DE19622485A1 - Dye preparations for ink jet printing - Google Patents

Abstract

A novel dye composition comprises, by wt. (A) 0.1-30, preferably 1-15%, anthraquinone and/or quinophthalone dye free of ionic groups; (B) 0.1-20, preferably 0.5-10%, dispersant based on an arylsulphonic acid-formaldehyde condensate; and optionally (C) water. Optionally present are (D) 0.1-30% carbohydrate and (E) 0.1-20% polyethylene glycol.

Description

The present invention relates to new dye formulations, containing, each based on the weight of the preparation, 0.1 up to 30% by weight of one or more dyes from the class of Anthraquinones or quinophthalones that are free of ionic Groups, 0.1 to 20 wt .-% of a dispersant based an arylsulfonic acid-formaldehyde condensation product and against also water, and their use as inks in ink-jet Process as well as for sublimation transfer printing.

Dye preparations are already contained in EP-A-655 527 tend disperse dyes and special dispersants, be knows.

The object of the present invention was to provide new dyes preparations containing anthraquinone or quinophthalone color to provide substances that are free of ionic groups. The new dye preparations should be advantageous for the An Use in the ink-jet process and sublimation transfer suitable for printing.

Accordingly, the dyes specified in the introduction were added preparations found.

Suitable anthraquinone dyes that are free of ionic groups are obey z. B. of formula I.

in the
L¹ is hydrogen, C₁-C₁₀-alkyl or phenyl optionally substituted by C₁-C--alkyl, C₁-C--alkoxy, halogen or nitro,
L² and L³ independently of one another each hydrogen, optionally substituted by phenyl or C₁-C₄-alkylphenyl, C₁-C₁₀-alkoxy, optionally substituted by phenyl, C₁-C₁₀-alkylthio, halogen, hydroxyphenyl, C₁-C₄-alkoxyphenyl, C₁-C₆-alkanoyl , C₁-C₆ alkoxycarbonyl or a residue of the For mel

wherein G¹ is oxygen or sulfur and G² is hydrogen or C₁-C₈-monoalkylsulfamoyl, whose alkyl chain can be interrupted by 1 or 2 oxygen atoms in ether function, and
L⁴ optionally substituted by phenyl or C₁-C₄-alkylphenyl amino, hydroxy or optionally substituted by phenyl C₁-C₁₀-alkylthio.

Suitable quinophthalone dyes that are free of ionic groups are obey z. B. of formula II

in which X is hydrogen, chlorine or bromine.

All alkyl groups occurring in the above formula I can be both straight-chain and branched.

When in the above formula I substituted alkyl groups occur, they usually have 1 or 2 substituents.

When substituted phenyl groups in the above formulas occur, they usually have 1 to 3, preferably 1 or 2, substituents.

The following is an exemplary list of residues as described in Formula I are defined.

Alkyl residues are e.g. B. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl or isodecyl (the designations isooctyl, isononyl and isodecyl are trivial names derived from those obtained by the oxo process alcohols -. cf. Ullmann's Encyclopedia of Industrial Chemistry, ^5th Edition, Vol A1, pages 290 to 293, and Vol. A 10, pages 284 and 285).

Phenyl radicals are e.g. B. phenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-ethylphenyl, 2-, 3- or 4-propylphenyl, 2-, 3- or 4-isopropylphenyl, 2-, 3- or 4-butylphenyl, 2,3-, 2,4- or 2,6-dimethylphenyl, 2-, 3- or 4-methoxyphenyl, 2-, 3- or 4-ethoxyphenyl, 2,3-, 2,4- or 2,6-dimethoxyphenyl, 2-, 3- or 4-fluorophenyl, 2-, 3- or 4-chlorophenyl, 2-, 3- or 4-bromo phenyl or 2-, 3- or 4-nitrophenyl.

Alkylthio and phenylthio residues are e.g. B. methylthio, ethylthio, Propylthio, isopropylthio, butylthio, isobutylthio, pentylthio, Hexylthio, heptylthio, octylthio, isooctylthio, 2-ethylhexylthio, Nonylthio, isononylthio, decylthio, isodecylthio, benzylthio or 1- or 2-phenylethylthio.

Alkoxy radicals are e.g. B. methoxy, ethoxy, propoxy, isopropoxy, Butoxy, isobutoxy, sec-butoxy, pentyloxy, isopentyloxy, neopen tyloxy, tert-pentyloxy, hexyloxy, 2-methylpentyloxy, heptyloxy, Octyloxy, isooctyloxy, 2-ethylhexyloxy, nonyloxy, isononyloxy, Decyloxy, isodecyloxy, benzyloxy or 1- or 2-phenylethoxy.

Halogen is e.g. B. fluorine, chlorine or bromine.

Alkoxycarbonyl radicals are e.g. B. methoxycarbonyl, ethoxycarbonyl, Propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxy carbonyl, sec-butoxycarbonyl, pentyloxycarbonyl, isopentyloxy carbonyl, neopentyloxycarbonyl or hexyloxycarbonyl.

Alkanoyl residues are e.g. B. formyl, acetyl, propionyl, butyryl, pen tanoyl or hexanoyl.

Sulfamoyl residues are e.g. B. methylsulfamoyl, ethylsulfamoyl, propyl sulfamoyl, isopropylsulfamoyl, butylsulfamoyl, pentylsulfamoyl, Hexylsulfamoyl, heptylsulfamoyl, octylsulfamoyl, 2-ethyl sulfamoyl, 2-methoxyethylsulfamoyl, 2-ethoxyethylsulfamoyl, 3,6-dioxaheptylsulfamoyl, 3,6-dioxaoctylsulfamoyl, 4,8-dioxano nylsulfarnoyl, 3,7-dioxaoctylsulfamoyl, 3,7-dioxanonylsulfamoyl, 4,7-dioxaoctylsulfamoyl, 4,7-dioxanonylsulfamoyl or 4,8-dioxa decylsulfamoyl.  

Dye preparations containing one or more are preferred rere anthraquinone dyes of the formula I in which L¹ is hydrogen, C₁-C₄ alkyl or phenyl optionally substituted by methyl and L⁴ hydroxy, amino or optionally by methyl substi tuiert Phenylamino mean.

Dye preparations containing one are also preferred or more anthraquinone dyes of the formula I in which L² C₁-C₄-alkoxy, acetyl, C₁-C Alk-alkoxycarbonyl or a radical of formula

means, wherein G¹ and G² each be the above meaning sit, G¹ is especially oxygen and G² ins especially for hydrogen.

Dye preparations containing the are also preferred Quinophthalone dye of the formula IIa

The dyes of the formula I and II are generally mean about known dyes. The anthraquinone dyes of Formula I are described, for example, in K. Venkataraman "The Chemistry of Synthetic Dyes ", Vol. III, pages 391 to 413, Academic Press, New York, London, 1970. The quinophthalone dyes Formula II are z. B. in EP-A-83 553 or the quote there described literature.

Preferred are dye preparations in which 99% of the in Preparation contained dye particles are smaller than 1 micron.

Also preferred are dye preparations that contain such dyes contain substances from the anthraquinone or quinophthalone series, whose sublimation temperature is 140 to 300 ° C.

An aryl sulfone is preferably used as the dispersant Acid-formaldehyde condensation product, which contains 3 up to 50% by weight, based on the weight of the dispersant,  one or more aromatic or long chain aliphatic Carboxylic acids, their salts, their anhydrides or a mixture from this.

As arylsulfonic acid-formaldehyde condensates, sol with a maximum content of sulfonic acid groups of 40 wt .-% used.

In particular, the starting product for the arylsulfonic acids is a mixture of such aromatic compounds into consideration by thermal splitting of a naphthenic residual oil and Fractionation of the cleavage products are available. The naphthe African residual oils fall off when cracking, for example Light petrol. You will e.g. B. in DE-A-29 47 005 as high called boiling aromatic hydrocarbon oils. That naph Thenische residual oil is preferably at a temperature of 1400 to 1700 ° C thermally split. The fission products are then a fractional distillation fed. The normal one pressure (1013 mbar) from 100 to 120 ° C passing fraction is ge collects and as an aromatic compound of sulfonation leads. Such a fraction is used in the known acetylene oil Quench process usually obtained as a by-product (Ullmann’s Encyclopedia of Industrial Chemistry, VCH publishing company mbH, Weinheim, 1985, Volume Al, pages 107 to 112).

This aromatic fraction consists of a mixture of many aromati substances whose structure and quantity are practically not individual can be determined. The following are aryl compounds the main representatives of this aromatic fraction:

The aromatics fraction also contains identified stocks share the following aryl compounds in amounts of 0.1 to about 2% by weight genes: fluorene, indane, methylstyrene, phenanthrene, methylindane, di methylnaphthalene, ethylnaphthalene, xylenes, tetralin, styrene, Me  ethyl ethylbenzene, anthracene, fluoranthrene, pyrene, acetonaphthylene and toluene.

As a rule, particularly suitable arylsulfonic acids contain α- and β-naphthalenesulfonic acids, the ratio of α- to β-isomers is 20: 1 to 1: 8, in particular 10: 1 to 1: 5.

Suitable aromatic carboxylic acids or their derivatives are in for example naphthalene carboxylic acid, naphthalic acid, terephthalic acid right, isophthalic acid, benzoic acid, trimellitic acid, phenylacetic acid right, phenoxyacetic acid, salicylic acid, p-hydroxybenzoic acid, diphe nylacetic acid, m-hydroxybenzoic acid, benzene tetracarboxylic acid or Acid anhydrides, such as phthalic anhydride, trimellitic anhydride, Benzene-1,2,4,5-tetracarboxylic acid dianhydride or naphthalic acid drid.

Suitable long-chain aliphatic carboxylic acids are in particular saturated or olefinically unsaturated, linear or branched aliphatic monocarboxylic acids with 8 to 22, preferably 8 to 18 Carbon atoms of natural or synthetic origin, for example higher fatty acids such as caprylic acid, capric acid, Lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, Linoleic acid or linolenic acid, or synthetically produced car bonic acids such as 2-ethylhexanoic acid, isononanoic acid or isotridecane acid.

Mixtures of anhydrides, mixtures of Carboxylic acids, mixtures of salts of the considered Carboxylic acids and mixtures of carboxylic acids and anhydrides from Interest. The alkas come as salts of the carboxylic acids mentioned Li, ammonium or alkaline earth metal salts into consideration, for example se by neutralizing these carboxylic acids with sodium hydroxide solution, Ka lilauge, lithium hydroxide, soda, magnesium carbonate, calcium oxide, Calcium hydroxide, ammonia or alkanolamines, such as ethanolamine, Diethanolamine or triethanolamine are available.

Sodium benzoate, sodium phenylacetate, Sodium salicylate, sodium 4-hydroxybenzoate, sodium terephthalate, Sodium 2-hydroxy-3-naphthalene carboxylate, naphthalene-1-carboxylic acid re, phthalic anhydride or benzoic acid in the dispersants used.

In the dye preparations according to the invention are preferred how to use such dispersants

• A) 50 to 97% by weight, in particular 70 to 95% by weight, one or several arylsulfonic acid-formaldehyde condensates and
• B) 3 to 50% by weight, in particular 5 to 30% by weight, one or several aromatic or long-chain aliphatic carbon acids, their salts or their anhydrides or a Mi contained in this.

Gelan for use in the invention as a dispersant arylsulfonic acid-formaldehyde condensation products are known products. You are e.g. B. in the US-A-5,186,846.

Dye preparations, each based on the weight of the preparation 1 to 15 wt .-% of one or more Dyes from the class of anthraquinones or quinophthalones, 0.5 to 10 wt .-% of a dispersant based on an aryl sulfonic acid-formaldehyde condensation product and optionally Contain water.

Dye preparations which additionally, each based on the weight of the preparation, 0.1 to 30% by weight, preferably 0.1 to 25% by weight, of a carbohydrate and 0.1 to 20% by weight, preferably 0.1 to 15% by weight, of one Contain polyethylene glycol.

Suitable carbohydrates in the dye according to the invention preparations can be included, for. B. sorbitol or glu cose.

Suitable polyethylene glycols in the color of the invention Preparations of substances can be included, for example an average molecular weight of 100 to 1000, preferably about 400.

Further constituents of the dye preparations according to the invention can e.g. B. auxiliaries such as preservatives, anti oxidants, anti-foaming agents or regulators the viscosity. These means are known per se and han usual. If these agents in the dye of the invention preparations are usually present, their total amount 1% by weight or less, based on the weight of the preparation.

If the sum of the components of the paint according to the invention fabric preparations gives a value that is less than 100 wt .-% the rest of the ingredient is usually water.  

The dye preparations according to the invention usually have a viscosity of 1 to 4 mm² / sec, preferably 2 to 3.5 mm² / sec.

The surface tension of the dye according to the invention preparations is usually 30 to 70 Nm / m, preferably 40 up to 60 Nm / m.

The pH of the dye preparations according to the invention is in the generally 5 to 11, preferably 7 to 10.

The new dye preparations are manufactured on familiar way. So you can the dye, for example in Form of a press cake, together with the dispersant and ge if necessary, mix polyethylene glycol in the presence of water and predispers in a suitable apparatus. The resulting mixture can then be treated in a grinder to set the desired size of the dye particles. Finally, you can make the final setting by still appropriate amounts of water, possibly polyethylene glycol and / or carbohydrates and optionally other auxiliaries sets and after mixing using a sieve, preferably with a pore size of 1 micron, filtered.

The dye preparations according to the invention are particularly suitable partly as inks in the ink jet process and for the Sublimation transfer printing.

Used in the ink-jet process usually aqueous inks, which are in small droplets directly be sprayed onto the substrate. One differentiates here continuous process in which the ink passes through evenly pressed a nozzle and through an electric field, depending on the pattern to be printed, directed onto the substrate, and an un broken ink jet or "drop on demand" process which only ejects the ink where there is a colored dot should be set. The latter method uses either via a piezoelectric crystal or a heated cannula (Bubble or thermal jet process) Pressure on the ink system exercised and thus an ink drop is thrown out. Such ver driving styles are in text. Chem. Color, volume 19 (8), pages 23 to 29, 1987, and volume 21 (6), pages 27 to 32, 1989 ben.  

The dyestuffs according to the invention are particularly suitable preparations as inks for the bubble jet process or for the Method using a piezoelectric crystal.

With sublimation transfer printing, a pattern is first opened preformed an intermediate carrier and then by heat effect transferred to a carrier. The dye can both during the transfer itself as well as in a subsequent fixing and Post-treatment process can be fixed. This procedure is common my known and z. B. in Ullmann’s Encyclopedia of Industrial Chemistry, 5th Edition, Volume A26, pages 499 to 501, described ben.

Suitable carriers are in particular textile materials, e.g. B. Fa terns, yarns, threads, knitwear, woven goods or non-wovens from Po lyester, modified polyester, e.g. B. anionically modified Polyester, blended fabric of polyester with cellulose, cotton, Viscose or wool, polyamide, polyacrylonitrile, triacetate or Acetate, polyester microfibers or others with polyester layered materials, such as plastic or metal foils.

The dye preparations according to the invention are particularly suitable good for sublimation transfer printing, where the pattern generated on the intermediate carrier by means of the ink jet process becomes.

The new dye preparations are characterized in that it does not clog the nozzles during the ink jet process ren. Furthermore, you get streak-free when used Prints.

The following examples are intended to explain the invention in more detail.

The following dyes were used:

Dye 1

Dye 2

Dye 3

Dye 4

Production of the dye preparation

15 g of dye, 15 g of polyethylene glycol (average molecular weight weight: 400), 7.5 g of a dispersant based on an aryl sulfonic acid-formaldehyde condensation product, the additional still contains benzoic acid and as in US-A-5 186 846 Dispersant 3 is described, 0.37 g 50 wt .-% aqueous Solution of glutardialdehyde and 0.75 g 47% by weight aqueous solution of tetramethylolacetylene diurea are combined with water to form Ge filled up to a total weight of 100 g and pasted in a mill. Then the pH is adjusted to 8.5 with 10% strength by weight sodium hydroxide solution poses.  

The mixture is then in a stirred ball mill ground so that 99% of the dye particles are small own 1 µm.

For the final setting, 26.7 g of regrind with a further 4 g of poly ethylene glycol (see above), 0.1 g 50% by weight aqueous solution of Glutardialdehyde, 0.3 g 47% by weight aqueous solution of tetrame thylolacetylenediourea and 20 g 70 wt .-% aqueous sorbitol solution mixed with water up to a total weight of 100 g filled, mixed and passed through a sieve with a pore size of 1 µm filtered.

The following dye preparations were obtained. (The percentages are percentages by weight.)

Table 1

The dye formulations have the following physical and printing properties.

Table 2

Test methods and evaluations 1) Surface tension

The surface tension was measured with the digital tensiometer K 10 from the Krüss company. The given in Table 2 Values are the average of 3 measurements.

2) viscosity

The viscosity was determined using the Ubbelohde method (DIN 51662) certainly.

3) pH

The pH was determined with a Knick 763 pH meter.

4) Particle size determination

The particle size distribution was determined using a CILAS granulome ter HR 850 from Alcatel measured.

5) Aging stability

The aging stability of the preparations (inks) became after 2 methods examined:

• a) after a thermal stress test (warm storage of the inks for 3 days at 60 ° C)  
• b) after a freeze / heat treatment cycle (freezing the inks for 4 h at 20 ° C and then heat treatment for 4 h at 70 ° C). This temperature cycle was run 4 times each.

After both aging tests the particle size distribution became of the contaminated inks were determined again using the CILAS method.

6) Kogation test

The behavior of the inks is particularly important during the printing process in the nozzles. The slope of the inks Deposits and blockages in the nozzles were created checked with the following test.

A modified Desk Jet Plus (bubble Jet printer) from Hewlett-Packard.

First, the mean drop weight became dependent the voltage applied to the nozzles. Subsequently were 1 million pulses to each nozzle at constant voltage given and then again the average drop weight one defined number of drops determined. This process was ins repeated 10 times in total.

With ideal behavior of the inks, the middle drop should weight remain constant over the test period.

The change in the drop weight of the individual inks is listed in Table 2.

7) Dispersion factor

100 ml of the corresponding ink was left in the room for 7 days temperature stored in a measuring cylinder. Then were 10 ml of the dispersion from the bottom and 10 ml from the surface removed and the color strength determined photometrically.

The dispersion factor is calculated from the color strength of the above ren dispersion / color strength of the lower dispersion × 100 = Dis persion factor.

Claims (8)

1. dye preparations containing, each based on the Weight of the preparation, 0.1 to 30 wt .-% of one or more dyes from the class of anthraquinones or chinos phthalones that are free of ionic groups, 0.1 to 20% by weight of a dispersant based on an aryl sulfone acid-formaldehyde condensation product and optionally Water. 2. dye preparations according to claim 1, characterized net that they, each based on the weight of the preparation 1 to 15% by weight of one or more dyes from the class the anthraquinones or quinophthalones, 0.5 to 10% by weight a dispersant based on an arylsulfonic acid form aldehyde condensation product and optionally water ent hold. 3. dye preparations according to claim 1, characterized net that they additionally, each based on the weight of the Preparation, 0.1 to 30% by weight of a carbohydrate and 0.1 contain up to 20 wt .-% of a polyethylene glycol. 4. dye preparations according to claim 1, characterized net, 99% of the dye contained in the preparation chen are smaller than 1 µm. 5. Dye preparations according to claim 1, characterized in that they contain anthraquinone dyes of the formula I. included in the
L¹ is hydrogen, C₁-C₁₀-alkyl or phenyl optionally substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen or nitro,
L² and L³ are each independently hydrogen, optionally substituted by phenyl or C₁-C₄-alkylphenyl C₁-C₁₀-alkoxy, optionally substituted by phenyl C₁-C₁₀-alkylthio, halogen, hydroxyphenyl, C₁-C₄-alkoxyphenyl, C₁-C₆ -Alkanoyl, C₁-C₆ alkoxycarbonyl or a radical of the formula in which G¹ represents oxygen or sulfur and G² represents hydrogen or C₁-C₈ monoalkylsulfamoyl, the alkyl chain of which may be interrupted by 1 or 2 oxygen atoms in ether function, and
L⁴ optionally substituted by phenyl or C₁-C₄-alkylphenyl amino, hydroxy or optionally substituted by phenyl C₁-C₁₀-alkylthio. 6. dye preparations according to claim 1, characterized in that they quinophthalone dyes of the formula II contain,
in which X is hydrogen, chlorine or bromine. 7. Use of the dye preparations according to claim 1 as Ink-jet inks. 8. Use of the dye preparations according to claim 1 as Sublimation transfer inks.