EP0885998A2 - Process for ink jet printing textile materials - Google Patents
Process for ink jet printing textile materials Download PDFInfo
- Publication number
- EP0885998A2 EP0885998A2 EP98810523A EP98810523A EP0885998A2 EP 0885998 A2 EP0885998 A2 EP 0885998A2 EP 98810523 A EP98810523 A EP 98810523A EP 98810523 A EP98810523 A EP 98810523A EP 0885998 A2 EP0885998 A2 EP 0885998A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- formula
- vinyl
- amino
- ink
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000007641 inkjet printing Methods 0.000 title claims abstract description 14
- 239000004753 textile Substances 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims description 48
- 239000000463 material Substances 0.000 title 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000985 reactive dye Substances 0.000 claims abstract description 29
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 19
- -1 2-(4-(3,7,8-trisulphonaphth-2-yl-azo)-3-ureido-phenylamino)-4- fluoro-1,3,5-triazin-6-yl-amino Chemical group 0.000 claims abstract description 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 7
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 3
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical group [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002657 fibrous material Substances 0.000 claims description 24
- 229920000742 Cotton Polymers 0.000 claims description 21
- 238000007639 printing Methods 0.000 claims description 19
- 229920000297 Rayon Polymers 0.000 claims description 9
- 239000012928 buffer substance Substances 0.000 claims 1
- 239000000976 ink Substances 0.000 abstract description 44
- 239000000975 dye Substances 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract 3
- 229910004727 OSO3H Inorganic materials 0.000 abstract 1
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract 1
- 125000004430 oxygen atom Chemical group O* 0.000 abstract 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 30
- 229910000029 sodium carbonate Inorganic materials 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 229910021538 borax Inorganic materials 0.000 description 13
- 229920006395 saturated elastomer Polymers 0.000 description 13
- 235000010339 sodium tetraborate Nutrition 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 12
- 239000004328 sodium tetraborate Substances 0.000 description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 10
- 239000004202 carbamide Substances 0.000 description 10
- 239000004744 fabric Substances 0.000 description 8
- 239000000654 additive Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 235000010443 alginic acid Nutrition 0.000 description 4
- 229920000615 alginic acid Polymers 0.000 description 4
- 229920003086 cellulose ether Polymers 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 0 *c(cc(*)c(S(O)(=O)=O)c1)c1N=Nc(c(*)cc1c2ccc(Nc3nc(NC*CO**4CC4)nc(F)n3)c1)c2O Chemical compound *c(cc(*)c(S(O)(=O)=O)c1)c1N=Nc(c(*)cc1c2ccc(Nc3nc(NC*CO**4CC4)nc(F)n3)c1)c2O 0.000 description 2
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 239000003752 hydrotrope Substances 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 229920003087 methylethyl cellulose Polymers 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 description 1
- 239000004324 sodium propionate Substances 0.000 description 1
- 235000010334 sodium propionate Nutrition 0.000 description 1
- 229960003212 sodium propionate Drugs 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 239000010981 turquoise Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/30—Ink jet printing
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
- D06P1/382—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes reactive group directly attached to heterocyclic group
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
- D06P1/384—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes reactive group not directly attached to heterocyclic group
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/642—Compounds containing nitrogen
- D06P1/6426—Heterocyclic compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/651—Compounds without nitrogen
- D06P1/65106—Oxygen-containing compounds
- D06P1/65118—Compounds containing hydroxyl groups
Definitions
- the present invention relates to methods for printing textile fiber materials with reactive dyes according to the inkjet printing process (jet and inkjet processes) as well as corresponding printing inks.
- Inkjet printing processes have been in the textile industry for several years applied. These methods make it possible to produce a Eliminate the printing stencil, so that considerable cost and time savings are achieved can be. Especially in the production of sample templates can within reacted to changing needs much less time.
- Corresponding inkjet printing processes should in particular be optimal have application properties. Worth mentioning in this Relationship properties such as viscosity, stability, surface tension and Conductivity of the inks used. There are also increased demands on quality of the prints obtained, e.g. regarding color strength, fiber-dye binding stability as well as wet fastness properties. Of the known methods these requirements are not met in all properties, so there is still a need for there are new processes for textile inkjet printing.
- the invention relates to a process for printing textile fiber materials by the inkjet printing process, which is characterized in that these fiber materials are printed with an aqueous ink which comprises at least one reactive dye of the formulas and wherein Z and Z 'are independently vinyl or a radical of the formula -CH 2 -CH 2 -OSO 3 H, B 1 and B 2 represent a C 2 -C 12 alkylene radical which can be interrupted by 1, 2 or 3 members -O- and is unsubstituted or substituted by hydroxy, sulfo, sulfato, cyano or carboxy and CuPhC is a copper phthalocyanine residue, and b) 1,2-propylene glycol or N-methyl-2-pyrrolidone contains.
- B 1 and B 2 are preferably a C 2 -C 12 alkylene radical which can be interrupted by 1 or 2 members -O- and is unsubstituted or substituted by hydroxy.
- B 1 and B 2 are particularly preferably C 2 -C 6 alkylene.
- B 1 is very particularly preferably 1,3-propylene and B 2 is 1,2-ethylene.
- Z is preferably vinyl.
- Z ' the meaning as radical of the formula -CH 2 -CH 2 -OSO 3 H is preferred.
- B 1 is preferably 1,3-propylene, B 2 1,2-ethylene, Z vinyl and Z 'is a radical of the formula -CH 2 -CH 2 -OSO 3 H.
- Preferred reactive dyes for the process according to the invention are those of Formulas (1a) to (1g), in particular of the formulas (1a) to (1f) and preferably those of the of the formulas (1a), (1b), (1d) and (1f).
- the reactive dyes of the formulas (1a) to (1i) are known or can be used in analogy to known compounds, e.g. through usual diazotization, Coupling and condensation reactions.
- the reactive dyes of the formulas (1a) to (1i) used in the inks should preferably low in salt, i.e. a total salt content of less than 0.5 wt .-%, based on the weight of the dyes.
- Reactive dyes that due to their manufacture and / or the subsequent addition of coupé agents have higher salt contents, e.g. by membrane separation processes, such as Ultrafiltration, reverse osmosis or dialysis.
- the inks preferably contain exclusively those of the above formulas as dyes (1a) to (1i).
- the inks preferably contain a total reactive dye content of the above Formulas (1a) to (1i) of 5 to 35% by weight, in particular 10 to 35% by weight and preferably 10 to 20% by weight based on the total weight of the ink.
- the content of N-methyl-2-pyrrolidone or 1,2-propylene glycol in the ink is usually 5 up to 30% by weight, in particular 5 to 20% by weight and preferably 10 to 20% by weight, based on the total weight of the ink.
- the inks preferably contain 1,2-propylene glycol, usually in an amount of 5 to 30% by weight, in particular 5 to 20% by weight and preferably 10 to 20% by weight on the total weight of the ink.
- the inks may also contain buffer substances, e.g. Borax, borate or citrate.
- buffer substances e.g. Borax, borate or citrate.
- borax sodium borate, sodium tetraborate and sodium citrate.
- she are used in particular in amounts of 0.1 to 3% by weight, preferably 0.1 to 1% by weight, based on the total weight of the ink used to achieve a pH of e.g. 4 to 9, especially 4 to 8.
- the inks can e.g. Alginate or in particular water-soluble, contain non-ionic cellulose ether.
- non-ionic cellulose ether come e.g. Methyl, ethyl, hydroxyethyl, methylhydroxyethyl, hydroxypropyl or Hydroxypropylmethyl cellulose into consideration.
- Methylcellulose or in particular are preferred Hydroxyethyl cellulose.
- Alkali alginates in particular and preferably come as alginates Sodium alginate into consideration.
- the cellulose ethers as well as the algnates are in the ink usually in an amount of 0.01 to 2% by weight, in particular 0.01 to 1 wt .-% and preferably 0.01 to 0.5 wt .-%, based on the total weight of the Ink, used.
- Both the water-soluble, non-ionic cellulose ethers and the Alginates are used as so-called thickeners and allow the setting of one certain viscosity of the ink.
- Preferred inks for the process according to the invention are those which have a viscosity from 1 to 40 mPa ⁇ s, in particular 1 to 20 mPa ⁇ s and preferably 1 to 10 mPa ⁇ s exhibit.
- the inks can also contain conventional additives, e.g. foam suppressants or in particular substances that inhibit fungal and / or bacterial growth. This are usually in amounts of 0.01 to 1 wt .-%, based on the total weight the ink used.
- the inks can be prepared in the usual way by mixing the individual components in the desired amount of water can be produced.
- the present invention also relates to a method for printing on textiles Fiber materials according to the inkjet printing process, which is characterized is that you print these fiber materials with an aqueous ink, which at least contains a reactive dye of the formulas (1a), (1b), (1d) and (1f) given above.
- aqueous inks can also be used which have at least one Reactive dye of the formulas (1a) to (1i) given above, in particular of the formulas (1a) to (1f), optionally at least one of the additives mentioned above for the inks contain and contain no thioglycol, preferably no further additives.
- the above preferences apply.
- the methods according to the invention for printing textile fiber materials can with inkjet printers known per se and suitable for textile printing be carried out.
- ink jet printing process individual drops of the ink are checked out sprayed onto a substrate using a nozzle.
- the continuous ink jet method is predominantly used for this as well as the drop on demand method.
- the ink-jet method creates the drops continuously, not for printing required drops are drained into a collecting container and recycled.
- Drop on demand method drops are created and printed as desired; i.e. drops are only generated when this is necessary for printing.
- the Generation of the drops can e.g. by means of a piezo inkjet head or by means of thermal Energy (bubble jet). Pressure is preferred for the method according to the invention according to the continuous ink jet method or the drop on demand method.
- fiber materials containing hydroxyl groups come as textile fiber materials into consideration.
- cellulose-containing fiber materials which are made up entirely or in part Cellulose exist.
- natural fiber materials such as cotton, linen or Hemp
- regenerated fiber materials such as Viscose.
- Viscose and lyocell or preferably cotton are particularly preferred here Viscose and lyocell or preferably cotton.
- the fiber materials mentioned are preferably in the form of flat textile fabrics, knitted fabrics or webs.
- the aqueous alkaline liquor contains at least one of the usual bases, which in conventional Reactive printing processes are used to fix the reactive dyes.
- the base is e.g. in an amount of 10 to 100 g / l liquor, preferably 10 to 50 g / l Fleet, deployed.
- Sodium bicarbonate is preferred, sodium carbonate or a mixture of water glass and sodium carbonate is used.
- the pH the alkaline liquor is usually 7.5 to 13.5, preferably 8.5 to 12.5.
- the aqueous alkaline liquor can contain other additives, e.g. Hydrotrope, contain.
- Urea is preferably used as the hydrotroping agent, e.g. in a Amount of 25 to 200 g / l liquor, preferably 50 to 150 g / l liquor is used.
- the fiber material is preferably dried after the above pretreatment.
- the fiber material is advantageously dried, preferably at temperatures up to 150 ° C, especially 80 to 120 ° C, and then a heat treatment process subjected to complete the print, or the dye to fix.
- the heat treatment can e.g. through a warm dwell process, a thermal insulation process or preferably be carried out by a steaming process.
- the printed fiber material is e.g. one treatment in one Damper with possibly superheated steam, conveniently at one temperature from 95 to 180 ° C, advantageously in saturated steam.
- the printed fiber material is usually washed with water in the usual way washed out to remove unfixed dye.
- the prints obtainable by the process according to the invention have good prints General realities on; e.g. they have high fiber-dye binding stability both in the acidic and in the alkaline range, good lightfastness, good Wet fastness properties, such as fastness to washing, water, sea water, over-dyeing and perspiration, one good chlorine fastness, rubbing fastness, ironing fastness and pleating fastness as well as sharp contours and high color strength.
- the printing inks used are characterized by good stability and good viscosity properties.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Coloring (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Ink Jet (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft Verfahren zum Bedrucken von textilen Fasermaterialien mit Reaktivfarbstoffen nach dem Tintenstrahldruck-Verfahren (Jet- und Ink-Jet-Verfahren) sowie entsprechende Drucktinten.The present invention relates to methods for printing textile fiber materials with reactive dyes according to the inkjet printing process (jet and inkjet processes) as well as corresponding printing inks.
Tintenstrahldruck-Verfahren werden bereits seit einigen Jahren in der Textilindustrie angewendet. Diese Verfahren ermöglichen es, auf die sonst übliche Herstellung einer Druckschablone zu verzichten, so dass erhebliche Kosten- und Zeiteinsparungen erzielt werden können. Insbesondere bei der Herstellung von Mustervorlagen kann innerhalb deutlich geringerer Zeit auf veränderte Bedürfnisse reagiert werden.Inkjet printing processes have been in the textile industry for several years applied. These methods make it possible to produce a Eliminate the printing stencil, so that considerable cost and time savings are achieved can be. Especially in the production of sample templates can within reacted to changing needs much less time.
Entsprechende Tintenstrahldruck-Verfahren sollten insbesondere optimale anwendungstechnische Eigenschaften aufweisen. Zu erwähnen seien in diesem Zusammenhang Eigenschaften wie die Viskosität, Stabilität, Oberflächenspannung und Leitfähigkeit der verwendeten Tinten. Femer werden erhöhte Anforderungen an die Qualität der erhaltenen Drucke gestellt, wie z.B. bezüglich Farbstärke, Faser-Farbstoff-Bindungsstabilität sowie Nassechtheitseigenschaften. Von den bekannten Verfahren werden diese Anforderungen nicht in allen Eigenschaften erfüllt, so dass weiterhin ein Bedarf nach neuen Verfahren für den textilen Tintenstrahldruck besteht.Corresponding inkjet printing processes should in particular be optimal have application properties. Worth mentioning in this Relationship properties such as viscosity, stability, surface tension and Conductivity of the inks used. There are also increased demands on quality of the prints obtained, e.g. regarding color strength, fiber-dye binding stability as well as wet fastness properties. Of the known methods these requirements are not met in all properties, so there is still a need for there are new processes for textile inkjet printing.
Gegenstand der Erfindung ist ein Verfahren zum Bedrucken von textilen Fasermaterialien
nach dem Tintenstrahldruck-Verfahren, welches dadurch gekennzeichnet ist, dass man
diese Fasermaterialien mit einer wässrigen Tinte bedruckt, welche mindestens einen
Reaktivfarbstoff der Formeln
und
worin
Z und Z' unabhängig voneinander Vinyl oder ein Rest der Formel -CH2-CH2-OSO3H sind,
B1 und B2 einen C2-C12-Alkylenrest bedeuten, welcher durch 1, 2 oder 3 Glieder -O-unterbrochen
sein kann und unsubstituiert oder durch Hydroxy, Sulfo, Sulfato, Cyano oder
Carboxy substituiert ist und
CuPhC ein Kupferphthalocyaninrest ist, und
b) 1,2-Propylenglykol oder N-Methyl-2-pyrrolidon
enthält.The invention relates to a process for printing textile fiber materials by the inkjet printing process, which is characterized in that these fiber materials are printed with an aqueous ink which comprises at least one reactive dye of the formulas and wherein
Z and Z 'are independently vinyl or a radical of the formula -CH 2 -CH 2 -OSO 3 H,
B 1 and B 2 represent a C 2 -C 12 alkylene radical which can be interrupted by 1, 2 or 3 members -O- and is unsubstituted or substituted by hydroxy, sulfo, sulfato, cyano or carboxy and
CuPhC is a copper phthalocyanine residue, and
b) 1,2-propylene glycol or N-methyl-2-pyrrolidone
contains.
B1 und B2 bedeuten vorzugsweise einen C2-C12-Alkylenrest, welcher durch 1 oder 2 Glieder -O- unterbrochen sein kann und unsubstituiert oder durch Hydroxy substituiert ist. B 1 and B 2 are preferably a C 2 -C 12 alkylene radical which can be interrupted by 1 or 2 members -O- and is unsubstituted or substituted by hydroxy.
Besonders bevorzugt bedeuten B1 und B2 einen C2-C6-Alkylenrest. Ganz besonders bevorzugt ist B1 1,3-Propylen und B2 1,2-Aethylen.B 1 and B 2 are particularly preferably C 2 -C 6 alkylene. B 1 is very particularly preferably 1,3-propylene and B 2 is 1,2-ethylene.
Z ist bevorzugt Vinyl. Für Z' ist die Bedeutung als Rest der Formel -CH2-CH2-OSO3H bevorzugt.Z is preferably vinyl. For Z 'the meaning as radical of the formula -CH 2 -CH 2 -OSO 3 H is preferred.
Vorzugsweise ist B1 1,3-Propylen, B2 1,2-Aethylen, Z Vinyl und Z' ein Rest der Formel -CH2-CH2-OSO3H.B 1 is preferably 1,3-propylene, B 2 1,2-ethylene, Z vinyl and Z 'is a radical of the formula -CH 2 -CH 2 -OSO 3 H.
Für das erfindungsgemässe Verfahren bevorzugte Reaktivfarbstoffe sind solche der Formeln (1a) bis (1g), insbesondere der Formeln (1a) bis (1f) und vorzugsweise solche der der Formeln (1a), (1b), (1d) und (1f).Preferred reactive dyes for the process according to the invention are those of Formulas (1a) to (1g), in particular of the formulas (1a) to (1f) and preferably those of the of the formulas (1a), (1b), (1d) and (1f).
Die Reaktivfarbstoffe der Formeln (1a) bis (1i) sind bekannt oder können in Analogie zu bekannten Verbindungen erhalten werden, wie z.B. durch übliche Diazotierungs-, Kupplungs- und Kondensationsreaktionen.The reactive dyes of the formulas (1a) to (1i) are known or can be used in analogy to known compounds, e.g. through usual diazotization, Coupling and condensation reactions.
Die in den Tinten verwendeten Reaktivfarbstoffe der Formeln (1a) bis (1i) sollten vorzugsweise salzarm sein, d.h. einen Gesamtgehalt an Salzen von weniger als 0,5 Gew.-%, bezogen auf das Gewicht der Farbstoffe, enthalten. Reaktivfarbstoffe, die, bedingt durch ihre Herstellung und/oder die nachträgliche Zugabe von Coupagemitteln grössere Salzgehalte aufweisen, können z.B. durch Membrantrennverfahren, wie Ultrafiltration, Umkehrosmose oder Dialyse, entsalzt werden.The reactive dyes of the formulas (1a) to (1i) used in the inks should preferably low in salt, i.e. a total salt content of less than 0.5 wt .-%, based on the weight of the dyes. Reactive dyes that due to their manufacture and / or the subsequent addition of coupé agents have higher salt contents, e.g. by membrane separation processes, such as Ultrafiltration, reverse osmosis or dialysis.
Vorzugsweise enthalten die Tinten als Farbstoffe ausschliesslich solche der obigen Formeln (1a) bis (1i).The inks preferably contain exclusively those of the above formulas as dyes (1a) to (1i).
Die Tinten enthalten bevorzugt einen Gesamtgehalt an Reaktivfarbstoffen der obigen Formeln (1a) bis (1i) von 5 bis 35 Gew.-%, insbesondere 10 bis 35 Gew.-% und vorzugsweise 10 bis 20 Gew.-%, bezogen auf das Gesamtgewicht der Tinte. The inks preferably contain a total reactive dye content of the above Formulas (1a) to (1i) of 5 to 35% by weight, in particular 10 to 35% by weight and preferably 10 to 20% by weight based on the total weight of the ink.
Der Gehalt an N-Methyl-2-pyrrolidon oder 1,2-Propylenglykol in der Tinte ist üblicherweise 5 bis 30 Gew.-%, insbesondere 5 bis 20 Gew.-% und vorzugsweise 10 bis 20 Gew.-%, bezogen auf das Gesamtgewicht der Tinte.The content of N-methyl-2-pyrrolidone or 1,2-propylene glycol in the ink is usually 5 up to 30% by weight, in particular 5 to 20% by weight and preferably 10 to 20% by weight, based on the total weight of the ink.
Bevorzugt enthalten die Tinten 1,2-Propylenglykol, üblicherweise in einer Menge von 5 bis 30 Gew.-%, insbesondere 5 bis 20 Gew.-% und vorzugsweise 10 bis 20 Gew.-%, bezogen auf das Gesamtgewicht der Tinte.The inks preferably contain 1,2-propylene glycol, usually in an amount of 5 to 30% by weight, in particular 5 to 20% by weight and preferably 10 to 20% by weight on the total weight of the ink.
Ferner können die Tinten Puffersubstanzen enthalten, wie z.B. Borax, Borat oder Citrat. Als Beispiele seien Borax, Natriumborat, Natriumtetraborat sowie Natriumcitrat genannt. Sie werden insbesondere in Mengen von 0,1 bis 3 Gew.-%, vorzugsweise 0,1 bis 1 Gew.-%, bezogen auf das Gesamtgewicht der Tinte, verwendet, um einen pH-Wert von z.B. 4 bis 9, insbesondere 4 bis 8, einzustellen.The inks may also contain buffer substances, e.g. Borax, borate or citrate. As Examples include borax, sodium borate, sodium tetraborate and sodium citrate. she are used in particular in amounts of 0.1 to 3% by weight, preferably 0.1 to 1% by weight, based on the total weight of the ink used to achieve a pH of e.g. 4 to 9, especially 4 to 8.
Als weitere Zusätze können die Tinten z.B. Alginat oder insbesondere wasserlösliche, nichtionogene Celluloseäther enthalten. Als wasserlösliche, nichtionogene Celluloseäther kommen z.B. Methyl-, Aethyl-, Hydroxyäthyl-, Methylhydroxyäthyl-, Hydroxypropyl- oder Hydroxypropylmethylcellulose in Betracht. Bevorzugt sind Methylcellulose oder insbesondere Hydroxyäthylcellulose. Als Alginate kommen insbesondere Alkalialginate und vorzugsweise Natriumalginat in Betracht. Die Celluloseäther sowie die Algnate werden in der Tinte üblicherweise in einer Menge von 0,01 bis 2 Gew.-%, insbesondere 0,01 bis 1 Gew.-% und vorzugsweise 0,01 bis 0,5 Gew.-%, bezogen auf das Gesamtgewicht der Tinte, verwendet. Sowohl die wasserlöslichen, nichtionogenen Celluloseäther als auch die Alginate werden als sogenannte Verdicker verwendet und erlauben die Einstellung einer bestimmten Viskosität der Tinte.As further additives, the inks can e.g. Alginate or in particular water-soluble, contain non-ionic cellulose ether. As a water-soluble, non-ionic cellulose ether come e.g. Methyl, ethyl, hydroxyethyl, methylhydroxyethyl, hydroxypropyl or Hydroxypropylmethyl cellulose into consideration. Methylcellulose or in particular are preferred Hydroxyethyl cellulose. Alkali alginates in particular and preferably come as alginates Sodium alginate into consideration. The cellulose ethers as well as the algnates are in the ink usually in an amount of 0.01 to 2% by weight, in particular 0.01 to 1 wt .-% and preferably 0.01 to 0.5 wt .-%, based on the total weight of the Ink, used. Both the water-soluble, non-ionic cellulose ethers and the Alginates are used as so-called thickeners and allow the setting of one certain viscosity of the ink.
Bevorzugt sind für das erfindungsgemässe Verfahren solche Tinten, welche eine Viskosität von 1 bis 40 mPa·s, insbesondere 1 bis 20 mPa·s und vorzugsweise 1 bis 10 mPa·s aufweisen.Preferred inks for the process according to the invention are those which have a viscosity from 1 to 40 mPa · s, in particular 1 to 20 mPa · s and preferably 1 to 10 mPa · s exhibit.
Weiterhin können die Tinten noch übliche Zusätze, wie z.B. schaumdämpfende Mittel oder insbesondere das Pilz- und/oder Bakterienwachstum hemmende Stoffe, enthalten. Diese werden üblicherweise in Mengen von 0,01 bis 1 Gew.-%, bezogen auf das Gesamtgewicht der Tinte, verwendet. Furthermore, the inks can also contain conventional additives, e.g. foam suppressants or in particular substances that inhibit fungal and / or bacterial growth. This are usually in amounts of 0.01 to 1 wt .-%, based on the total weight the ink used.
Die Tinten können in üblicher Weise durch Mischen der einzelnen Bestandteile in der gewünschten Menge Wasser hergestellt werden.The inks can be prepared in the usual way by mixing the individual components in the desired amount of water can be produced.
Gegenstand der vorliegenden Erfindung ist ferner ein Verfahren zum Bedrucken von textilen Fasermaterialien nach dem Tintenstrahldruck-Verfahren, welches dadurch gekennzeichnet ist, dass man diese Fasermaterialien mit einer wässrigen Tinte bedruckt, welche mindestens einen Reaktivfarbstoff der oben angegebenen Formeln (1a), (1b), (1d) und (1f) enthält. Als wässrige Tinten können femer auch solche verwendet werden, welche mindestens einen Reaktivfarbstoff der oben angegebenen Formeln (1a) bis (1i), insbesondere der Formeln (1a) bis (1f), gegebenenfalls mindestens einen der oben für die Tinten genannten Zusätze enthalten und keinThioglykol, vorzugsweise keine weiteren Zusätze, enthalten. Hierbei gelten die obigen Bevorzugungen.The present invention also relates to a method for printing on textiles Fiber materials according to the inkjet printing process, which is characterized is that you print these fiber materials with an aqueous ink, which at least contains a reactive dye of the formulas (1a), (1b), (1d) and (1f) given above. As aqueous inks can also be used which have at least one Reactive dye of the formulas (1a) to (1i) given above, in particular of the formulas (1a) to (1f), optionally at least one of the additives mentioned above for the inks contain and contain no thioglycol, preferably no further additives. Here the above preferences apply.
Die erfindungsgemässen Verfahren zum Bedrucken von textilen Fasermaterialien können mit an und für sich bekannten für den textilen Druck geeigneten Tintenstrahldruckern ausgeführt werden.The methods according to the invention for printing textile fiber materials can with inkjet printers known per se and suitable for textile printing be carried out.
Im Falle des Tntenstrahldruck-Verfahrens werden einzelne Tropfen der Tinte kontrolliert aus einer Düse auf ein Substrat gespritzt. Ueberwiegend werden hierzu die kontinuierliche Ink-Jet-Methode sowie die Drop on demand-Methode verwendet. Im Falle der kontinuierlichen Ink-Jet-Methode werden die Tropfen kontinuierlich erzeugt, wobei nicht für den Druck benötigte Tropfen in einen Auffangbehälter abgeleitet und rezykliert werden. Im Falle der Drop on demand-Methode hingegen werden Tropfen nach Wunsch erzeugt und gedruckt; d.h. es werden nur dann Tropfen erzeugt, wenn dies für den Druck erforderlich ist. Die Erzeugung der Tropfen kann z.B. mittels eines Piezo-Inkjet-Kopfes oder mittels thermischer Energie (Bubble Jet) erfolgen. Bevorzugt ist für das erfindungsgemässe Verfahren der Druck nach der kontinuierlichen Ink-Jet-Methode oder der Drop on demand-Methode.In the case of the ink jet printing process, individual drops of the ink are checked out sprayed onto a substrate using a nozzle. The continuous ink jet method is predominantly used for this as well as the drop on demand method. In the case of continuous The ink-jet method creates the drops continuously, not for printing required drops are drained into a collecting container and recycled. In case of Drop on demand method, however, drops are created and printed as desired; i.e. drops are only generated when this is necessary for printing. The Generation of the drops can e.g. by means of a piezo inkjet head or by means of thermal Energy (bubble jet). Pressure is preferred for the method according to the invention according to the continuous ink jet method or the drop on demand method.
Als textile Fasermaterialien kommen insbesondere hydroxylgruppenhaltige Fasermaterialien in Betracht. Bevorzugt sind cellulosehaltige Fasermaterialien, die ganz oder teilweise aus Cellulose bestehen. Beispiele sind natürliche Fasermaterialien wie Baumwolle, Leinen oder Hanf und regenerierte Fasermaterialien wie z.B. Viskose. Besonders bevorzugt sind hierbei Viskose sowie Lyocell oder vorzugsweise Baumwolle. Die genannten Fasermaterialien liegen vorzugsweise als flächige textile Gewebe, Gewirke oder Bahnen vor.In particular, fiber materials containing hydroxyl groups come as textile fiber materials into consideration. Preference is given to cellulose-containing fiber materials which are made up entirely or in part Cellulose exist. Examples are natural fiber materials such as cotton, linen or Hemp and regenerated fiber materials such as Viscose. Are particularly preferred here Viscose and lyocell or preferably cotton. The fiber materials mentioned are preferably in the form of flat textile fabrics, knitted fabrics or webs.
Gemäss einer bevorzugten Ausführungsform der vorliegenden Erfindung erfolgt vor dem Bedrucken eine Vorbehandlung des Fasermaterials, worin man das zu bedruckende Fasermaterial zuerst mit einer wässrigen alkalischen Flotte behandelt und das behandelte Fasermaterial gegebenenfalls trocknet.According to a preferred embodiment of the present invention, before Printing a pretreatment of the fiber material, in which one is to be printed Fiber material first treated with an aqueous alkaline liquor and the treated Fiber material dries if necessary.
Die wässrige alkalische Flotte enthält mindestens eine der üblichen Basen, welche in konventionellen Reaktivdruckverfahren zur Fixierung der Reaktivfarbstoffe eingesetzt werden. Die Base wird z.B. in einer Menge von 10 bis 100 g/l Flotte, vorzugsweise 10 bis 50 g/l Flotte, eingesetzt. Als Base kommen beispielsweise Natriumcarbonat, Natriumhydroxid, Dinatriumphosphat, Trinatriumphosphat, Natriumacetat, Natriumpropionat, Natriumhydrogencarbonat, wässriges Ammoniak oder Alkalispender, wie z.B. Natriumchloracetat oder Natriumformiat in Betracht. Vorzugsweise wird Natriumhydrogencarbonat, Natriumcarbonat oder eine Mischung aus Wasserglas und Natriumcarbonat verwendet. Der pH-Wert der alkalischen Flotte beträgt in der Regel 7,5 bis 13,5, vorzugsweise 8,5 bis 12,5. Die wässrige alkalische Flotte kann ausser den Basen weitere Zusätze, z.B. Hydrotropiermittel, enthalten. Als Hydrotropiermittel wird bevorzugt Harnstoff verwendet, der z.B. in einer Menge von 25 bis 200 g/l Flotte, vorzugsweise 50 bis 150 g/l Flotte eingesetzt wird. Vorzugsweise wird das Fasermaterial nach der obigen Vorbehandlung getrocknet.The aqueous alkaline liquor contains at least one of the usual bases, which in conventional Reactive printing processes are used to fix the reactive dyes. The base is e.g. in an amount of 10 to 100 g / l liquor, preferably 10 to 50 g / l Fleet, deployed. Sodium carbonate, sodium hydroxide, Disodium phosphate, trisodium phosphate, sodium acetate, sodium propionate, sodium hydrogen carbonate, aqueous ammonia or alkali dispensers, e.g. Sodium chloroacetate or sodium formate. Sodium bicarbonate is preferred, sodium carbonate or a mixture of water glass and sodium carbonate is used. The pH the alkaline liquor is usually 7.5 to 13.5, preferably 8.5 to 12.5. The aqueous alkaline liquor can contain other additives, e.g. Hydrotrope, contain. Urea is preferably used as the hydrotroping agent, e.g. in a Amount of 25 to 200 g / l liquor, preferably 50 to 150 g / l liquor is used. The fiber material is preferably dried after the above pretreatment.
Nach dem Bedrucken wird das Fasermaterial vorteilhafterweise getrocknet, vorzugsweise bei Temperaturen bis 150°C, insbesondere 80 bis 120°C, und anschliessend einem Hitzebehandlungsprozess unterworfen, um den Druck zu vervollständigen, bzw. den Farbstoff zu fixieren.After printing, the fiber material is advantageously dried, preferably at temperatures up to 150 ° C, especially 80 to 120 ° C, and then a heat treatment process subjected to complete the print, or the dye to fix.
Die Hitzebehandlung kann z.B. durch ein Warmverweilverfahren, einen Thermosolierprozess oder vorzugsweise durch ein Dämpfverfahren durchgeführt werden.The heat treatment can e.g. through a warm dwell process, a thermal insulation process or preferably be carried out by a steaming process.
Beim Dämpfverfahren wird das bedruckte Fasermaterial z.B. einer Behandlung in einem Dämpfer mit gegebenenfalls überhitztem Dampf, zweckmässigerweise bei einer Temperatur von 95 bis 180° C, vorteilhafterweise im Sattdampf, unterzogen. In the steaming process, the printed fiber material is e.g. one treatment in one Damper with possibly superheated steam, conveniently at one temperature from 95 to 180 ° C, advantageously in saturated steam.
Im Anschluss wird das bedruckte Fasermaterial in der Regel in üblicher Weise mit Wasser ausgewaschen um nichtfixierten Farbstoff zu entfernen.Subsequently, the printed fiber material is usually washed with water in the usual way washed out to remove unfixed dye.
Gegenstand der vorliegenden Erfindung sind ferner wässrige Drucktinten für das
Tintenstrahldruck-Verfahren, welche dadurch gekennzeichnet sind, dass sie
Für die Drucktinten sowie für die Reaktivfarbstoffe der Formeln (1a) bis (1i) gelten hierbei die weiter oben angegebenen Bedeutungen und Bevorzugungen.The same applies here for the printing inks and for the reactive dyes of the formulas (1a) to (1i) meanings and preferences given above.
Die nach den erfindungsgemässen Verfahren erhältlichen Drucke weisen gute Allgemeinechtheiten auf; sie besitzen z.B. eine hohe Faser-Farbstoff-Bindungsstabilität sowohl im sauren als auch im alkalischen Bereich, eine gute Lichtechtheit, gute Nassechtheiten, wie Wasch-, Wasser-, Seewasser-, Überfärbe-und Schweissechtheit, eine gute Chlorechtheit, Reibechtheit, Bügelechtheit und Plissierechtheit sowie scharfe Konturen und eine hohe Farbstärke. Die verwendeten Drucktinten zeichnen sich durch gute Stabilität und gute Viskositätseigenschaften aus.The prints obtainable by the process according to the invention have good prints General realities on; e.g. they have high fiber-dye binding stability both in the acidic and in the alkaline range, good lightfastness, good Wet fastness properties, such as fastness to washing, water, sea water, over-dyeing and perspiration, one good chlorine fastness, rubbing fastness, ironing fastness and pleating fastness as well as sharp contours and high color strength. The printing inks used are characterized by good stability and good viscosity properties.
Die nachfolgenden Beispiele dienen zur Erläuterung der Erfindung. Die Temperaturen sind in Celsiusgraden angegeben, Teile sind Gewichtsteile, die Prozentangaben beziehen sich auf Gewichtsprozente, sofern nicht anders vermerkt. Gewichtsteile stehen zu Volumenteilen im Verhältnis von Kilogramm zu Liter.The following examples serve to explain the invention. The temperatures are stated in degrees Celsius, parts are parts by weight, the percentages refer percentages by weight, unless stated otherwise. Parts by weight relate to parts by volume in the ratio of kilograms to liters.
- 15 Gew.-% des Reaktivfarbstoffs der Formel
- 15 Gew.-% 1,2-Propylenglykol,
- 0,5 Gew.-% Borax und
- 69,5 Gew.-% Wasser
- 15% by weight of the reactive dye of the formula
- 15% by weight of 1,2-propylene glycol,
- 0.5% by weight of borax and
- 69.5 wt% water
- 15 Gew.-% des Reaktivfarbstoffs der Formel
- 15 Gew.-% 1,2-Propylenglykol,
- 0,5 Gew.-% Borax und
- 69,5 Gew.-% Wasser
- 15% by weight of the reactive dye of the formula
- 15% by weight of 1,2-propylene glycol,
- 0.5% by weight of borax and
- 69.5 wt% water
- 15 Gew.-% des Reaktivfarbstoffs der Formel
- 15 Gew.-% 1,2-Propylenglykol,
- 0,5 Gew.-% Borax und
- 69,5 Gew.-% Wasser
- 15% by weight of the reactive dye of the formula
- 15% by weight of 1,2-propylene glycol,
- 0.5% by weight of borax and
- 69.5 wt% water
- 15 Gew.-% des Reaktivfarbstoffs der Formel
- 15 Gew.-% 1,2-Propylenglykol,
- 0,5 Gew.-% Borax und
- 69,5 Gew.-% Wasser
- 15% by weight of the reactive dye of the formula
- 15% by weight of 1,2-propylene glycol,
- 0.5% by weight of borax and
- 69.5 wt% water
- 15 Gew.-% des Reaktivfarbstoffs der Formel
- 15 Gew.-% 1,2-Propylenglykol und
- 70 Gew.-% Wasser
- 15% by weight of the reactive dye of the formula
- 15% by weight of 1,2-propylene glycol and
- 70% by weight water
- 15 Gew.-% des Reaktivfarbstoffs der Formel
- 15 Gew.-% 1,2-Propylenglykol,
- 0,5 Gew.-% Borax und
- 69,5 Gew.-% Wasser
- 15% by weight of the reactive dye of the formula
- 15% by weight of 1,2-propylene glycol,
- 0.5% by weight of borax and
- 69.5 wt% water
- 15 Gew.-% des Reaktivfarbstoffs der Formel
- 15 Gew.-% 1,2-Propylenglykol,
- 0,5 Gew.-% Natriumcitrat und
- 69,5 Gew.-% Wasser
- 15% by weight of the reactive dye of the formula
- 15% by weight of 1,2-propylene glycol,
- 0.5% by weight sodium citrate and
- 69.5 wt% water
- 15 Gew.-% des Reaktivfarbstoffs der Formel
- 15 Gew.-% 1,2-Propylenglykol und
- 70 Gew.-% Wasser
- 15% by weight of the reactive dye of the formula
- 15% by weight of 1,2-propylene glycol and
- 70% by weight water
- 15 Gew.-% des Reaktivfarbstoffs der Formel (101),
- 0,5 Gew.-% Borax und
- 84,5 Gew.-% Wasser
- 15% by weight of the reactive dye of the formula (101),
- 0.5% by weight of borax and
- 84.5 wt% water
- 15 Gew.-% des Reaktivfarbstoffs der Formel (102),
- 0,5 Gew.-% Borax und
- 84,5 Gew.-% Wasser
- 15% by weight of the reactive dye of the formula (102),
- 0.5% by weight of borax and
- 84.5 wt% water
- 15 Gew.-% des Reaktivfarbstoffs der Formel (104),
- 0,5 Gew.-% Borax und
- 84,5 Gew.-% Wasser
- 15% by weight of the reactive dye of the formula (104),
- 0.5% by weight of borax and
- 84.5 wt% water
- 15 Gew.-% des Reaktivfarbstoffs der Formel (106),
- 0,5 Gew.-% Borax und
- 84,5 Gew.-% Wasser
- 15% by weight of the reactive dye of the formula (106),
- 0.5% by weight of borax and
- 84.5 wt% water
Verfährt man wie in einem der Beispiele 1 bis 8 angegeben, verwendet jedoch anstelle von 15 Gew.-% 1,2-Propylenglykol 15 Gew.-% N-Methyl-2-pyrrolidon, so erhält man analoge Drucke mit guten Waschechtheiten.The procedure is as given in one of Examples 1 to 8, but is used instead of 15% by weight of 1,2-propylene glycol and 15% by weight of N-methyl-2-pyrrolidone give analogous results Print with good wash fastness.
Claims (14)
Z und Z' unabhängig voneinander Vinyl oder ein Rest der Formel -CH2-CH2-OSO3H sind,
B1 und B2 einen C2-C12-Alkylenrest bedeuten, welcher durch 1, 2 oder 3 Glieder -O-unterbrochen sein kann und unsubstituiert oder durch Hydroxy, Sulfo, Sulfato, Cyano oder Carboxy substituiert ist und
CuPhC ein Kupferphthalocyaninrest ist, und
Z and Z 'are independently vinyl or a radical of the formula -CH 2 -CH 2 -OSO 3 H,
B 1 and B 2 represent a C 2 -C 12 alkylene radical which can be interrupted by 1, 2 or 3 members -O- and is unsubstituted or substituted by hydroxy, sulfo, sulfato, cyano or carboxy and
CuPhC is a copper phthalocyanine residue, and
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH147397 | 1997-06-17 | ||
CH147397 | 1997-06-17 | ||
CH1473/97 | 1997-06-17 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0885998A2 true EP0885998A2 (en) | 1998-12-23 |
EP0885998A3 EP0885998A3 (en) | 2000-02-23 |
EP0885998B1 EP0885998B1 (en) | 2004-11-03 |
Family
ID=4211312
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98810523A Revoked EP0885998B1 (en) | 1997-06-17 | 1998-06-09 | Process for ink jet printing textile materials |
Country Status (13)
Country | Link |
---|---|
US (1) | US6015454A (en) |
EP (1) | EP0885998B1 (en) |
JP (1) | JPH1112962A (en) |
KR (1) | KR100538664B1 (en) |
CN (1) | CN1202549A (en) |
BR (1) | BR9802380A (en) |
DE (1) | DE59812197D1 (en) |
ES (1) | ES2230665T3 (en) |
ID (1) | ID20434A (en) |
PT (1) | PT885998E (en) |
SG (1) | SG73519A1 (en) |
TR (1) | TR199801116A2 (en) |
TW (1) | TW514659B (en) |
Families Citing this family (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9813475D0 (en) * | 1998-06-23 | 1998-08-19 | Zeneca Ltd | Compounds,compositions and use |
DE60008698T2 (en) | 1999-02-05 | 2004-07-29 | Ciba Specialty Chemicals Holding Inc. | BLACK INKING INKS AND THEIR USE |
US6371610B1 (en) * | 2000-01-28 | 2002-04-16 | Seiren Co., Ltd. | Ink-jet printing method and ink-jet printed cloth |
DE10004954A1 (en) * | 2000-02-04 | 2001-08-16 | Dystar Textilfarben Gmbh & Co | Aqueous printing inks for use by the inkjet printing process, their production and their use on textile fiber materials |
GB0019464D0 (en) * | 2000-08-09 | 2000-09-27 | Clariant Int Ltd | Organic compounds |
WO2002028659A2 (en) * | 2000-10-02 | 2002-04-11 | Kimberly-Clark Worldwide, Inc. | Recording medium with nanoparticles and methods of making the same |
US6561642B2 (en) | 2001-09-28 | 2003-05-13 | Hewlett-Packard Development Company | Ink jet printer system for printing an image on a web overlaying a removable substrate and method of assembling the printer system |
US20030199611A1 (en) * | 2002-03-08 | 2003-10-23 | Chandrasekaran Casey K. | Inkjet ink for textiles |
PL374193A1 (en) * | 2002-06-13 | 2005-10-03 | Clariant Finance (Bvi) Limited | Disazo dyes having adapted affinity |
US6780896B2 (en) * | 2002-12-20 | 2004-08-24 | Kimberly-Clark Worldwide, Inc. | Stabilized photoinitiators and applications thereof |
US8409618B2 (en) | 2002-12-20 | 2013-04-02 | Kimberly-Clark Worldwide, Inc. | Odor-reducing quinone compounds |
US7666410B2 (en) * | 2002-12-20 | 2010-02-23 | Kimberly-Clark Worldwide, Inc. | Delivery system for functional compounds |
WO2008055245A2 (en) | 2006-10-31 | 2008-05-08 | Sensient Colors Inc. | Inks comprising modified pigments and methods for making and using the same |
KR101575913B1 (en) | 2007-08-23 | 2015-12-08 | 센션트 컬러스 인크. | Self-dispersed pigments and methods for making and using the same |
US20090163887A1 (en) * | 2007-12-20 | 2009-06-25 | Arehart Kelly D | Odor control cellulose granules with quinone compounds |
CN105062217B (en) * | 2008-02-22 | 2019-02-15 | 日本化药株式会社 | Printing ink composition and the method for printing textile for using the printing ink composition |
CN101519551B (en) * | 2008-02-25 | 2011-07-20 | 明德国际仓储贸易(上海)有限公司 | Ink composition |
JP2010007192A (en) * | 2008-06-25 | 2010-01-14 | Konica Minolta Ij Technologies Inc | Inkjet printing method |
WO2010109867A1 (en) * | 2009-03-27 | 2010-09-30 | 日本化薬株式会社 | Ink composition and method for producing dyed polyamide-based fiber |
CN102858886A (en) * | 2009-04-07 | 2013-01-02 | 森馨颜色有限责任公司 | Self-dispersing particles and methods for making and using the same |
TWI425055B (en) * | 2009-08-21 | 2014-02-01 | Everlight Chem Ind Corp | Reactive printing dye and its aqueoues composition application |
US8987544B2 (en) | 2010-12-17 | 2015-03-24 | Kimberly-Clark Worldwide, Inc. | Article with heat-activatable expandable structures |
US8740869B2 (en) | 2011-03-11 | 2014-06-03 | Kimberly-Clark Worldwide, Inc. | Personal care articles with tactile visual cues |
CN102337045B (en) * | 2011-07-13 | 2014-03-26 | 丽源(湖北)科技有限公司 | Blue active dye mixture and preparation and application thereof |
CN102504583B (en) * | 2011-09-29 | 2014-10-08 | 刘卫斌 | Scarlet azo dye and its preparation and application |
CN106752077B (en) * | 2016-11-28 | 2018-07-24 | 浙江瑞华化工有限公司 | A kind of blue active dye composition and its preparation method and application |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2252335A (en) * | 1991-01-30 | 1992-08-05 | Ici Plc | Printing process and formulation |
US5542972A (en) * | 1994-05-20 | 1996-08-06 | Hoechst Ag | Reactive dyes for inkjet printing |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61101574A (en) * | 1984-10-23 | 1986-05-20 | Ricoh Co Ltd | Water based ink |
JPS60185886A (en) * | 1985-01-29 | 1985-09-21 | キヤノン株式会社 | Printing liquid medium |
US5250121A (en) * | 1991-09-26 | 1993-10-05 | Canon Kabushiki Kaisha | Ink-jet textile printing ink and ink-jet textile printing process |
GB9300065D0 (en) * | 1992-03-06 | 1993-03-03 | Zeneca Ltd | Chemical compositions |
GB9325454D0 (en) * | 1993-01-12 | 1994-02-16 | Zeneca Ltd | Azo compound |
DE4335958A1 (en) * | 1993-10-21 | 1995-04-27 | Bayer Ag | New copper phthalocyanine dyes and their use |
US5843217A (en) * | 1996-10-11 | 1998-12-01 | Minolta Co., Ltd. | Ink for ink jet recording |
-
1998
- 1998-06-02 US US09/089,146 patent/US6015454A/en not_active Expired - Lifetime
- 1998-06-09 ES ES98810523T patent/ES2230665T3/en not_active Expired - Lifetime
- 1998-06-09 DE DE59812197T patent/DE59812197D1/en not_active Revoked
- 1998-06-09 EP EP98810523A patent/EP0885998B1/en not_active Revoked
- 1998-06-09 PT PT98810523T patent/PT885998E/en unknown
- 1998-06-11 SG SG1998001395A patent/SG73519A1/en unknown
- 1998-06-11 ID IDP980857A patent/ID20434A/en unknown
- 1998-06-15 TW TW087109455A patent/TW514659B/en not_active IP Right Cessation
- 1998-06-15 BR BR9802380A patent/BR9802380A/en not_active Application Discontinuation
- 1998-06-16 CN CN98103228A patent/CN1202549A/en active Pending
- 1998-06-16 KR KR1019980022467A patent/KR100538664B1/en not_active IP Right Cessation
- 1998-06-16 TR TR1998/01116A patent/TR199801116A2/en unknown
- 1998-06-16 JP JP10168059A patent/JPH1112962A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2252335A (en) * | 1991-01-30 | 1992-08-05 | Ici Plc | Printing process and formulation |
US5542972A (en) * | 1994-05-20 | 1996-08-06 | Hoechst Ag | Reactive dyes for inkjet printing |
Non-Patent Citations (1)
Title |
---|
DATABASE WPI Section Ch, Week 198544 Derwent Publications Ltd., London, GB; Class A60, AN 1985-273488 XP002124482 & JP 60 185886 A (CANON KK), 21. September 1985 (1985-09-21) * |
Also Published As
Publication number | Publication date |
---|---|
SG73519A1 (en) | 2000-06-20 |
EP0885998B1 (en) | 2004-11-03 |
BR9802380A (en) | 1999-07-20 |
KR100538664B1 (en) | 2006-03-14 |
DE59812197D1 (en) | 2004-12-09 |
TR199801116A3 (en) | 1999-10-21 |
CN1202549A (en) | 1998-12-23 |
TR199801116A2 (en) | 1999-10-21 |
ID20434A (en) | 1998-12-17 |
ES2230665T3 (en) | 2005-05-01 |
PT885998E (en) | 2005-03-31 |
TW514659B (en) | 2002-12-21 |
JPH1112962A (en) | 1999-01-19 |
EP0885998A3 (en) | 2000-02-23 |
KR19990007011A (en) | 1999-01-25 |
US6015454A (en) | 2000-01-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0885998B1 (en) | Process for ink jet printing textile materials | |
EP0885999B1 (en) | Process for ink jet printing textile materials | |
EP1325945B1 (en) | Method for dyeing or printing and new reactive dyes | |
EP0886000B1 (en) | Process for ink jet printing textile materials | |
DE102008054404A1 (en) | Fiber-reactive azo dyes and dye mixtures, process for their preparation and their use | |
MXPA98004842A (en) | Process for printing textile vibra materials according to the it jet printing process | |
EP0832939B1 (en) | Mixtures of reactive azo dyes dyeing in blue and their use for dyeing fibrous material containing hydroxy and/or carbonamide groups | |
DE19511689A1 (en) | Mixture of blue-coloring fiber-reactive dyes and their use for dyeing fiber material containing hydroxyl and / or carbonamide groups | |
EP1737915A1 (en) | Mixtures of fiber-reactive azo dyes, their production and their use | |
EP0885997A2 (en) | Process for printing fibrous materials | |
JP2003306627A (en) | Ink composition for ink jet printing of textile product | |
EP1666540B1 (en) | Mixtures of fibre-reactive azo dyes, process for their preparation and their use | |
DE60101051T2 (en) | USE OF A DYE COMPOSITION IN THE INK JET PRINTING PROCESS | |
EP1086993B1 (en) | Copper complexes of azo dyestuffs, their production and use | |
DE102009000417A1 (en) | Fiber-reactive azo dyes, process for their preparation and their use | |
DE10064496A1 (en) | Black dye mixtures of fiber-reactive azo dyes and their use for dyeing fiber material containing hydroxyl and / or carbonamide groups | |
WO2000003082A1 (en) | Method for printing fibrous textile materials using the ink jet technique | |
DE19930866A1 (en) | Ink-jet printing on textile, especially cellulose, e.g. cotton or viscose, with aqueous ink containing reactive dye comprises treatment with fixing alkali only during or after printing | |
DE10035805A1 (en) | Water-soluble fiber-reactive dyes, processes for their preparation and their use | |
EP3521379A1 (en) | Fibre-reactive azo dyes and mixtures of dyestuffs, method for their preparation and their use for dyeing or printing | |
DE102004002577A1 (en) | Reactive azo dyes, process for their preparation and their use | |
WO2007085574A2 (en) | Water-soluble fiber-reactive dyes, methods for the production thereof, and use thereof | |
DE102005029383A1 (en) | Dye mixture of water-soluble fiber-reactive dyes, process for their preparation and their use | |
DE19922825A1 (en) | New brilliant yellow dyes containing fluorotriazine, processes for their preparation and their use for dyeing materials containing hydroxyl and amide groups | |
WO2003093371A1 (en) | Water-soluble fiber-reactive dyes, method for the production and use thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): BE CH DE ES FR GB IT LI PT |
|
AX | Request for extension of the european patent |
Free format text: AL;LT;LV;MK;RO;SI |
|
17P | Request for examination filed |
Effective date: 19990528 |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE |
|
AX | Request for extension of the european patent |
Free format text: AL;LT;LV;MK;RO;SI |
|
AKX | Designation fees paid |
Free format text: BE CH DE ES FR GB IT LI PT |
|
17Q | First examination report despatched |
Effective date: 20031217 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE CH DE ES FR GB IT LI PT |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REF | Corresponds to: |
Ref document number: 59812197 Country of ref document: DE Date of ref document: 20041209 Kind code of ref document: P |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 20050114 |
|
REG | Reference to a national code |
Ref country code: PT Ref legal event code: SC4A Free format text: AVAILABILITY OF NATIONAL TRANSLATION Effective date: 20050127 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2230665 Country of ref document: ES Kind code of ref document: T3 |
|
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
PLAX | Notice of opposition and request to file observation + time limit sent |
Free format text: ORIGINAL CODE: EPIDOSNOBS2 |
|
26 | Opposition filed |
Opponent name: DYSTAR TEXTILFARBEN GMBH & CO DEUTSCHLAND KG Effective date: 20050802 |
|
ET | Fr: translation filed | ||
PLBB | Reply of patent proprietor to notice(s) of opposition received |
Free format text: ORIGINAL CODE: EPIDOSNOBS3 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PUE Owner name: HUNTSMAN ADVANCED MATERIALS (SWITZERLAND) GMBH Free format text: CIBA SPECIALTY CHEMICALS HOLDING INC.#KLYBECKSTRASSE 141#4057 BASEL (CH) -TRANSFER TO- HUNTSMAN ADVANCED MATERIALS (SWITZERLAND) GMBH#KLYBECKSTRASSE 200#4057 BASEL (CH) |
|
RAP2 | Party data changed (patent owner data changed or rights of a patent transferred) |
Owner name: HUNTSMAN ADVANCED MATERIALS (SWITZERLAND) GMBH |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: PT Payment date: 20070529 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20070615 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20070622 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20070628 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20070621 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20070614 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20070711 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20070615 Year of fee payment: 10 |
|
RDAF | Communication despatched that patent is revoked |
Free format text: ORIGINAL CODE: EPIDOSNREV1 |
|
RDAG | Patent revoked |
Free format text: ORIGINAL CODE: 0009271 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: PATENT REVOKED |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
27W | Patent revoked |
Effective date: 20080628 |
|
GBPR | Gb: patent revoked under art. 102 of the ep convention designating the uk as contracting state |
Effective date: 20080628 |
|
REG | Reference to a national code |
Ref country code: PT Ref legal event code: MP4A Effective date: 20081114 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080609 |