DE10026465A1 - Aqueous coloring agent composition, useful for ink jet printing, contains a low molecular weight polytetrahydrofuran, optionally mixed with a water soluble or miscible solvent of low volatility - Google Patents

Abstract

A coloring agent composition (I) comprises (A) a dispersed (A1) or dissolved (A2) coloring agent (B) a dispersing agent in the case of (A1) (C) a low mol. wt. polytetrahydrofuran (C1) optionally mixed with a water soluble or miscible solvent (C2) of low volatility and (D) water. An Independent claim is included for a process for the printing of flat or three dimensional substrates by an ink jet process, whereby the coloring agent composition (I) is printed onto the substrate and the resulting print is optionally fixed.

Description

The present invention relates to new colorant preparations which

• A) at least one dispersed (A1) or dissolved (A2) colorant tel,
• B) in the case of a colorant (A1), a dispersant,
• C) a low molecular weight polytetrahydrofuran (C1), desired if mixed with one or more difficult to evaporate, water-soluble or water-miscible organic Solvents (C2) and
• D) water

included as essential components.

The invention further relates to the use of these colorants tel formulations as inks for the ink jet process and a Process for printing on flat or three-dimensional ge designed substrates in the ink-jet process, in which these Colorant preparations are used.

To the inks used in the ink jet process (ink jet printing drive like Thermal Ink Jet, Piezo Ink Jet, Continuous Ink Jet, Valve Jet) are used to meet a number of requirements put: You need suitable viscosity and upper for printing have surface tension, they must be stable in storage, d. that is, they should not coagulate or flocculate, and they must not lead to blockage of the printer nozzle, which is particularly the case with dis pergiert, ie containing undissolved colorant particles Inks can be problematic. The requirements for the bearings The stability of these inks also means that the dis do not settle the colorant particles. Finally have to In the case of the continuous ink jet, the inks are stable against the ink of conductive salts and none when the ion content is increased Show tendency to flocculate. In addition, the received Prints meet the color requirements, d. H. high glasses Show lance and depth of color, and good fastness properties, e.g. B. Rubbing fastness fastness, light fastness, water fastness and wet rub fastness, and good exhibit drying behavior.  

Ink-jet inks containing pigment are known from WO-A-99/01516. which, however, differ from the present colorant preparations distinguish by component (C).

The object of the present invention was to add new colorants to provide which advantageous application in ink Jet process can find and especially good write and continuous write behavior with good drying behavior exhibit.

Accordingly, the colorant preparations defined at the outset found.

The colorant preparations according to the invention can essentially Chen insoluble, dispersed colorant (A1) (finely divided, or ganic or inorganic pigments or in water / solvent Mixture of insoluble dyes) or dissolved colorant (A2) (in Water / solvent mixture containing soluble dyes). Of course, the colorant accessories according to the invention Reitungen also contain colorant mixtures, preferably lies however only one colorant. Preferred according to the invention Colorant preparations based on pigments. As a fining agent these pigment preparations can be similar in color to the pigment soluble dyes, especially direct, acid or reactive dyes included.

The following are examples of suitable pigments (A1) the vat dyes due to the overlap with the organic pigments are listed.

Organic pigments

• - monoazo pigments:
  CI Pigment Brown 25;
  CI Pigment Orange 5, 13, 36 and 67;
  CI 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;
  CI Pigment Yellow 1, 3, 73, 74, 65, 97, 151 and 183;
• - disazo pigments:
  CI Pigment Orange 16, 34 and 44;
  CI Pigment Red 144, 166, 214 and 242;
  CI Pigment Yellow 12, 13, 14, 16, 17, 81, 83, 106, 113, 126, 127, 155, 174, 176 and 188;
• - Anthanthrone pigments:
  CI Pigment Red 168 (CI Vat Orange 3);
• - Anthraquinone pigments:
  CI Pigment Yellow 147 and 177;
  CI Pigment Violet 31;
• - Anthraquinone pigments:
  CI Pigment Yellow 147 and 177;
  CI Pigment Violet 31;
• - anthrapyrimidine pigments:
  CI Pigment Yellow 108 (CI Vat Yellow 20);
• - Quinacridone pigments:
  CI Pigment Red 122, 202 and 206;
  CI Pigment Violet 19;
• - Quinophthalone pigments:
  CI Pigment Yellow 138;
• - Dioxazine pigments:
  CI Pigment Violet 23 and 37;
• - Flavanthrone pigments:
  CI Pigment Yellow 24 (CI Vat Yellow 1);
• - Indanthrone pigments:
  CI Pigment Blue 60
  (CI Vat Blue 4) and 64 (CI Vat Blue 6);
• - Isoindoline pigments:
  CI Pigment Orange 69;
  CI Pigment Red 260;
  CI Pigment Yellow 139 and 185;
• - Isoindolinone pigments:
  CI Pigment Orange 61;
  CI Pigment Red 257 and 260;
  CI Pigment Yellow 109, 110, 173 and 185;
• - Isoviolanthrone pigments:
  CI Pigment Violet 31 (CI Vat Violet 1);
• - Metal complex pigments:
  CI Pigment Yellow 117, 150 and 153;
  CI Pigment Green 8;
• - Perinone pigments:
  CI Pigment Orange 43
  CI Vat Orange 7);
  CI Pigment Red 194 (CI Vat Red 15);
• - Perylene pigments:
  CI Pigment Black 31 and 32;
  CI Pigment Red 123, 149, 178, 179 (CI Vat Red 23), 190 (CI Vat Red 29) and 224;
  CI Pigment Violet 29;
• - phthalocyanine pigments:
  CI 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:
  CI Pigment Red 88 and 181 (CI Vat Red 1);
  CI Pigment Violet 38 (CI Vat Violet 3);
• - Triaryl carbonium pigments:
  CI Pigment Blue 1, 61 and 62;
  CI Pigment Green 1;
  CI Pigment Red 81, 81: 1 and 169;
  CI Pigment Violet 1, 2, 3 and 27
• - C.I. Pigment Black 1 (aniline black);
• - C.I. Pigment Yellow 101 (Aldazine Yellow);
• CI Pigment Brown 22;
  Vat dyes (except those already mentioned above):
• - C.I. Vat Yellow 2, 3, 4, 5, 9, 10, 12, 22, 26, 33, 37, 46, 48, 49 and 50;  
• - C.I. Vat Orange 1, 2, 5, 9, 11, 13, 15, 19, 26, 29, 30 and 31;
• - C.I. Vat Red 2, 10, 12, 13, 14, 16, 19, 21, 31, 32, 37, 41, 51, 52 and 61;
• - C.I. Vat Violet 2, 9, 13, 14, 15, 17 and 21;
• - C.I. Vat Blue 1 (C.I. Pigment Blue 66), 3, 5, 10, 12, 13, 14, 16, 17, 18, 19, 20, 22, 25, 26, 29, 30, 31, 35, 41, 42, 43, 64, 65, 66, 72 and 74;
• - C.I. Vat Green 1, 2, 3, 5, 7, 8, 9, 13, 14, 17, 26, 29, 30, 31, 32, 33, 40, 42, 43, 44 and 49;
• - C.I. Vat Brown 1, 3, 4, 5, 6, 9, 11, 17, 25, 32, 33, 35, 38, 39, 41, 42, 44, 45, 49, 50, 55, 57, 68, 72, 73, 80, 81, 82, 83 and 84;
• - C.I. Vat Black 1, 2, 7, 8, 9, 13, 14, 16, 19, 20, 22, 25, 27, 28, 29, 30, 31, 32, 34, 36, 56, 57, 58, 63, 64 and 65;

Inorganic pigments

• - white pigments:
  Titanium dioxide (CI Pigment White 6), zinc white, colored zinc oxide; Zinc sulfide, lithopone;
  Lead white;
• - black pigments:
  Iron oxide black (CI Pigment Black 11), iron-manganese black, spinel black (CI Pigment Black 27); Carbon black (CI Pigment Black 7);
• - Colored pigments:
  Chromium oxide, chromium oxide hydrate green; Chrome green (CI Pigment Green 48); Cobalt green (CI Pigment Green 50); Ultramarine green;
  Cobalt blue (CI Pigment Blue 28 and 36); Ultramarine blue; Iron blue (CI Pigment Blue 27); Manganese blue; Ultramarine violet; Cobalt and gan violet;
  Iron oxide red (CI Pigment Red 101); Cadmium sulfoselenide (CI Pigment Red 108); Molybdate red (CI Pigment Red 104); Ultramarine red;
  Iron oxide brown, mixed brown, spinel and corundum phases (CI Pigment Brown 24, 29 and 31), chrome orange;
  Iron oxide yellow (CI Pigment Yellow 42); Nickel titanium yellow (CI Pigment Yellow 53; CI Pigment Yellow 157 and 164); Chrome titanium yellow; Cadmium sulfide and cadmium zinc sulfide (CI Pigment Yellow 37 and 35); Chrome yellow (CI Pigment Yellow 34), zinc yellow, alkaline earth metal chromates; Naples yellow; Bis mutvanadat (CI Pigment Yellow 184);
• - interference pigments:
  Metallic effect pigments based on coated metal flakes; Pearlescent pigments based on metal oxide coated mica platelets; Liquid crystal pigments.

Monoazo pigments (in particular lacquered BONS pigments, naphthol AS pigments), disazo pigments (especially diaryl yellow pigments, bisacetoacetic acid acetanilide pig elements, disazopyrazolone pigments), quinacridone pigments, quinophtha ion pigments, perinone pigments, phthalocyanine pigments, triarylcar bonium pigments (alkali blue pigments, lacquered rhodamines, color substance salts with complex anions), isoindoline pigments and carbon black call.

The following are examples of particularly preferred pigments: C.I. Pigment Yellow 138, C.I. Pigment Red 122, C.I. Pigment Vio let 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.

These pigments can be advantageous for creating ink jet tin tensets based on the colorant preparations according to the invention be used. The content of the individual inks in the respective pigments is adapted to the respective requirements (e.g. Trichromatic).

The following pigment combinations are particularly recommended:

• - 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, I. 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;
• - 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 5 and C.I. 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 38 and C.I. 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.

As dyes (A1) in the water / solvent mixture in we are insoluble, are suitable in addition to those already mentioned Ten vat dyes in particular azo, anthraquinone, quinophone thalon, benzodifuran, methine and azamethine dyes that are free of acidic or ionic groups.

Examples of suitable dyes (A1) are:

• - C.I. Disperse Yellow 1, 2, 3, 4, 5, 6, 7, 8, 9, 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, 39, 40, 41, 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, 14, 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, 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 1, 2, 3, 3: 3, 4, 5, 6, 7, 8, 9, 10, 11, 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, 37, 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, 76, 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;
• - C.I. Disperse Red 1, 2, 3, 4, 5, 5: 1, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 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, 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, 320, 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, 356 and 367;
• - C.I. 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 1, 1: 1, 2, 3, 3: 1, 4, 5, 6, 7, 7: 1, 8, 9, 10, 11, 12, 13, 13: 1, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 23: 1, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 38, 39, 40, 12, 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, 102, 103, 104, 105, 106, 107, 108, 109, 111, 112, 113, 114, 115, 116, 117, 118, 119, 121, 122, 123, 124, 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 and 349;
• - 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.I. 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;
• - C.I. Solvent Yellow 2, 3, 7, 12, 13, 14, 16, 18, 19, 21, 25, 25: 1, 27, 28, 29, 30, 33, 34, 36, 42, 43, 44, 47, 56, 62, 72, 73, 77, 79, 81, 82, 83, 83: 1, 88, 89, 90, 93, 94, 96, 98, 104, 107, 114, 116, 117, 124, 130, 131, 133, 135, 141, 143, 144, 145, 146, 157, 160: 1, 161, 162, 163, 167, 169, 172, 173, 176, 179, 180, 181, 182, 183, 184, 185, 186, 187, 189, 190 and 191;
• - C.I. Solvent Orange 1, 2, 3, 4, 5, 7, 11, 14, 20, 23, 25, 31A, 40: 1, 41, 45, 54, 56, 58, 60, 62, 63, 70, 75, 77, 80, 81, 86, 99, 102, 103, 105, 106, 107, 108, 109, 110, 111, 112 and 113;
• - C.I. Solvent Red 1, 2, 3, 4, 8, 16, 17, 18, 19, 23, 24, 25, 26, 27, 30, 33, 35, 41, 42, 45, 48, 49, 52, 68, 69, 72, 73, 83: 1, 84: 1, 89, 90, 90: 1, 91, 92, 106, 109, 111, 118, 119, 122, 124, 125, 127, 130, 132, 135, 141, 143, 145, 146, 149, 150, 151, 155, 160, 161, 164, 164: 1, 165, 166, 168, 169, 172, 175, 179, 180, 181, 182, 195, 196, 197, 198, 207, 208, 210, 212, 214, 215, 218, 222, 223, 225, 227, 229, 230, 233, 234, 235, 236, 238, 239, 240, 241, 242, 243, 244, 245, 247 and 248;
• - C.I. Solvent Violet 2, 8, 9, 11, 13, 14, 21, 21: 1, 26, 31, 36, 37, 38, 45, 46, 47, 48, 49, 50, 51, 55, 56, 57, 58, 59, 60 and 61;
• - C.I. Solvent Blue 2, 3, 4, 5, 7, 18, 25, 26, 35, 36, 37, 38, 43, 44, 45, 48, 51, 58, 59, 59: 1, 63, 64, 67, 68, 69, 70, 78, 79, 83, 94, 97, 98, 99, 100, 101, 102, 104, 105, 111, 112, 122, 124, 128, 129, 132, 136, 137, 138, 139 and 143;
• - C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34 and 35;  
• - C.I. Solvent Brown 1, 3, 4, 5, 12, 20, 22, 28, 38, 41, 42, 43, 44, 52, 53, 59, 60, 61, 62 and 63;
• - C.I. Solvent Black 3, 5, 5: 2, 7, 13, 22, 22: 1, 26, 27, 28, 29, 34, 35, 43, 45, 46, 48, 49 and 50.

In addition, substituted benzodifuranone dyes are suitable, the main body of the formula

corresponds. Such dyes can be on one or both phenyl wrestle be substituted. Halogen, Al. Come as substituents kyl, which may be due to non-adjacent oxygen atoms is interrupted, alkoxy, whose alkyl radical by oxygen atoms can be interrupted and can also be substituted, Hydroxy, optionally substituted amino, cyano, nitro and Alkoxycarbonyl into consideration.

Dyes of the following formulas are also suitable:

Further examples of insoluble dyes (A1) are in the WO-A-97/46623, 98/24850 and 99/29783.

The undissolved, dispersed colorant (A1) should be as possible be finely divided. Preferably 95%, particularly preferably 99%, the colorant particles (A1) a particle size 1 im, preferred as 0.5 µm.

As dyes (A2), which are soluble in the water / solvent mixture are particularly suitable arylmethane, azo, methine, rhod amine and metal complex dyes, the acidic or ionic group pen included.

Examples of suitable dyes (A2) are:

• - C.I. Basic Yellow 2, 37, 78, 94, 96, 97, 98, 102 and 111;
• - C.I. Basic Orange 2, 60, 62 and 63;
• - C.I. Basic Red 1, 14, 49, 108 and 111;
• - C.I. Basic Violet 1, 3, 4, 10, 11, 49 and 50;  
• - C.I. Basic Blue 26, 152, 157, 158 and 161;
• - C.I. Basic Green 1 and 4;
• - C.I. Basic Brown 1;
• - C.I. Acid Orange 7 and 8;
• - C.I. Acid Blue 9;
• - C.I. Direct Yellow 4, 5, 11, 15, 127, 131 and 147;
• - C.I. Direct Red 239 and 254;
• - C.I. Direct Blue 161, 199, 279 and 281;
• - C.I. Reactive Red 120.

The colorant preparations according to the invention contain in the Rule 0.01 to 20% by weight, preferably 0.2 to 10% by weight, particularly preferably 1 to 6% by weight of colorant (A), with colorant (A1) Amounts in the range from 1 to 6% by weight and for colorants (A2) Amounts in the range from 1 to 10% by weight are particularly suitable.

The colorant preparations according to the invention are based on unge dissolved colorants (A1), then they contain a dispersant (B). In the case of dissolved colorants (A2), the component is (B) of course not necessary.

In principle, all of them are suitable as component (B) for aqueous Sy known dispersants.

Water-soluble dispersants on the Base of one or more water soluble oxyalkylated phenols (B1), one or more arylsulfonic acid-formaldehyde condensates onproducts (B2), one or more condensation products one at least difunctional isocyanate, each with an isocyanate treactive group-bearing compounds (B3) or one or several alkoxylated hydroxynaphthalenes (B4).

The dispersants (B1) are oxyalkylated phenols of the formula I or II

in which
a 0 to 125 on average,
b on average 37 to 250, where in the case of b <37 the ratio b: a is at least 1: 1, and
d is 0 or 1,
or mixtures thereof are preferred.

The products of the formulas I and II can be represented by reacting the phenol derivatives of the formula III or IV

with propylene oxide and subsequent reaction of the adduct with Ethylene oxide or by reacting III and / or IV with ethylene oxide can be obtained. If necessary, the adducts with Chlorosulfonic acid or sulfur trioxide completely or partially converted to sulfuric acid half-esters and the half-esters obtained neutralized with alkaline agents.

The phenols of the formula III and IV can be obtained by reacting phenol or 2,2- (pp'-bishydroxydiphenyl) propane with 3 or 4 mol of styrene in the presence of acid as a catalyst. The phenols III and IV are first reacted by known processes with ethylene oxide or only with ethylene oxide in the presence of acidic or alkaline catalysts to give the corresponding oxyalkylation products I and II with d = 0. The oxyalkylation can e.g. B. by the method described in US-A-2 979 528. For the case b <37 the quotient must be
b / a <1.

The sulfuric acid semi-esters are obtained by reaction of the oxalkyly products with chlorosulfonic acid or sulfur trioxide provides, the amount can be chosen so that all free Hydroxy groups or only a part is sulfated. In the latter Traps form mixtures of compounds of formula I and II, which contain free and sulfated hydroxy groups. For Use as dispersants in the implementation obtained half ester of sulfuric acid in water-soluble salts transferred. The alkali metal salts, e.g. B. the sodium or potassium salts. Here are in Two equivalents for chlorosulfonic acid, for sulfur trioxide an equivalent of basic compounds is required. As  the latter is advantageously used in aqueous alkali metal hydroxide. Bai of neutralization, the temperature should not be 70 ° C exceed. The salts obtained can be in the form of aqueous Solutions or as such isolated and in solid form be used.

Dispersants (B1) in which a is 0 to on average are preferred 2.5, b on average 37 to 25Q and d 0 to 0.5 in the middle. Especially are preferred dispersants (B1) in which a 0 to im Average 2.5, b average 50 to 100 and d average 0.5.

The dispersants (B1) are known and z. See, for example, US-A-4,218,218 described.

The condensation products (B2) are aromatic by sulfonation contain compounds such as naphthalene itself or naphthalene tender mixtures and subsequent condensation of the formed Arylsulfonic acids available with formaldehyde.

As a starting product for the production of arylsulfonic acids comes z. B. a mixture of such aromatic compounds in Be tracht by thermal fission of a naphthenic back base oil and fractionation of the fission products are available. The naphthenic residual oils fall, for example, at the Crac of light petrol and are also known as high-boiling aromati called hydrocarbon oils. The naphthenic back base oil is preferably at a temperature of 1400 to Thermally split at 1700 ° C. The fission products then become one fractional distillation fed. The at normal pressure (1013 mbar) from 100 to 120 ° C passing fraction is collected and fed to the sulfonation as an aromatic compound. A such fraction is used in the known acetylene oil quench process usually obtained as a by-product (Ullmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft mbE, Weinheim, 1985, Volume A1, pages 107 to 112).

This aromatic fraction consists of a mixture of many aromatic substances, the structure and amount of which can practically not be determined in detail. The following aryl compounds are the main representatives of this aromatic fraction:

The aromatics fraction also contains identified stocks share the following aryl compound in amounts of 0.1 to about 2% by weight : fluorene, indane, methylstyrene, phenanthrene, methylindane, Dimethylnaphthalene, ethylnaphthalene, xylenes, tetralin, styrene, Methylethylbenzene, anthracene, fluoranthrene, pyrene, acetonaphthylene and toluene.

Particularly suitable arylsulfonic acids usually contain a- and b-naphthalenesulfonic acids, the ratio of the a to b-isomers usually 20: 1 to 1: 8, in particular 10: 1 to 1: 5 is.

The condensation products show when using the above. Aromatic fraction prefers a sulfonic acid group content of ma ximal 40% by weight.

The dispersant (B2) can be prepared in the presence of aromatic or long-chain aliphatic carboxylic acids, the Salts, anhydrides or mixtures of these compounds vorgenom men.

Examples of suitable aromatic carboxylic acids or their Derivatives are naphthalene carboxylic acid, naphthalic acid, terephthalate acid, isophthalic acid, benzoic acid, trimellitic acid, phenylacetic acid acid, phenoxyacetic acid, salicylic acid, p-hydroxybenzoic acid, Diphenylacetic acid, m-hydroxybenzoic acid, benzene tetracarboxylic acid or acid anhydrides such as phthalic anhydride, trimellitic acid anhydride, benzene-1,2,4,5-tetracarboxylic acid dianhydride or Naphthalic anhydride.

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 Carboxylic acids such as 2-ethylhexanoic acid, isononanoic acid or isotri decanoic acid.

The salts of the carboxylic acids mentioned are the alkali, Ammonium or alkaline earth metal salts, for example by neutralizing these carboxylic acids with sodium hydroxide solution, potassium lye, lithium hydroxide, soda, magnesium carbonate, calcium oxide,  Calcium hydroxide, ammonia or alkanolamines such as ethanolamine, Diethanolamine or triethanolamine are available.

Sodium benzoate, sodium phenylacetate and sodium are preferred salicylate, sodium 4-hydroxybenzoate, sodium terephthalate, Sodium 2-hydroxy-3-naphthalene carboxylate, naphthalene-1-carbon acid, phthalic anhydride or benzoic acid.

In this case, the most suitable dispersants (B2) are such mixtures, the 50 to 97 wt .-%, in particular 70 to 95% by weight, arylsulfonic acid-formaldehyde condensation products and 3 up to 50 wt .-%, in particular 5 to 30 wt .-%, aromatic or long chain aliphatic carboxylic acids, their salts or their Contain anhydrides or mixtures thereof.

One can advantageously in the production of arylsulfonic acid Formaldehyde condensation products (B2) also from pure naphthalene (Purity usually <95%).

The condensation is generally 0.5 to 1.5 mol, preferably 0.7 to 1 mol, formaldehyde per mol of naphthalene puts.

The sulfonic acid group content of these condensation products is expediently at about 40 to 50% by weight.

The dispersants (B2) are known and z. See, for example, US-A-5,186 846, DE-A-11 37 005 or EP-A-380 778.

The dispersants (B3) are condensation products of min least difunctional isocyanates, which act as a linking point serve with a polymeric compound attached to one chain end is terminated with an isocyanate-reactive group and which too dispersing solid particles with the dispersion medium inert (hereinafter called "stabilizer block"), and a (homo- or co-) polymer of a nitrogen-containing monomer or a phosphonic acid ester, each via an isocycana treactive group and adhere to the dispersed Attach solid particles (in the following "anchor group block" ge called).

This is the linking of the stabilizer block and anchor group block effecting isocyanate is a diisocyanate or a high function bright polyisocyanate with an average NCO functionality of 2.0 to 4.5.  

The diisocyanates can be aromatic or aliphatic before aliphatic diisocyanates such as tetramethylene diisocyanate Hexamethylene diisocyanate, octamethylene diisocyanate, decamethylene di isocyanate, dodecamethylene diisocyanate, tetradecamethylene diiso cyanate, trimethylhexane diisocyanate, tetramethylhexane diisocyanate, 1,4-, 1,3- or 1,2-diisocyanatocyclohexane, 4,4'-di (isocyanato cyclohexyl) methane, 1-isocyanato-3,3,5-trimethyl-5- (isocyanato methyl) cyclohexane (isophorone diisocyanate) and 2,4- and 2,6-diiso cyanato-1-methylcyclohexane, where hexamethylene diisocyanate and Isophorone diisocyanate are particularly preferred.

The higher functional polyisocyanates can also be aromatic or aliphatic. Here too, the aliphatic polyisocyanates are preferred, especially those with an average NCO functionality of 1.7 to 5, in particular about 3. The following groups are examples:

• a) Isocyanurate group-containing polyisocyanates from aliphati and / or cycloaliphatic diisocyanates. Especially the corresponding isocyanato isocya are preferred nurates based on hexamethylene diisocyanate and isophorondi isocyanate. These isocyanurates are ins especially simple tris-isocyanatoalkyl or triisocyanas tocycloalkyl isocyanurates, which cyclic trimers of Represent diisocyanates, or mixtures with their higher, homologues with more than one isocyanurate ring. The Isocyanato isocyanurates generally have an NCO content from 10 to 30% by weight, in particular 15 to 25% by weight, and a average NCO functionality from 2.6 to 4.5.
• b) uretdione diisocyanates with aliphatic and / or cycloali phatic bound isocyanate groups, which are preferred of hexamethylene diisocyanate or isophorone diisocyanate deduce. Uretdione diisocyanates are cycli cal dimerization products of diisocyanates.
• c) Biuret group-containing polyisocyanates with aliphatic ge bound isocyanate groups, especially tris (6-isocyanato hexyl) biuret or its mixtures with its higher homolo gen. These biuret polyisocyanates have in generally an NCO content of 18 to 25 wt .-% and average NCO functionality from 3 to 4.5.
• d) polyiso containing urethane and / or allophanate groups cyanates with aliphatic or cycloaliphatic iso cyanate groups, such as, for example, by reacting excess amounts of hexamethylene diisocyanate or iso  phorone diisocyanate with simple polyhydric alcohols, such as Trimethylolpropane, glycerin, 1,2-dihydroxypropane or their Mixtures can be obtained. This urethane and / or Polyisocyanates containing allophanate groups generally have mean an NCO content of 12 to 20 wt .-% and an average More NCO functionality from 2.5 to 3.
• e) Polyisocyanates containing oxadiazinetrione groups, preferably example of hexamethylene diisocyanate or isophorone diisocyanate derived. Such poly containing oxadiazinetrione groups Isocyanates can be produced from diisocyanate and carbon dioxide.
• f) Uretonimine-modified polyisocyanates.

The polymeric compound forming the stabilizer block is preferably a polymeric compound of the general formula V

R ¹ -M _n -XH (V)

wherein
R ¹ for hydrogen, optionally branched C ₁ -C ₂₈ alkyl, optionally branched, optionally polyunsaturated C ₂ -C ₂₈ alkenyl, optionally branched, optionally polyunsaturated C ₂ -C ₂₈ alkynyl or the rest of a polymerization initiator or a chain regulator,
M represents identical or different polymerized units of monomers selected from a, b-ethylenically unsaturated mono- or dicarboxylic acids, optionally substituted with hydroxy, C ₁ -C ₆ alkoxy, polyalkyleneoxy or halogen-mono- or polysubstituted C ₁ -C ₂₀ - ( Cyclo) alkyl or C ₇ -C ₂₀ aralkyl esters, amides, nitriles or anhydrides of a, b-ethylenically unsaturated mono- or dicarboxylic acids, vinyl or allyl star aliphatic or aromatic carboxylic acids, vinyl or allyl ethers, ethylenically unsaturated sulfonic acids or sulfonic acid derivatives , optionally halogenated ethylenically unsaturated aliphatic C ₂ -C ₂₀ hydrocarbons, aromatic ethylenically unsaturated compounds or compounds polymerizable to polyphosphacenes, or for

or -CO-OR ⁷ -O-CO-R ⁸ -
in which R ² , R ³ , R ⁴ and R ⁵ independently of one another are H, C ₁ -C ₆ alkyl, C ₆ -C ₂₀ aryl, -CH ₂ -C ₁ or -CH ₂ -OH, and R ⁶ , R ⁷ and R ⁸ independently of one another represent a C ₂ -C ₂₀ alkylene, arylene or aralkylene group,
n stands for an integer between 0 and 10,000, where n is preferably ≧ 2, in particular ≧ 3 and particularly preferably 30 to 1000, and
X represents COO, O, S or NR ⁹ , wherein R ^{9 represents} H or a C ₁ -C ₆ alkyl group.

VC ₁ -C ₈ -alkyl (meth) acrylates are preferably used to construct the polymeric compound. One or more C ₁ -C ₄ -alkyl methacrylates, in particular methyl methacrylate and / or butyl methacrylate, are particularly preferably polymerized. The isocyanate-reactive group XH is preferably a hydroxyl group which can be introduced terminally into the polyacrylate with the aid of initiators which give a hydroxyl radical on decomposition and / or with the aid of chain regulators which contain a hydroxyl group.

Very particularly preferred as the polymeric compound V are mono- (usually C ₁ -C ₁₈ -, preferably C ₁ -C ₄ -) alkyl ethers of poly (in particular C ₂ -C ₄ -) alkylene glycols which, for. B. can be obtained by reacting an alkanol with alkene oxides, such as ethylene oxide, propylene oxide and butylene oxide, or epichlorohydrin. Particularly suitable are 5 to 10,000, preferably 5 to 80 mol of ethylene oxide and / or propylene oxide alkoxylated C ₁ -C ₁₈ - (in particular C ₁ -C ₄ -) alkanols, polyethylene glycol monomethyl ether being very particularly suitable.

The weight average molecular weight of the stabilizer block be preferably carries about 250 to 100,000, especially about 500 to 7000.  

An embodiment suitable for building up the dispersant (B3) The shape of the anchor group block is based on homo- or copolymers seed of one or more monomers from the group of the N-Vinyla mide, N-vinyl lactams and vinyl or allyl substituted stick containing heterocycles. Examples of particularly suitable ones Monomers are N-vinyl pyrrolidone, N-vinyl pyridine, N-vinyl caprolac tam, N-vinylimidazole and N-vinylformamide, where N-vinylpyrrolidone is preferred. The homo- or copolymer preferably has one K value from 10 to 100, in particular 10 to 30. The Terminie tion by a hydroxyl group as an isocyanate-reactive group by performing the polymerization in water or a low ren alcohol such as isopropanol or by polymerization in counter were a corresponding chain regulator and / or initiator be enough.

Another embodiment of the anchor group block suitable for building up the dispersant (B3) are phosphonic acid esters of the formula VI

in the
R ¹⁰ and R ¹¹ independently of one another are C ₁ -C ₄ alkyl, in particular R ¹⁰ = R ^{11 are} methyl or ethyl;
Q represents NR _(2-p) or CR _(3-p) (R = H or C ₁ -C ₈ alkyl);
R ¹² and R ¹³ independently of one another represent a chemical bond or C ₁ -C ₁₀ alkylene which is optionally substituted by C ₁ -C ₈ alkyl or aryl, which is optionally by O, NR, CO, COO, OCO, CONR or NRCO can be interrupted;
p represents 1 or 2; and
Y is COO, O, S or NR ¹⁴ , where R ^{14 is} H or a C ₁ -C ₆ alkyl group.

Preferred examples of these phosphonic acid esters are N, N- Bis (hydroxyethyl) aminomethylphosphonic acid diethyl ester, dimethyl and diethyl ester of 3-hydroxymethylamino-3-oxopropylphosphon acid, 3-aminopropylphosphonic acid, 1-aminopropylphosphonic acid, 2-aminooctylphosphonic acid, 1-aminooctylphosphonic acid, 1-aminobu  tylphosphonic acid, hydroxymethylphosphonic acid and 1-hydroxyethyl phosphonic acid.

The implementation of the di- or polyisocyanate with the stabilizer block and the anchor group block can be two-stage or in one One-pot reaction take place. The conversion is preferably carried out in each case but in two stages, with the di- or poly Isocyanate is implemented with the stabilizer block. The implementation can be carried out in bulk or in a solvent, the Reaction in a solvent such as acetone, THF, toluene, Dioxane is preferred. If the stabilizer block is replaced by Polymeri tion of an ethylenically unsaturated compound the stabilizer block can be implemented with the Di- or polyisocyanate advantageously in the same solvent as that radical polymerization can be carried out. The reaction can without catalyst or preferably in the presence of a catalyze catalysts, such as a tertiary amine, especially triethylamine, or a metal salt, in particular tin octoate or lead octoate, or an organometallic compound such as dibutyltin dilaurate or titanium tetramethylate. The implementation will generally at a temperature from room temperature to 125 ° C, in particular 40 to 90 ° C, carried out.

Further details on the dispersants (B3) are in the DE-A-198 42 952.

The dispersants (84) are alkoxylated Hydroxynaphthalenes, with ethoxylated β-hydroxynaphthalenes before are moving. The dispersants (B4) usually have average molecular weight Mw from 2000 to 40,000 g / mol, ins particularly 20,000 to 35,000 g / mol, especially 25,000 to 30,000 g / mol on.

The dispersants (84) are generally known and are customary Way accessible by alkoxylation of hydroxynaphthalene.

The colorant preparations according to the invention have in the case of an undissolved colorant (A1) usually has a content of 0.1 to 25% by weight, preferably from 0.5 to 10% by weight Dispersant (B).

The colorants according to the invention contain as component (C) preparations organic solvent. Low molecular weight poly tetrahydrofuran (C1) is an essential component of the component (C), it can be used alone or preferably in a mixture with one or several difficult to evaporate, soluble in water or with water miscible organic solvents (C2) are used.  

The polytetrahydrofuran (C1) used according to the invention usually has an average molecular weight M _w of 150 to 500 g / mol, preferably from 200 to 300 g / mol and particularly preferably of about 250 g / mol (corresponding to a molecular weight distribution of 225 to 275 g / mol; poly-THF 250, BASF).

The polytetrahydrofuran (C1) can in a known manner via cat ionic polymerization of tetrahydrofuran. This creates linear polytetramethylene glycols.

If the polytetrahydrofuran (C1) mixed with other organi The solvents (C2) are present, for this purpose according to vaporisable (i.e. usually a boiling point < 100 ° C) and thus a water-retaining effect sedentary organic solvents used, which dissolve in water Lich or miscible with water.

Polyvalent alcohols are suitable as solvents (C2) before moves unbranched and branched polyhydric alcohols with 2 to 8, in particular 3 to 6, carbon atoms, such as ethylene glycol, 1,2- and 1,3-propylene glycol, glycerin, erythritol, pentaerythritol, Pentites such as arabite, adonite and xylitol and hexites such as sorbitol, Man nit and dulcite.

Other suitable solvents (C2) are polyethylene and poly propylene glycols, including the lower polymers (di-, tri- and tetramers), and their mono- (especially C ₁ -C ₆ -, especially C ₁ - C ₄ -) alkyl ether. Polyethylene and polypropylene glycols with average molecular weights of 100 to 1500 g / mol, in particular from 200 to 800 g / mol, especially from 300 to 500 g / mol, are preferred. Examples include di-, tri- and tetraethylene glycol, diethylene glycol monomethyl, ethyl, propyl and butyl ether, triethylene glycol monomethyl, ethyl, propyl and butyl ether, di-, tri- and tetra-1,2 - and -1,3-propylene glycol and di-, tri- and tetra-1,2- and -1,3-propylene glycol monomethyl, ethyl, propyl and butyl ether.

Also suitable as solvents (C2) are pyrrolidone and N- Alkylpyrrolidones, the alkyl chain of which is preferably 1 to 4, above al contains 1 to 2 carbon atoms. Examples of suitable ones Alkylpyrrolidones are N-methylpyrrolidone, N-ethylpyrrolidone and N- (2-hydroxyethyl) pyrrolidone.

Examples of particularly preferred solvents (C2) are 1,2- and 1,3-propylene glycol, glycerol, sorbitol, diethylene glycol, polyethylene glycol (M _w 300 to 500 g / mol), diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, pyrrolidone, N-methylpyrrolidone and N- (2-hydroxyethyl) pyrrolidone.

The polytetrahydrofuran (C1) can be mixed with one or more (e.g. two, three or four) solvents (C2) are mixed.

The colorant preparations according to the invention contain in the Rule 0.1 to 40% by weight, preferably 5 to 30% by weight, particularly preferably 10 to 25% by weight, and very particularly preferably 10 to 20 wt .-%, solvent component (C).

The weight ratio of (C2) to (C1) is preferably in the range range from 20: 1 to 1: 1. The colorants of the invention added Accordingly, preparations preferably contain 0.5 to 20 % By weight, in particular 1 to 10% by weight, of polytetrahydrofuran (C1) and 1 to 30% by weight, in particular 1 to 20% by weight, of solvent (C2).

An example of a particularly preferred solvent component (C) is the combination of 1 to 10% by weight of polytetrahydrofuran (M _w 150 to 500 g / mol), 1 to 10% by weight of glycerol, sorbitol and / or propylene glycol, 1 to 10 wt .-% polyethylene glycol (M _w 300 to 500 g / mol) and 1 to 10 wt .-% di- and / or triethylene glycol monobutyl ether (amounts based on the weight of the colorant preparation).

The solvent component (C), in particular also the one mentioned particularly preferred solvent combination, can be advantageous by urea (usually 0.5 to 3 wt .-%, based on the Weight of the colorant preparation), which is what sretaining effect of the solvent mixture (C) still ver strengthens.

Water is the main component (D) of the invention Colorant preparations. Its content is usually 50 up to 95% by weight. For binder-free preparations there is a Water content of 60 to 80 wt .-% preferred, in binder In the case of preparations, the water content is preferably 50 to 75 % By weight.

The colorants according to the invention can of course also be added preparations other aids, such as those for (Water-based) ink-jet inks and in the printing and coating industry are included. May be mentioned for. B. Preservatives (such as 1,2-benzisothiazolin-3-one and its alkali metal salts, Glutardialdehyde and / or tetramethylolacetylene diurea), anti oxidants, degassers / defoamers (such as acetylenediols and ethoxy  gated acetylenediols, usually 20 to 40 moles of ethylene oxide contain per mole of acetylenediol and at the same time also disperse act), means for regulating the viscosity, flow auxiliaries, wetting agents (e.g. wetting surfactants on the Basis of ethoxylated or propoxylated fat or oxo alcohols, propylene oxide / ethylene oxide block copolymers, ethoxylates of oleic acid or alkylphenols, alkylphenol ether sulfates, alkyl polyglycosides, alkylphosphonates, alkylphenylphosphonates, Al kylphosphaten, Alkylphenylphosphaten or preferably Polyethersi loxane copolymers, especially alkoxylated 2- (3-hydroxy propyl) heptamethyltrisiloxanes, which is usually a block 7 to 20, preferably 7 to 12, ethylene oxide units and one Block of 2 to 20, preferably 2 to 10 propylene oxide units have and in amounts of 0.05 to 1 wt .-% in the colorant preparations may be included), anti-settling agents, gloss additive better, lubricant, adhesion improver, skin preventing agent, Matting agents, emulsifiers, stabilizers, water repellents medium, light protection additives, grip improvers, antistatic agents and bases such as triethanolamine to regulate the pH. If these agents are part of the pigment according to the invention preparations, their total amount is usually ≦ 2 % By weight, in particular ≦ 1% by weight, based on the weight of the inks preparation of agent.

Binder-free colorant preparations according to the invention usually have a dynamic viscosity of 1 to 7 mm ² / sec, preferably 1 to 5 mm ² / sec, in particular 1 to 3 mm ² / sec. Binder-containing colorant preparations according to the invention generally have a dynamic viscosity of 1 to 25 mm ² / sec, preferably 1 to 15 mm ² / sec, especially 1 to 10 mm ² / sec.

The surface tension of the (binder-free or binder-containing) colorant preparations in the Rule 24 to 70 mN / m, especially 30 to 60 mN / m.

The pH of the colorant preparations according to the invention is generally 5 to 10, preferably 7 to 9.

The preparation of the colorant preparations based on undissolved colorant (A1) is advantageously carried out as follows:
The colorant (A1), for example in the form of a presscake containing water, is mixed together with the dispersant (B) in the presence of water and dispersed in a suitable apparatus. The resulting mixture is then ground in a mill in order to achieve the desired particle size distribution (generally ≦ 1 μm, preferably 0.5 μm). After the desired colorant concentration has been set by adding solvent (C), water and, if appropriate, other auxiliaries, filtration is carried out using a filter device with fine separation in the range from 1 to 0.5 μm.

As a starting material for preparations with dissolved dye (A2) are more concentrated dye solutions, e.g. B. 10 to 30 % by weight liquid formulations of paper dyes, especially suitable. If necessary, these are desalted and filtered (e.g. nanofiltration) before the desired dye concentration tration is set.

The colorant preparations according to the invention can be advantageous in the method according to the invention for printing on flat or three-dimensional substrates in ink-jet Method is used, which is characterized in that one prints the colorant preparations on the substrate and then, if desired, fixed the pressure obtained.

In the ink jet process, the usually aqueous inks sprayed directly onto the substrate in small droplets. One under separates a continuous process in which the ink evenly pressed through a nozzle and through an electric Field, depending on the pattern to be printed, directed onto the substrate and an interrupted inkjet or "drop-on de mand "process in which ink is ejected only where a colored dot is to be set. With the latter The process is either over a piezoelectric crystal or a heated cannula (bubble or thermo-jet process) Pressure is applied to the ink system and so an ink drop thrown out. Such procedures are in text. Chem. Co lor, volume 19 (8), pages 23 to 29, 1987, and volume 21 (6), pages 27-32, 1989.

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

If you want to fix the pressure, you can use known ones Procedure and as described in WO-A-99/01516 and z. B. a binder, if desired in the form of a dispersion or Emulsion, apply to the printed substrate and harden or laminate a film.  

However, the colorant preparations according to the invention can also already the thermally or radiation chemically curable binder tel, usually in an amount of 2 to 20 wt .-% (calc. 100% Solid).

As thermally curable binders such. B. especially Crosslinking binders based on me acrylates containing thylol groups.

Mixtures of
1 to 10% by weight of N-methylol (meth) acrylamide or their C ₁ -C ₄ -alkyl ethers and, if desired, monomers containing halohydrin groups, such as 2-hydroxy-3-chloropropylene acrylate and
90 to 99 wt .-% comonomers, e.g. B. from the group of butadiene, styrene, (meth) acrylic acid, (meth) acrylonitrile, (meth) acrylic acid and vinyl esters with up to 12 carbon atoms, vinyl chloride and N-vinyl pyrrolidone
called, as described for example in DE-A-16 19 656.

Under the action of acids or under the influence of heat protons splitting compounds such as ammonium phosphates cause me acrylic acid derivatives containing thylol groups additional crosslinking.

As further examples of suitable thermally curable binders tel are based on polyurethane prepolymers binders named, which also crosslink through polycondensation.

The radiation-curable binders are According to the invention to binders that are caused by radiation higher Energy, d. H. electromagnetic radiation especially from 220 up to 450 nm (UV radiation) or electron beams are. Both radical and cationic poly are suitable merizable binder components as well as their mixtures.

Examples include those containing acrylate groups and those containing vinyl groups and / or monomers, prepolymers and polymers containing epoxy groups and their mixtures called.

More details on these binders are given in the WO-A-99/01516.  

The colorant preparations according to the invention can be applied to all types substrate materials. As a substrate materials are e.g. B.

• - Cellulose-containing materials such as paper, cardboard, cardboard, wood and wood-based materials, which can also be painted or otherwise can be stratified
• - metallic materials such as foils, sheets or workpieces made of aluminum, iron, copper, silver, gold, zinc or alloy of these metals, which are painted or otherwise can be stratified
• - silicate materials such as glass, porcelain and ceramics can also be coated,
• - polymeric materials of any kind such as polystyrene, polyamides, Polyester, polyethylene, polypropylene, melamine resins, poly acrylates, polyacrylonitrile, polyurethanes, polycarbonates, poly vinyl chloride, polyvinyl alcohols, polyvinyl acetates, polyvinyl pyrrolidones and corresponding copolymers and block copolymers, biodegradable polymers and natural polymers such as Ge latin,
• - textile materials such as fibers, yarns, threads, knitwear, Woven goods, non-wovens and made-up goods made of polyester, modified polyester, polyester blend, cellulose materials like cotton, blended cotton, jute, Flax, hemp and ramie, viscose, wool, silk, polyamide, buttocks lyamide blend, polyacrylonitrile, triacetate, acetate, poly carbonate, polypropylene, polyvinyl chloride, polyester microfa ser and fiberglass fabrics,
• - Leather, both natural leather and synthetic leather, as smooth, Nappa or suede,
• - Food and cosmetics

called.

The substrate material can be flat or three-dimensional be designed and with the Colorant preparations according to the invention are printed.

The colorant preparations according to the invention are notable for Ink-jet inks with overall advantageous application properties above all, good writing behavior and good long-term writing  behavior (kogation) and, especially when using the be particularly preferred solvent combination (C), good drying behavior, and result in high quality print images, d. H. high brilliance and color depth as well as high friction, light, water and wet rub fastness. They are particularly suitable for printing on coated and uncoated paper.

Examples I) Preparation of colorant preparations according to the invention example 1

15 g C.I. Pigment Yellow 138, 5 g 1,2-propylene glycol and 10 g of a dispersant (B1) based on an oxyalkylated Phe nols, which was described as dispersant 13 in US-A-4,218,218 ben is 0.37 g of 50% by weight aqueous solution of glutardialdehyde and 0.75 g of 47% by weight aqueous solution of tetramethylolacetylene diurea was added to the total weight with deionized water filled up of 100 g and predispersed in a dissolver. Then the pH was adjusted to 8.5 with triethanolamine.

The mixture was then kept in a vertical position for so long Agitator ball mill with double grinding disc at 10 m / s circumference speed using 660 g of yttrium stabilized Zirconium oxide beads (diameter 0.3-0.4 mm) ground, up to 99% the pigment particles had a size of less than 1 μm.

For the final setting (4% by weight preparation), 37.5 g of meal well with 0.25 g of 50% by weight aqueous solution of glutardialdehyde, 0.22 g 47% by weight aqueous solution of tetramethylolacetylenedi urea, 10 g triethylene glycol monobutyl ether and 10 g poly tetrahydrofuran 250 (BASF) mixed with water to a level filled up to a total weight of 100 g, mixed and passed through a sieve filtered to a pore size of 1 µm.

Examples 2 to 69

The pigment preparations of Examples 2 to 69 were analogous Example 1 prepared. In Examples 20 and 21 and 22 and 23 However, a dispersant (B3) or (B3 ') based on a Reaction product of a triisocyanate with two iso each Compounds containing cyanate-reactive group used (Bei game 1 or example 4 of DE-A-198 42 952).  

Dispersant (B3)

To a 35% by weight solution of polyethylene heated to 50 ° C. glycol monomethyl ether (MW 2000, 1 mol) in acetone was a han standard trifunctional isocyanate (Basonat® HB 100, BASF; 1 mol) and dibutyltin dilaurate as a catalyst. Ent was then the remaining isocyanate content OH-monofunctionalized polyvinylpyrrolidone (PVP, K value approximately 17) added. The reaction continued until no iso cyanate groups were more detectable.

Dispersant (B3 ')

To a 45% by weight solution of polyethylene heated to 50 ° C. glycol monomethyl ether (MW 2000, 1 mol) in tetrahydrofuran a commercially available trifunctional isocyanate (Basonat HB 100, BASF; 1 mol) and dibutyltin dilaurate as a catalyst. The remaining isocyanate content was then determined N, N-bis (hydroxyethyl) aminomethyldiethyl (phosphonate (Fyrol® 6, Akzo; about 2 moles; 50 wt .-% in tetrahydrofuran). The The reaction was continued until no more isocyanate groups to assign.

In Examples 41 to 57 and 64 to 69, a dispersant (B4) based on an ethoxylated β-hydroxynaphthalene (M _w 27000 g / mol) was used.

In addition, a commercially available ther mix-curable textile binder based on an acrylate / styrene copo lymerisats used.

Further information on the pigment preparations obtained can be found in Table 1 compiled. The percentages are each by% by weight.

Here mean:
Biocide A: 50% aqueous solution of glutaraldehyde
Biocide B: 4% aqueous solution of tetramethylolacetylenediurea
Biocide C: 20% solution of 1,2-benzisothiazolon-3-one in aqueous ethylene glycol
Biocide D: 10% solution of 1,2-benzisothiazolon-3-one in aqueous propylene glycol
Wetting agent: 2- (3-hydroxypropyl) heptamethyltrisiloxane, first ethoxylated and then propoxylated (11 mol EO / 5 mol PO)

Example 70

2.5 g of an 80% by weight water-moist press cake of the dye of the formula VII

were dissolved in 87.5 g of water with stirring and with a filter MX 07 from Osmonics ultrafiltered. After adding 8 g 1,2-propylene glycol and 2 g of polytetrahydrofuran 250 was the Mix with a filter KS 80 from Seitz filtered to To separate suspended matter.

Examples 71 to 86

The dye preparations of Examples 71 to 86 were analogous Example 70 prepared.

Further details on the dye preparations obtained are summarized in Table 2. The percentages are in each case% by weight.

II) Testing of colorant preparations according to the invention

All colorant preparations showed when printing with trade usual ink jet printers on both coated and on uncoated paper excellent cover and through writing behavior and gave prints of high brilliance.

The physi. Examined in the case of Examples 24 to 57 as follows Potash and printing properties are shown in Table 3 compiled:

1) Surface tension

The surface tension was measured with the digital tensiometer K 10 determined by Krüss. The values given in Table 3 are the mean values from 3 measurements.

2) viscosity

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

3) pH

The pH was measured using a Knick 763 pH meter Right.

The printing properties were measured on an ink jet Mimaki JV2 / 130 printer examined.

4) Writing behavior

The rating behavior was assessed according to the following rating system:
Note 1: Printer writes with all nozzles after 72 hours.
Note 2: Printer writes with all nozzles after 72 hours after cleaning.
Note 3: Printer writes with all nozzles after 72 h after multiple cleaning.
Grade 4: After 72 hours one or more nozzles are irreversibly clogged.

5) Continuous writing behavior

The permanent writing behavior was assessed according to the following rating system:
Note 1: 100 pages A4 format are included without cleaning
printed on all nozzles.
Note 2: 100 pages of A4 format are printed without cleaning with a maximum of 4 missing (clogged) nozzles.
Note 3: 100 pages DIN A4 format are printed with all nozzles with intermediate cleaning.
Note 4: Less than 100 A4 pages are printed with all nozzles with intermediate cleaning.

6) Drying behavior

The drying behavior was assessed visually while printing on a commercially available premium ink jet paper (basis weight 140 g / m ² ; Cham Tenero) according to the following rating system:
Note 1: The print is dry while printing 10 lines without a drying unit.
Note 2: The print is dry when winding up without a drying device.
Note 3: The print is dry when winding with a drying device.
Note 4: The print is not dry when winding despite the drying device.

Table 3

Claims (12)

1. Colorant preparations containing

• A) at least one dispersed (A1) or dissolved (A2) colorant,
• B) in the case of a colorant (A1), a dispersant,
• C) a low molecular weight polytetrahydrofuran (C1), if desired in a mixture with one or more difficult to evaporate, water-soluble or water-miscible organic solvents (C2) and
• D) water

as essential components. 2. Colorant preparations according to claim 1, which, based in each case on the weight of the preparation,
0.01 to 20% by weight of component (A),
in the event that the colorant is essentially undissolved, 0.01 to 20% by weight of component (B),
0.1 to 40 wt .-% of component (C) and
at least 50% by weight of component (D)
contain. 3. Colorant preparations according to claim 1 or 2, which contain as component (C1) one or more polytetrahydrofurans with an average molecular weight M _w of 150 to 500 g / mol. 4. Colorant preparations according to claims 1 to 3, the 1st to 10 wt .-% of component (C1) and 1 to 30 wt .-% of Component (C2) included.   5. Colorant preparations according to claims 1 to 4, which as Component (C2) one or more solvents from the group polyhydric alcohols, polyethylene and polypropylene glycols as well as their monoalkyl ethers and pyrrolidone and N-alkylpyrroli done included. 6. Colorant preparations according to claims 1 to 5, the component (C2), each based on the weight of the preparation, 1 to 10 wt .-% glycerol, sorbitol and / or propylene glycol, 1 to 10 wt .-% polyethylene glycol with an average molecular weight M _w of 300 to 500 g / mol and 1 to 10 wt .-% di- and / or triethylene glycol mono-C ₁ -C ₄ alkyl ether. 7. colorant preparations according to claims 1 to 6, which as Component (A) is a finely divided, organic or inorganic contain pigment. 8. Colorant preparations according to claims 1 to 7, which as Component (B) a dispersant based on aryl sulfonic acid-formaldehyde condensation products (B1), from oxalkylated phenols (B2), one of condensation products at least difunctional isocyanate, each with one iso cyanate-reactive compounds (B3) or of alkoxylated hydroxynaphthalenes (B4) contain. 9. Colorant preparations according to claims 1 to 8, which additionally contain urea and a polyether siloxane copolymer ten. 10. Colorant preparations according to claims 1 to 9, which additionally a thermally or radiation chemically curable bin contains agent. 11. Use of colorant preparations according to claims 1 to 10 as inks for the ink jet process. 12. Process for printing flat or three-dimensional designed substrates in the ink jet process, characterized records that colorant preparations according to claims Chen 1 to 10 printed on the substrate and the obtained If desired, the print is then fixed.