USOO6332943B1 (12) United States Patent (10) Patent No.: US 6,332,943 B1 Herrmann et al. (45) Date of Patent: Dec. 25, 2001 (54) METHOD OF INK-JET PRINTING WITH (56) References Cited PGMENT PREPARATIONS HAVING A DSPERSANT U.S. PATENT DOCUMENTS 2.979,528 4/1961 Lundated. (75) Inventors: Manfred Herrmann, Ludwigshafen; 4,204,010 5/1980 Kramm et al. ....................... 427/508 Ginther König, Maxdorf; Ridiger 4,218.218 8/1980 Daubach et al. Sens, Ludwigshafen; Bernd Siegel, 4,287,039 9/1981 Buethe et al. Otterstadt; Karl Siemensmeyer, 5,186.846 2/1993 Brueckmann et al. Frankenthal, all of (DE) 5,538,549 7/1996 Kato et al. (73) Assignee: BASF Aktiengesellschaft, Ludwigshafen (DE) FOREIGN PATENT DOCUMENTS 2185245 10/1995 (CA). (*) Notice: Subject to any disclaimer, the term of this 36 41677 6/1988 (DE). patent is extended or adjusted under 35 44 13 242 10/1995 (DE). 0 012339 6/1980 (EP). U.S.C. 154(b) by 0 days. O 279 303 8/1988 (EP). (21) Appl. No.: 09/446,894 O 412 548 2/1991 (EP). O 518 621 12/1992 (EP). (22) PCT Filed: Jun. 18, 1998 O 542 052 5/1993 (EP). O 658 607 6/1995 (EP). (86) PCT No.: PCT/EP98/03708 0 704 469 4/1996 (EP). 0 753 552 1/1997 (EP). S371 Date: Mar. 31, 2000 1551829 9/1979 (GB). S 102(e) Date: Mar. 31, 2000 8-48922 2/1996 (JP). (87) PCT Pub. No.: WO99/01516 * cited by examiner PCT Pub. Date:Jan. 14, 1999 (30) Foreign Application Priority Data Primary Examiner Michael A. Tolin (74) Attorney, Agent, or Firm-Oblon, Spivak, McClelland, Jun. 30, 1997 (DE) .............................................. 197 27 766 Maier & Neustadt, P.C. Dec. 5, 1997 (DE) .............................................. 19753,831 (57) ABSTRACT (51) Int. Cl." ......................... B32B 31/12; CO9D 11/100; B41J 2/O1 Pigment preparation for the ink-jet process which comprises (52) U.S. Cl. .......................... 156/277; 427/496; 427/508; A) at least one finely divided, organic or inorganic pigment, 427/521; 427/3722; 427/256; 347/100; B) a dispersant based on arylsulfonic acid/formaldehyde 106/31.86; 106/31.87; 106/31.9; 106/503 condensation products or an alkoxylated phenols, and C) (58) Field of Search .............................. 156/275.5, 275.7, water, as essential constituents. It provides for prints of high 156/277; 427/508, 521, 496, 372.2, 407.1, light fastness, wash fastness and rub fastness. 256; 106/499, 503, 31.86, 31.87, 31.9; 516/77, 909, 920; 8/583, 589; 347/100 5 Claims, No Drawings US 6,332,943 B1 1 2 METHOD OF INK-JET PRINTING WITH Examples of Suitable pigments (A) are: PGMENT PREPARATIONS HAVING A organic pigments: DSPERSANT FIELD OF THE INVENTION monoazo pigments: C.I. Pigment Brown 25; C.I. Pigment Orange 5, 13, 36 and 67; The present invention relates to the novel pigment prepa C.I Pigment Red 1, 2, 3, 5, 8, 9, 12, 17, rations for the ink-jet process, comprising 22, 23, 31, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 52:1, 52:2, 53, A) at least one finely divided, organic or inorganic 53:1, 53:3, 57:1, 63, 251, 112, 146, 170, 184, 210 and 245; pigment, C.I. Pigment Yellow 1, 3, 73, 74, 65, B) a dispersant based on arylsulfonic acid/formaldehyde 97, 151 and 183; condensation products or on alkoxylated phenols, and disazopigments: C.I. Pigment Orange 16, 34 and 44; C.I. Pigment Red 144, 166, 214 and 242; C) water, C.I. Pigment Yellow 12, 13, 14, 16, as essential constituents. 15 17, 81, 83, 106, 113, 126, 127, 155, 174, 176 and 188: anthanthrone pigments: C.I. Pigment Red 168 BACKGROUND OF THE INVENTION (C.I. Vat Orange 3); anthraquinone pigments: C.I. Pigment Yellow 147 and 177; C.I. Pigment Violet 31; This invention further relates to a process for printing anthrapyrimidine pigments: C.I. Pigment Yellow 108 sheetlike or three-dimensionally configured Substrates by (C.I. Vat Yellow 20); the ink-jet process using these pigment preparations. quinacridone pigments: C.I. Pigment Red 122, 202 and 206 C.I. Pigment Violet 19: InkS for use in the ink-jet proceSS have to meet a whole quinophthalone pigments: C.I. Pigment Yellow 138; Series of requirements: They have to have a Viscosity and dioxazine pigments: C.I. Pigment Violet 23 and 37; Surface tension Suitable for printing, they have to be stable flavanthrone pigments: C.I. Pigment Yellow 24 25 (C.I. Vat Yellow 1); in Storage, ie. they should not coagulate and the dispersed, indanthrone pigments: C.I. Pigment Blue 60 undissolved colorant should not settle out, they must not (C.I. Vat Blue 4) lead to blockage of the printer nozzle, which can likewise be and 64 (C.I. Vat Blue 6): problematical especially in the case of pigmented inks, ie. isolindoline pigments: C.I. Pigment Orange 69; C.I. Pigment Red 260: inkS comprising dispersed colorant particles, and finally they C.I. Pigment Yellow 139 and 185: should be environmentally compatible, ie. be substantially isolindolinone pigments: C.I. Pigment Orange 61; based on water as liquid phase and include organic Solvents C.I. Pigment Red 257 and 260: only in Small amounts, if at all. In addition, the prints C.I. Pigment Yellow 109, 110, 173 and 185: obtained have to meet coloristic requirements, ie. Show isoviolanthrone pigments: C.I. Pigment Violet 31 brilliance and depth, and have good fastneSS properties, eg. 35 (C.I. Vat Violet 1); rub fastness, lightfastneSS and water fastneSS or washfast metal complex pigments: C.I. Pigment Yellow 117, 150 and neSS in the case of textile printing. 153; C.I. Pigment Green 8: Existing ink-jet inks include not only pigment, dispersant perinone pigments: C.I. Pigment Orange 43 (C.I. Vat Orange 7); and optionally further assistants but also, at the same time, C.I. Pigment Red 194 a binder component, for example a UV-curable binder 40 (C.I. Vat Red 15); (EP-A-658 607, JP-A-48922/1996) or a thermally curable perylene pigments: C.I. Pigment Black 31 and 32: C.I. Pigment Red 123, 149, 178, 179 binder (EP-A-753 552, EP-A-412548). (C.I. Vat Red 23), In these inks, the individual constituents have to be in 190 (C.I. Vat Red 29) and 224; C.I. Pigment Violet 29; perfect harmony to obtain Storage-Stable, noncoagulating 45 phthalocyanine pigments: C.I. Pigment Blue 15, 15:1, 15:2, inks having good flow behavior and good fastness 15:3, 15:4, 15:6 and 16; properties, which can lead to difficulties. C.I. Pigment Green 7 and 36; pyranthrone pigments: C.I. Pigment Orange 51; C.I. Pigment Red 216 BRIEF SUMMARY OF THE INVENTION (C.I. Vat Orange 4): 50 thioindigo pigments: C.I. Pigment Red 88 and 181 (C.I. Vat Red 1); It is an object of the present invention to provide novel C.I. Pigment Violet 38 pigment preparations having advantageous application prop (C.I. Vat Violet 3): erties for the ink-jet process. triarylcarbonium pigments: C.I. Pigment Blue 1, 61 and 62; C.I. Pigment Green 1: 55 C.I. Pigment Red 81, 81:1 and DETAILED DESCRIPTION OF THE 169: INVENTION AND PREFERRED C.I. Pigmen Violet 1, 2, 3 and 27: EMBODIMENTS THEREOF C.I. Pigment Black 1 (aniline black); We have found that this object is achieved by the pigment C.I. Pigment Yellow 101 (aldazine yellow); preparations defined at the beginning. 60 C.I. Pigment Brown 22; vat dyes (in addition to those already mentioned above): The pigment preparations of the invention comprise a C.I. Vat Yellow 2, 3, 4, 5, 9, 10, 12, 22, 26, 33, 37, 46, 35 finely divided, organic or inorganic pigment. The expression 48, 49 and 50; “organic pigment' includes vat dyes. The pigment prepara C.I. Vat Orange 1, 2, 5, 9, 11, 13, 15, 19, 26, 29, 30 and tions of the invention may also comprise mixtures of various 65 31; organic or various inorganic pigments or of organic and C.I. Vat Red 2, 10, 12, 13, 14, 16, 19, 21, 31, 32, 37, 41, inorganic pigments. 51, 52 and 61; US 6,332,943 B1 3 4 C.I. Vat Violet 2, 9, 13, 14, 15, 17 and 21; particles generally produce leSS Viscous preparations at the C.I. Vat Blue 1 (C.I. Pigment Blue 66), 3, 5, 10, 12, 13, Same pigment concentration and usually exhibit Newtonian 14, 16, 17, 18, 19, 20, 22, 25, 26, 29, 30, 31, 35, 41, 42, flow characteristics. 43, 64, 65, 66, 72 and 74; The pigment preparations of the invention generally com prise from 0.1 to 20% by weight, preferably from 0.2 to 10% C.I. Vat Green 1,2,3,5,7,8,9, 13, 14, 17, 26, 29, 30, 31, by weight, of pigment (A). 32, 33, 40, 42, 43, 44 and 49; Component (B) of the pigment preparations of the inven C.I. Vat Brown 1, 3, 4, 5, 6, 9, 11, 17, 25, 32, 33, 35, 38, tion is a water-Soluble dispersant based on one or more 39, 41,42, 44, 45, 49, 50, 55, 57, 68,72, 73,80, 81, 82, arylsulfonic acid/formaldehyde condensation products (B1) 83 and 84; or one or more water-soluble alkoxylated phenols (B2). C.I. Vat Black 1, 2, 7, 8, 9, 13, 14, 16, 19, 20, 22, 25, 27, Preferred dispersants (B1) are condensation products hav 28, 29, 30, 31, 32, 34, 36,56, 57, 58, 63, 64 and 65; ing a Sulfonic acid group content of not more than 40% by inorganic pigments: weight.