N~-BASF Aktiengesell~chaft 940541 O.Z. 0050/45402 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.

Claims

1. Dye preparations 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.

2. Dye preparations as claimed in claim 1, 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.

3. Dye preparations as claimed in claim 1 or 2 containing at least one red reactive dye from the series of the azo dyes and at least one blue reactive dye from the series of the anthraquinone dyes.

4. Dye preparations as claimed in any of claims 1 to 3 containing the dye of the formula I

(I).

5. Dye preparations as claimed in any of claims 1 to 4 containing the dye of the formula II

(II).

6. Dye preparations as claimed in any of claims 1 to 5 containing from 84 to 94 parts by weight of the dye of the formula I, from 3.5 to 6 parts by weight of the dye of the formula II and also from 2 to 20 parts by weight of polyethyleneimine.

7. Dye preparations as claimed in any of claims 1 to 6 containing polyethyleneimine having an average molecular weight of from 1500 to 3000.

8. Dye preparations as claimed in any of claims 1 to 6 containing polyethyleneimine having an average molecular weight of from 600,000 to 1,000,000.

9. Dye preparations as claimed in any of claims 1 to 6 containing polyethyleneimine having an average molecular weight of from 20,000 to 25,000.

10. The use of the dye preparations of claim 1 for preparing recording fluids for the inkjet process.

11. Recording fluids for the inkjet process containing from 6 to 20 parts by weight of a dye preparation as claimed in claim 1, from 5 to 20 parts by weight of a water-miscible diluent and also from 75 to 105 parts by weight of water.