EP1692228A1

EP1692228A1 - Colouring preparations

Info

Publication number: EP1692228A1
Application number: EP04763244A
Authority: EP
Inventors: Ulrike Hees; Jürgen WEISER; Michael Kluge; John Provost
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2003-08-15
Filing date: 2004-07-15
Publication date: 2006-08-23
Also published as: WO2005017047A1; US20060230550A1; DE10338142A1; JP2007502335A

Abstract

The invention relates to colouring preparations, comprising: a) at least one dye in particulate form, b) at least one organic solvent with a boiling point of at least 247 °C, measured at atmospheric pressure, c) water and less than 0.25 wt. % of organic solvent with a boiling point below 247 °C, measured at atmospheric pressure.

Description

Colorant preparations

The present invention relates to colorant preparations containing

a) at least one colorant in particulate form, b) at least one organic solvent with a boiling point of at least 247 ° C., measured at atmospheric pressure and c) water,

and less than 0.25% by weight of organic solvents with a boiling point below 247 ° C, measured at atmospheric pressure.

A number of requirements are placed on colorant preparations and in particular inks used in the ink jet process (ink jet printing processes such as thermal ink jet, piezo ink jet, continuous ink jet, valve jet, transfer printing process): They must be suitable for printing They have viscosity and surface tension, they have to be stable on storage, ie they should not coagulate or flocculate, and they must not clog the printer nozzle, which can be problematic especially with dispersed inks that contain undissolved colorant particles. The requirements for the storage stability of these inks additionally include that the dispersed colorant particles do not settle. Furthermore, in the case of the continuous ink jet, the inks must be stable against the addition of conductive salts and show no tendency to flocculate when the ion content is increased. In addition, the prints obtained must meet the color requirements, i.e. show high brilliance and depth of color, and good fastness properties, e.g. Rub fastness, light fastness, water fastness and wet rub fastness, if necessary after post-treatment such as fixation, and have good drying behavior.

In addition, it is necessary for the inks to dry on the substrate as quickly as possible so that images or lettering to be printed do not run and for example the ink droplets of different colors do not mix. In order to produce razor-sharp prints, it is necessary that not only is the drying time of the prints minimized, but that these droplets do not run even during the time that the ink droplets are on the substrate to be printed. This ability of the ink is also called stand. The state of the inks known to date, also known as the definition of the prints, is still to be improved.

From US Pat. No. 5,141,556, aqueous inks and their use in inkjet printing are known which contain a dye or a dispersed pigment and, as component c), hexene-1,2-diol or an aliphatic 1,2-diol or 1,3- Diol, with branched 1,2-diols being preferred. However, the inks can still be improved. EP 0 649 888 describes ink compositions for the ink-jet printing process which, in addition to water and a soluble dye, contain propylene glycol mono-n-butyl ether and / or dipropylene glycol mono-n-butyl ether and another water-soluble butyl ether. The inks available in this way produce good images on recycled paper; however, the level of ink droplets on less absorbent materials is unsatisfactory.

Aqueous inks are known from EP-A 0 514 159 which contain soluble dyes and a selection of organic solvents. The inks described in EP-A 0 514 159 can also be improved.

The object was therefore to provide colorant preparations and in particular inks for the inkjet process which do not have the disadvantages mentioned above. A further object was to provide a method for producing improved colorant preparations. Furthermore, there was the task of providing printed substrates.

Accordingly, the colorant preparations defined at the outset were found.

The colorant preparations according to the invention contain colorants in particulate form a), for example pigments or disperse dyes. In the context of the present invention, pigments are to be understood as meaning practically insoluble, dispersed, finely divided, organic or inorganic colorants as defined in DIN 55944.

Pigments selected as examples are

Monoazo Pigments: C.I. Pigment brown 25; C.I. Pigment Orange 5, 13, 36 and 67; C.I. Pigment Red 1, 2, 3, 5, 8, 9, 12, 17, 22, 23, 31, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 52: 1, 52: 2, 53, 53: 1, 53: 3, 57: 1, 63, 112, 146, 170, 184, 210, 245 and 251; C. Pigment Yellow 1, 3, 73, 74, 65, 97, 151 and 183;

Disazo Pigments: C.I. Pigment Orange 16, 34 and 44; C.I. Pigment Red 144, 166, 214 and 242; C.I. Pigment Yellow 12, 13, 14, 16, 17, 81, 83, 106, 113, 126, 127, 155, 174, 176 and 188;

Anthanthrone pigments: Cl Pigment Red 168 (Cl Vat Orange 3); Anthraquinone pigments: CI Pigment Yellow 147 and 177; CI Pigment Violet 31; Anthraquinone pigments: Cl Pigment Yellow 147 and 177; CI Pigment Violet 31;

Anthrapynmidine Pigments: C.I. Pigment Yellow 108 (C.I. Vat Yellow 20);

Quinacridone Pigments: C.I. Pigment Red 122, 202 and 206; C.I. Pigment violet 19;

Quinophthalone Pigments: C.I. Pigment yellow 138;

Dioxazine pigments: C.I. Pigment violet 23 and 37;

Flavanthrone Pigments: C.I. Pigment Yellow 24 (C.I. Vat Yellow 1);

Indanthrone Pigments: C.I. Pigment Blue 60 (C.I. Vat Blue 4) and 64 (C.I. Vat Blue 6);

Isoindoline Pigments: C.I. Pigment orange 69; C.I. Pigment Red 260; C.I. Pigment Yellow 139 and 185;

Isoindolinone Pigments: C.I. Pigment Orange 61; C.I. Pigment Red 257 and 260; C.I. Pigment Yellow 109, 110, 173 and 185;

Isoviolanthrone Pigments: C.I. Pigment Violet 31 (C.I. Vat Violet 1);

Metal complex pigments: C.I. Pigment Yellow 117, 150 and 153; C.I. Pigment green 8;

Perinone Pigments: C.I. Pigment Orange 43 (C.I. Vat Orange 7); C.I. Pigment Red 194 (C.I. Vat Red 15);

Perylene Pigments: C.I. Pigment black 31 and 32; C.I. Pigment Red 123, 149, 178, 179 (C.I. Vat Red 23), 190 (C.I. Vat Red 29) and 224; C.I. Pigment violet 29;

Phthalocyanine Pigments: Cl Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 and 16; CI Pigment Green 7 and 36; Pyranthrone Pigments: CI Pigment Orange 51; CI Pigment Red 216 (CI Vat Orange 4);

Thioindigo Pigments: C.I. Pigment Red 88 and 181 (C.I. Vat Red 1); C.I. Pigment Violet 38 (C.I. Vat Violet 3);

Triaryl carbonium pigments: C.I. Pigment Blue 1, 61 and 62; C.I. Pigment green 1; C.I. Pigment Red 81, 81: 1 and 169; C.I. Pigment violet 1, 2, 3 and 27; C.I. Pigment black 1 (aniline black);

C.I. Pigment Yellow 101 (Aldazine Yellow);

C.I. Pigment Brown 22

Examples of inorganic pigments are:

White pigments: titanium dioxide (C.I. Pigment White 6), zinc white, colored zinc oxide; Zinc sulfide, lithopone; White lead;

Black pigments: iron oxide black (C.I. Pigment Black 11), iron-manganese black, spinel black (C.I. Pigment Black 27); Carbon black (C.I. Pigment Black 7);

- Colored pigments: chromium oxide, chromium oxide hydrate green; Chrome green (C.I. Pigment Green 48); Cobalt green (C.I. Pigment Green 50); Ultramarine green; Cobalt blue (C.I. Pigment Blue 28 and 36); Ultramarine blue; Iron blue (C.I. Pigment Blue 27); Manganese blue; Ultramarine violet; Cobalt and manganese violet; Iron oxide red (C.I. Pigment Red 101); Cadmium sulfoselenide (C.I. Pigment Red 108); Molybdate red (C.I. Pigment Red 104); ultramarine;

Iron oxide brown, mixed brown, spinel and corundum phases (C.I. Pigment Brown 24, 29 and 31), chrome orange;

Iron oxide yellow (CI Pigment Yellow 42); Nickel titanium yellow (Cl Pigment Yellow 53; Cl Pigment Yellow 157 and 164); Chromium titanium yellow; Cadmium sulfide and cadmium zinc sulfide (CI Pigment Yellow 37 and 35); Chrome yellow (Cl Pigment Yellow 34), zinc yellow, alkaline earth metal chromates; Naples yellow; Bismuth vanadate (CI Pigment Yellow 184);

Interference pigments: metallic effect pigments based on coated metal plates; Pearlescent pigments based on metal oxide coated mica flakes; Liquid crystal pigments.

As preferred pigments, disazo pigments are monoazo pigments (naphthol AS pigments especially laked BONS pigments) (especially Diarylgelb- pigments, Bisacetessigsäureacetanilidpigmente, disazo pyrazolone pigments), Chinacri- donpigmente, quinophthalone pigments, perinone pigments, phthalocyanine pigments, triarylcarbonium (alkali blue pigments, laked rhodamines, dye salts with complex anions), isoindoline pigments and carbon blacks.

The following are examples of particularly preferred pigments: C.I. Pigment Yellow 138, C.I. Pigment Red 122, C.I. Pigment Violet 19, C.I. Pigment Blue 15: 3 and 15: 4, C.I. Pigment Black 7, C.I. Pigment Orange 5, 38 and 43 and C.I. Pigment Green 7.

The pigments listed above can advantageously be used to produce ink-jet ink sets based on the colorant preparations according to the invention. The content of the individual pigments or inks in the respective pigments must be adapted to the respective requirements (e.g. trichromatic), i.e. The content of cyan, magenta, yellow and black pigments must be coordinated.

The following pigment combinations are particularly recommended for trichromatic requirements:

C.I. Pigment Yellow 138, C.I. Pigment Violet 19, C.I. Pigment Blue 15: 3 and C.I. Pigment black 7;

C.I. Pigment Yellow 138, C.I. Pigment Red 122, C.I. Pigment Blue 15: 3 or 15: 4 and C.I. Pigment black 7;

- C.l. Pigment Yellow 138, C.I. Pigment Violet 19, C.I. Pigment Blue 15: 3, C.I. Pigment Black 7, C.I. Pigment Orange 43 and C.I. Pigment green 7;

Cl Pigment Yellow 138, Cl Pigment Red 122, Cl Pigment Blue 15: 3 or 15: 4, Cl Pigment Black 7, Cl Pigment Orange 5 and Cl Pigment Green 7; Cl Pigment Yellow 138, Cl Pigment Red 122, Cl Pigment Blue 15: 3 or 15: 4, Cl Pigment Black 7, Cl Pigment Orange 38 and Cl Pigment Green 7;

C.I. Pigment Yellow 138, C.I. Pigment Red 122, C.I. Pigment Blue 15: 3 or 15: 4, C.I. Pigment Black 7, C.I. Pigment Orange 43 and C.I. Pigment Green 7.

Specifically selected disperse dyes are in detail:

C.I. Disperse Yellow 2, 4, 5, 6, 7, 8, 10, 11.11: 1, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 40, 41, 42, 43, 44, 45, 46, 47, 48, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 179, 180, 181, 182,183,184, 184: 1, 198,200,201,202,203,204,205, 206, 207, 208, 209, 210, 211, 212, 213, 214, 215, 216, 217, 218, 219, 220, 221, 222, 223, 224, 225, 226, 227 and 228;

C.I. Disperse Orange 2, 4, 5, 6, 7, 8, 9, 10, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 25: 1, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 38, 39, 40, 41, 41: 1, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 126, 127, 128, 129, 130, 131, 136, 137, 138, 139, 140, 141, 142, 143, 145, 146, 147 and 148;

Cl Disperse Red 2, 3, 4, 5, 5: 1, 6, 7, 8, 9, 10, 12, 13, 14, 15, 16, 18, 19, 20, 21, 22, 23, 24, 25 , 26, 27, 28, 29, 30, 30: 1, 31, 32, 33, 34, 35, 36, 38, 39, 40, 41, 43, 43: 1, 46, 48, 50, 51, 52 , 53, 54, 55, 55: 1, 56, 58, 59, 60, 61, 63, 65, 66, 69, 70, 72, 73, 74, 75, 76, 77, 79, 80, 81, 82 , 84, 85, 86, 86: 1, 87, 88, 89, 90, 91, 92, 93, 94, 96, 97, 98, 100, 102, 103, 104, 105, 106, 107, 108, 109 , 110, 111, 112, 113, 115, 116, 117, 118, 120, 121, 122, 123, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137 , 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, 150, 151, 151: 1, 152, 153, 154, 155, 156, 157, 158, 159, 160 , 161, 162, 163, 164, 165, 166, 167, 167: 1, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 178, 179, 180, 181, 182, 183 , 184, 185, 186, 187, 188, 189, 190, 190: 1, 191, 191: 1, 192, 193, 194, 195, 211, 223, 224, 273, 274, 275, 276, 277, 278 , 279, 280, 281, 302: 1, 305, 306, 307, 308, 309, 310, 311, 312, 313, 314, 315, 316, 317, 318, 319, 32 0, 321, 322, 323, 324, 325, 326, 327, 328, 329, 330, 331, 332, 333, 334, 335, 336, 338, 339, 340, 341, 342, 343, 344, 346, 347, 348, 349, 352, 356 and 367; Cl Disperse Violet 1, 2, 3, 4, 4: 1, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22 , 23, 24, 25, 26, 27, 28, 29, 31, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49 , 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 70, 81, 86, 87, 88, 89, 91, 92, 93, 94, 96 and 97;

C.I. Disperse Blue 2, 4, 5, 6, 8, 9, 10, 11, 12, 13, 13: 1, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 23: 1, 24, 25, 27, 28, 29, 30, 31, 32, 33, 34, 36, 38, 39, 40, 42, 43, 44, 45, 47, 48, 49, 51, 52, 53, 54, 55, 56, 58, 60, 60: 1, 61, 62, 63, 64, 64: 1, 65, 66, 68, 70, 72, 73, 75, 76, 77, 79, 80, 81, 81: 1, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 103, 104, 105, 107, 108, 109, 111, 112, 113, 114, 115, 116, 117, 118, 119, 121, 122, 123, 125, 126, 127, 128, 130, 131, 132, 133, 134, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, 150, 151, 152, 153, 154, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 165: 2, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 195, 281, 282, 283, 283: 1, 284, 285, 286, 287, 288, 289, 290, 291, 292, 293, 294, 316, 317, 318, 319, 320, 321, 322, 323, 324, 325, 326, 327, 328, 329, 330, 331, 332, 333, 334, 335, 336, 337, 338, 339, 340, 341, 342, 343, 344, 345, 346, 347, 349, 351 and 359;

C.I. Disperse Green 1, 2, 5, 6 and 9;

C.I. Disperse Brown 1,2,3,4,4: 1,5,7,8,9, 10, 11, 18, 19, 20 and 21;

- C.l. Disperse Black 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 22, 24, 25, 26, 27, 28, 29, 29: 1, 30, 31, 32, 33, 34 and 36;

In addition, substituted benzodifuranone dyes are suitable, the main body of which corresponds to formula A.

Such dyes can be substituted on one or both phenyl rings. Substituents X ¹ and X ² include halogen, alkyl, which may be interrupted by non-adjacent oxygen atoms, alkoxy, the alkyl radical of which may be interrupted by oxygen atoms and may also be substituted, hydroxy, optionally substituted amino, cyano, nitro and alkoxycarbonyl into consideration.

The dye of the following formula B is also suitable:

Further examples of disperse dyes are listed in WO 97/46623, WO 98/24850 and WO 99/29783.

The colorant preparations according to the invention can contain mixtures of two or more different colorants. However, colorant preparations according to the invention preferably do not contain mixtures of two or more different colorants, but only one colorant. The colorant preparations according to the invention contain colorants which are in particulate form, ie in the form of particles. The particles can have regular or irregular shape, for example the particles can be in spherical or approximately spherical shape or in needle shape.

In one embodiment of the present invention, the particles are in spherical or approximately spherical form, i.e. the ratio of longest diameter to smallest diameter is in the range from 1.0 to 2.0, preferably to 1.5.

Colorants in particulate form contained in the colorant preparations according to the invention should be as fine as possible. Preferably 95% by weight, particularly preferably 99% by weight, of the colorant particles have an average particle diameter of 1 μm, preferably 0.5 μm and in particular an average particle diameter of 0.2 μm.

In a preferred embodiment of the present invention, a colorant preparation according to the invention contains in the range from 10 to 100 g / l, preferably 12 to 70 g / l, of colorant in particulate form.

Colorant preparations according to the invention and in particular inks according to the invention for the ink jet process contain at least one organic solvent as component b), the organic solvent or solvents b) having a boiling point of at least 247 ° C., preferably at least 250 ° C., measured at atmospheric pressure.

Organic solvents b) contained in the colorant preparations according to the invention are preferably characterized in that their decomposition point is at least 200 ° C. or higher.

Low molecular weight polytetrahydrofuran is a preferred organic solvent b), it can be used alone or preferably in a mixture with one or more difficult to evaporate, water-soluble or water-miscible organic solvents.

The preferably used low molecular weight polytetrahydrofuran usually has an average molecular weight M _w of 150 to 500 g / mol, preferably 200 to 300 g / mol and particularly preferably approximately 250 g / mol (corresponding to a molecular weight distribution). Polytetrahydrofuran can be prepared in a known manner via cationic polymerization of tetrahydrofuran. This creates linear polytetramethylene glycols.

When polytetrahydrofuran is used in a mixture with other organic solvents, organic solvents which are difficult to evaporate (i.e. usually have a boiling point> 247 ° C at normal pressure) are used, which are soluble in water or miscible with water.

Suitable solvents are polyhydric alcohols, preferably unbranched and branched polyhydric alcohols having 3 to 8, in particular 3 to 6, carbon atoms, such as e.g. Glycerol.

Other suitable solvents are polyethylene and polypropylene glycols, including the lower polymers (tri- and tetramers). Polyethylene and polypropylene glycols with average molecular weights M _{n of} from 120 to 1500 g / mol, in particular from 200 to 800 g / mol, especially from 300 to 500 g / mol, are preferred. Examples include tri and tetraethylene glycol, triethylene glycol monomethyl, -. ethyl, propyl and butyl ether, tri- and tetra-1, 2- and -1, 3-propylene glycol and tri- and tetra-1, 2- and -1, 3-propylene glycol monomethyl, -ethyl, - called propyl and butyl ether.

Examples of particularly preferred solvents are glycerol, polyethylene glycol (M _n 300 to 500 g / mol), diethylene glycol monobutyl ether and triethylene glycol monobutyl ether.

Polytetrahydrofuran can also be mixed with one or more (e.g. two, three or four) of the solvents listed above.

In one embodiment of the present invention, colorant preparations according to the invention and in particular inks according to the invention for the ink jet process can contain 0.1 to 45% by weight, preferably 5 to 30% by weight, particularly preferably 10 to 25% by weight, and very particularly preferably contain 10 to 20% by weight of organic solvents.

Organic solvents in the sense of the present invention are liquid at room temperature.

Colorant preparations according to the invention and in particular inks according to the invention for the ink jet process do not contain any organic solvents which have a boiling point below 247 ° C., measured at atmospheric pressure, even under normal pressure designated. For the purposes of the present invention, “no solvents” is understood to mean that the proportion of organic solvents which may be present as impurities and have a boiling point below 247 ° C. is less than 0.25% by weight in total, preferably less than 0.1 % By weight and particularly preferably less than 0.05% by weight, details in% by weight being based in each case on the colorant preparation according to the invention.

Examples of organic solvents with a boiling point below 247 ° C. are, for example, ethylene glycol, diethylene glycol, N-methylpyrrolidone, propylene glycol, propylene carbonate, diethylene monomethyl ether, diethylene monoethyl ether, diethylene mono-n-butyl ether, di-n-butyl ether, 1, 2-dimethoxyethane, isopropanol and ethanol.

The organic solvents, in particular also the particularly preferred solvent combinations mentioned, can advantageously be supplemented by urea (preferably 0.1 to 5% by weight, based on the weight of the colorant preparation according to the invention or the ink according to the invention for the inkjet process) , which enhances the water-retaining effect of the solvent mixture.

The colorant preparations according to the invention and in particular the inks according to the invention for the ink jet process can contain further auxiliaries, such as are customary in particular for aqueous ink jet inks and in the printing and coating industry. Examples include erythritol, pentaerythritol, pentites such as arabite, adonite and xylitol and hexites such as sorbitol, mannitol and dulcitol. Polyethylene glycols with an M _w of more than 2000 g / mol to about 10,000 g / mol, preferably up to 800 g / mol, may also be mentioned. Preservatives such as 1, 2-

Benzisothiazolin-3-one and its alkali metal salts, degassers / defoamers such as, for example, ethoxylated acetylenediols, which usually contain 20 to 40 moles of ethylene oxide per mole of acetylenediol and can also have a dispersing action, agents for regulating the viscosity, flow control agents, wetting agents (for example wetting surfactants) based on ethoxylated or propoxylated fatty or oxoalcohols, propylene oxide / ethylene oxide block copolymers, ethoxylates of oleic acid or alkylphenols, alkylphenol ether sulfates, alkylpolyglycosides, alkylphosphonates, alkylphenylphosphonates, alkylphosphates, alkylphenylphosphates or preferably 2-ether-siloxane-alkoxylated-copolymerized (3-hydroxypropyl) heptamethyltrisiloxanes, which generally have a block of 7 to 20, preferably 7 to 12, ethylene oxide units and a block of 2 to 20, preferably 2 to 10, propylene oxide units and in amounts of 0.05 to 1% by weight in the colorant accessories can be included), anti-settling agents, gloss improvers, lubricants, adhesion promoters, skin preventives, matting agents, emulsifiers, stabilizers, water repellents, light protection additives, handle improvers, antistatic agents, bases such as for example K ₂ CO ₃ or acids, especially carboxylic acids such as lactic acid or citric acid to regulate the pH. If these agents are part of colorant preparations according to the invention and in particular inks according to the invention for the ink jet process, their total amount is generally 2% by weight, in particular 1% by weight, based on the weight of the colorant preparations according to the invention and in particular of the inks according to the invention for the ink jet process.

The colorant preparations according to the invention can furthermore contain dispersants. For example, alkoxylated and partially sulfated alkylphenols, such as, for example, the substances described in US Pat. No. 4,218,218, or condensation products of naphthalenesulfonic acid and formaldehyde or mixtures of arylsulfonic acid-formaldehyde condensation products, as are described, for example, in US Pat. No. 5,186,846.

Other suitable dispersants are ethoxylated fatty alcohols of the formula

where x is an integer in the range from 12 to 30, preferably up to 18 and y is an integer in the range from 3 to 50.

Other suitable dispersants are maleic acid / acrylic acid copolymers, in particular those with a molecular weight M _n in the range from 2000 to 10,000 g / mol, which are suitable in the form of statistical copolymers or block copolymers. Other suitable dispersants are N-vinylpyrrolidone homopolymers and acrylate-N-vinylpyrrolidine copolymers, in particular those N-vinylpyrrolidone homopolymers and acrylate-N-vinylpyrrolidine copolymers with molecular weight M _n in the range from 2000 to 10,000 g / mol, in the form of statistical copolymers or block copolymers.

In one embodiment of the present invention, colorant preparations according to the invention and in particular inks according to the invention for the ink jet process contain binders. Binders can be selected from the group of radiation-curable binders, thermally curable binders and air-drying binders. Suitable binders are described, for example, in WO 99/01516 and WO 02/36695. Dispersing binder systems as in WO 03/29318 are also suitable as additives.

In one embodiment of the present invention, colorant preparations according to the invention and in particular inks according to the invention for ink jet Process a dynamic viscosity of 1 to 30 mPa-s, preferably 1 to 20 mPa-s, particularly preferably 2 to 15 mPa-s, each determined at 20 ° C.

The surface tension of colorant preparations according to the invention and in particular inks according to the invention for the ink jet process is generally 20 to 70 mN / m at 20 ° C., in particular 20 to 40 mN / m, particularly preferably 25 to 35 mN / m.

The pH of colorant preparations according to the invention and in particular inks according to the invention for the ink jet process is generally in the range from 5 to 10, preferably in the range from 7 to 9.

The colorant preparations according to the invention contain water, preferably deionized water, as component c). The preferred water content is at least 30% by weight, preferably at least 45% by weight and particularly preferably at least 65% by weight.

In one embodiment of the present invention, colorant preparations according to the invention and in particular inks according to the invention for the ink jet process contain less than 500 ppm of free heavy metal ions, preferably less than 400 ppm, based in each case on the mass of the colorant preparation according to the invention or ink according to the invention for the ink. jet process. Examples of heavy metal ions are: Cu ²⁺ , Co ²⁺ , Co ³⁺ , Fe ²⁺ , Fe ³⁺ , Ni ²⁺ , Zn ⁺ , Ca ²⁺ . In particular, colorant preparations according to the invention or inks according to the invention for the ink jet process contain up to 300 ppm iron.

Colorant preparations according to the invention and in particular inks according to the invention for the ink jet process with less than 500 ppm of heavy metal ions can be produced, for example, by using purified pigments or by producing the colorant preparations according to the invention and in particular the inks according to the invention for the ink. Jet process uses steps such as precipitation, salting out, ion exchange process, filtering, electrolytic process or other processes for deionization known per se to the person skilled in the art. It is also possible to use appropriately purified organic solvents and demineralized water.

In one embodiment of the present invention, colorant preparations according to the invention and in particular inks according to the invention for the ink jet process contain less than 0.05% by weight of chloride, determined as sodium chloride. Colorant preparations according to the invention and in particular inks according to the invention are generally environmentally friendly.

Another aspect of the present invention is a process for the preparation of colorant preparations according to the invention, hereinafter also referred to as the production process according to the invention. The manufacturing method according to the invention usually contains one or more steps in which different components are mixed. Such steps are carried out in the usual mixing apparatus, for example in dissolvers, kettles, mills, ball mills or agitator ball mills.

In one embodiment of the production process according to the invention, colorants are mixed in particulate form (a), for example in the form of a water-containing press cake, together with at least one organic solvent (b), water (c) in a suitable apparatus, for example in a dissolver. The resulting mixture is then ground in a mill in order to achieve the desired particle size (generally a maximum diameter of 1 μm, preferably 0.5 μm and particularly preferably 0.2 μm).

Colorant preparations according to the invention can be used directly as or for the production of inks. In particular, colorant preparations according to the invention can be used directly as or for the production of inks for the ink jet process. Other suitable inks are, for example, inks for fountain pens.

In order to produce inks from colorant preparations according to the invention, it is sufficient in one embodiment of the present invention to set the desired colorant concentration by adding further water to the colorant preparations according to the invention, optionally adding further additives and finally using a filter device with fine separation in the range from 1 to 0.5 μm to filter. Ink-jet inks according to the invention can thus be obtained.

Another aspect of the present invention is a method for printing substrates, which can be flat or three-dimensional, for example, by the ink jet method using colorant preparations according to the invention or inks according to the invention. For this purpose, colorant preparations according to the invention or ink jet inks according to the invention are printed on the substrate and the print obtained is then optionally fixed.

In the ink jet process, the usually aqueous inks are sprayed directly onto the substrate in small droplets. A distinction is made between a continuous process in which the ink is pressed evenly through a nozzle and electric field, depending on the pattern to be printed, is directed onto the substrate, and an interrupted ink jet or "drop-on-demand" process in which the ink is ejected only where a colored dot is to be set. In the latter method, pressure is exerted on the ink system either by means of a piezoelectric crystal or a heated cannula (bubble or thermo-jet method) and an ink drop is thus ejected. Such procedures are in text. Chem. Color, volume 19 (8), pages 23 to 29, 1987, and volume 21 (6), pages 27 to 32, 1989.

The inks according to the invention are particularly suitable for the bubble jet process and for the process using a piezoelectric crystal.

Suitable substrate materials are:

cellulose-containing materials such as paper, cardboard, cardboard, wood and wood-based materials, which can also be lacquered or otherwise coated,

metallic materials such as foils, sheets or workpieces made of aluminum, iron, copper, silver, gold, zinc or alloys of these metals, which can be painted or otherwise coated,

silicate materials such as glass, porcelain and ceramics, which can also be coated,

polymeric materials of all kinds such as polystyrene, polyamides, polyesters, polyethylene, polypropylene, melamine resins, polyacrylates, polyacrylonitrile, polyurethanes, polycarbonates, polyvinyl chloride, polyvinyl alcohols, polyvinyl acetates, polyvinylpyrrolidones and corresponding copolymers and block copolymers, biodegradable polymers and natural polymers such as gelatin,

Leather, both natural leather and synthetic leather, as smooth, nappa or suede leather,

Food and cosmetics,

and particularly

textile substrates and fabrics such as fabrics, knitted fabrics, woven goods, nonwovens and made-up goods made of, for example, polyester, modified polyester, blended fabrics made of more than two materials such as polyester blended fabrics and cotton blended fabrics, cellulose-containing materials such as cotton, jute, flax, hemp and ramie, viscose, wool, silk, polyamide, polyamide blend, polyacrylonitrile,

Polyurethane, poly-THF, triacetate, acetate, polycarbonate, polypropylene, polyvinyl chloride,

Polyester microfibers and glass fiber fabrics.

Colorant preparations according to the invention and in particular inks according to the invention for the ink-jet process show overall advantageous application properties, above all good writing behavior and good long-term writing behavior (kogation) and good stand, and give high-quality print images, i.e. high brilliance and depth of color as well as high rub, light, water and wet rub fastness, wash fastness and chemical resistance to cleaning. They are particularly suitable for printing on coated and uncoated paper as well as textile substrates.

Another embodiment of the present invention are substrates, in particular textile substrates, which have been printed by one of the above-mentioned methods according to the invention and which are distinguished by particularly sharply printed images or drawings and an excellent grip.

According to a further embodiment of the present invention, at least two, preferably at least three, different inks according to the invention can be combined into sets for the ink jet process.

The invention is illustrated by a working example.

example 1

1 a) Dispersing a pigment

The following were milled in a Drais Superflow DCP SF 12 agitator ball mill:

1800 g Pigment Blue 15: 3

450 g nC ₁₈ H ₃₇ θ (CH ₂ CH ₂ O) ₂₅ H

3700 g of distilled water

The milling was continued until the pigment particles had an average diameter of 100 nm.

1 b) Production of a colorant preparation according to the invention

The following were mixed in a beaker: 17 g of the dispersed pigment from 1 a)

15 g glycerin (boiling point: 290 ° C)

1 g polyethylene glycol (M _n 8000 g / mol)

7 g polyethylene glycol (M _n 400 g / mol) 5 g poly-THF (M „250 g / mol)

0.2 g Tego Wet® 250, a wetting agent with a boiling point of »250 ° C

1 g urea

53.8 g of fully demineralized water

The colorant preparation thus obtained was then filtered through a sieve with a pore diameter of 1 μm.

The glycerin, polyethylene glycols and poly-THF used had a free heavy metal ion content of less than 500 ppm, based in each case on glycerol, polyethylene glycols and poly-THF used.

The colorant preparation according to the invention could be used as an ink for the ink jet process. Very good results were achieved when printing on substrates such as textiles (cotton).

The level of the droplets on substrates, especially textiles such as cotton, was very good.

Claims

claims

1. Colorant preparations containing a) at least one colorant in particulate form, b) at least one organic solvent with a boiling point of at least 247 ° C., measured at atmospheric pressure, and c) water, and less than 0.25% by weight of organic solvents with a boiling point below 247 ° C, measured at atmospheric pressure.

2. Colorant preparations according to claim 1, characterized in that all organic solvents b) have a boiling point of at least 250 ° C, measured at atmospheric pressure.

3. Colorant preparations according to claim 1 or 2, characterized in that all organic solvents b) have a decomposition point of at least 200 ° C.

4. Colorant preparations according to claim 1 to 3, characterized in that they contain at least 30 wt .-% water c).

5. Colorant preparations according to claim 1 to 4, characterized in that they have less than 500 ppm free heavy metal ions.

6. Use of colorant preparations according to claim 1 to 5 as or for the preparation of inks.

7. Use of colorant preparations according to claim 1 to 5 as or for the preparation of inks for the ink jet process.

8. A method for producing ink jet inks using colorant preparations according to at least one of claims 1 to 5.

Process for printing substrates by the ink jet process using colorant preparations according to at least one of claims 1 to 5 or using inks according to claim 7 or 8.

10. The method according to claim 9, characterized in that it is textile substrates.

11. Printed substrates, obtainable according to claim 10 or 11.