EP0143969B1 - Verfahren zur Herstellung von Ätzreservedrucken auf hydrophoben Textilmaterialien - Google Patents
Verfahren zur Herstellung von Ätzreservedrucken auf hydrophoben Textilmaterialien Download PDFInfo
- Publication number
- EP0143969B1 EP0143969B1 EP84112741A EP84112741A EP0143969B1 EP 0143969 B1 EP0143969 B1 EP 0143969B1 EP 84112741 A EP84112741 A EP 84112741A EP 84112741 A EP84112741 A EP 84112741A EP 0143969 B1 EP0143969 B1 EP 0143969B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- printing paste
- etching
- salts
- acid
- discharge
- 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.)
- Expired
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- 239000004753 textile Substances 0.000 title claims description 31
- 239000000463 material Substances 0.000 title claims description 29
- 238000000034 method Methods 0.000 title claims description 29
- 230000008569 process Effects 0.000 title claims description 22
- 230000002209 hydrophobic effect Effects 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 238000007639 printing Methods 0.000 claims description 68
- 239000003795 chemical substances by application Substances 0.000 claims description 34
- 150000003839 salts Chemical class 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 22
- 150000007944 thiolates Chemical group 0.000 claims description 18
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical class OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical class SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 9
- 150000007529 inorganic bases Chemical class 0.000 claims description 6
- 150000007530 organic bases Chemical class 0.000 claims description 6
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 claims description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- SKOLWUPSYHWYAM-UHFFFAOYSA-N carbonodithioic O,S-acid Chemical class SC(S)=O SKOLWUPSYHWYAM-UHFFFAOYSA-N 0.000 claims description 3
- 239000012991 xanthate Substances 0.000 claims description 2
- 238000010019 resist printing Methods 0.000 claims 9
- 238000007599 discharging Methods 0.000 claims 7
- 239000012990 dithiocarbamate Substances 0.000 claims 1
- 150000004659 dithiocarbamates Chemical class 0.000 claims 1
- 238000005530 etching Methods 0.000 description 89
- -1 aliphatic disulfides Chemical class 0.000 description 53
- 239000000975 dye Substances 0.000 description 48
- 125000004432 carbon atom Chemical group C* 0.000 description 35
- 239000000986 disperse dye Substances 0.000 description 22
- 239000000835 fiber Substances 0.000 description 21
- 150000003254 radicals Chemical class 0.000 description 14
- 229920000728 polyester Polymers 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 10
- 239000004744 fabric Substances 0.000 description 10
- 125000004434 sulfur atom Chemical group 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 description 7
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 230000001603 reducing effect Effects 0.000 description 7
- 239000002562 thickening agent Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 125000003342 alkenyl group Chemical group 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
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- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 150000002431 hydrogen Chemical group 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920000151 polyglycol Polymers 0.000 description 4
- 239000010695 polyglycol Substances 0.000 description 4
- JCBJVAJGLKENNC-UHFFFAOYSA-M potassium ethyl xanthate Chemical compound [K+].CCOC([S-])=S JCBJVAJGLKENNC-UHFFFAOYSA-M 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Substances C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 4
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical class 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 235000012054 meals Nutrition 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- LEGWLJGBFZBZSC-UHFFFAOYSA-N n-[2-[(2,6-dicyano-4-nitrophenyl)diazenyl]-5-(diethylamino)phenyl]acetamide Chemical compound CC(=O)NC1=CC(N(CC)CC)=CC=C1N=NC1=C(C#N)C=C([N+]([O-])=O)C=C1C#N LEGWLJGBFZBZSC-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229940072033 potash Drugs 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 235000015320 potassium carbonate Nutrition 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 235000000346 sugar Nutrition 0.000 description 3
- 150000008163 sugars Chemical class 0.000 description 3
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- VGKYEIFFSOPYEW-UHFFFAOYSA-N 2-methyl-4-[(4-phenyldiazenylphenyl)diazenyl]phenol Chemical compound Cc1cc(ccc1O)N=Nc1ccc(cc1)N=Nc1ccccc1 VGKYEIFFSOPYEW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JGLMVXWAHNTPRF-CMDGGOBGSA-N CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O Chemical compound CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O JGLMVXWAHNTPRF-CMDGGOBGSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
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- 125000001931 aliphatic group Chemical class 0.000 description 2
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001448 anilines Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- HDFRDWFLWVCOGP-UHFFFAOYSA-N carbonothioic O,S-acid Chemical class OC(S)=O HDFRDWFLWVCOGP-UHFFFAOYSA-N 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- TUXJTJITXCHUEL-UHFFFAOYSA-N disperse red 11 Chemical compound C1=CC=C2C(=O)C3=C(N)C(OC)=CC(N)=C3C(=O)C2=C1 TUXJTJITXCHUEL-UHFFFAOYSA-N 0.000 description 2
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- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
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- RQLMZSLFKGNXTO-UHFFFAOYSA-N 1-amino-4-hydroxy-2-(6-hydroxyhexoxy)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=CC(OCCCCCCO)=C2N RQLMZSLFKGNXTO-UHFFFAOYSA-N 0.000 description 1
- MHXFWEJMQVIWDH-UHFFFAOYSA-N 1-amino-4-hydroxy-2-phenoxyanthracene-9,10-dione Chemical compound C1=C(O)C=2C(=O)C3=CC=CC=C3C(=O)C=2C(N)=C1OC1=CC=CC=C1 MHXFWEJMQVIWDH-UHFFFAOYSA-N 0.000 description 1
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- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
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- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- POJOORKDYOPQLS-UHFFFAOYSA-L barium(2+) 5-chloro-2-[(2-hydroxynaphthalen-1-yl)diazenyl]-4-methylbenzenesulfonate Chemical compound [Ba+2].C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O.C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O POJOORKDYOPQLS-UHFFFAOYSA-L 0.000 description 1
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical compound C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000005521 carbonamide group Chemical group 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- HIZCIEIDIFGZSS-UHFFFAOYSA-N carbonotrithioic acid Chemical class SC(S)=S HIZCIEIDIFGZSS-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- LIFQNDHZCABWSO-UHFFFAOYSA-N cyanomethanedithioic acid Chemical class SC(=S)C#N LIFQNDHZCABWSO-UHFFFAOYSA-N 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 125000004473 dialkylaminocarbonyl group Chemical group 0.000 description 1
- 125000004472 dialkylaminosulfonyl group Chemical group 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000010017 direct printing Methods 0.000 description 1
- 150000002016 disaccharides Chemical class 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical class CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- QJQZEJFUIOWFMS-UHFFFAOYSA-N formaldehyde;sulfanediol Chemical class O=C.OSO QJQZEJFUIOWFMS-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003165 hydrotropic effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- VDTIMXCBOXBHER-UHFFFAOYSA-N hydroxy-bis(sulfanyl)-sulfanylidene-$l^{5}-phosphane Chemical class OP(S)(S)=S VDTIMXCBOXBHER-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 1
- WREDNSAXDZCLCP-UHFFFAOYSA-N methanedithioic acid Chemical class SC=S WREDNSAXDZCLCP-UHFFFAOYSA-N 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- IFDAYERULSQJSP-UHFFFAOYSA-N n-(2,2-dicyanoethyl)formamide Chemical compound O=CNCC(C#N)C#N IFDAYERULSQJSP-UHFFFAOYSA-N 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- ZWWQICJTBOCQLA-UHFFFAOYSA-N o-propan-2-yl (propan-2-yloxycarbothioyldisulfanyl)methanethioate Chemical compound CC(C)OC(=S)SSC(=S)OC(C)C ZWWQICJTBOCQLA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001522 polyglycol ester Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 150000003342 selenium Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000446 sulfanediyl group Chemical class *S* 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003558 thiocarbamic acid derivatives Chemical class 0.000 description 1
- 150000003566 thiocarboxylic acids Chemical class 0.000 description 1
- 150000003579 thiophosphoric acid derivatives Chemical class 0.000 description 1
- 235000010487 tragacanth Nutrition 0.000 description 1
- 239000000196 tragacanth Substances 0.000 description 1
- 229940116362 tragacanth Drugs 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 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
- D06P5/12—Reserving parts of the material before dyeing or printing ; Locally decreasing dye affinity by chemical means
-
- 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
- D06P5/15—Locally discharging the 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
- D06P1/65168—Sulfur-containing 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
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/15—Locally discharging the dyes
- D06P5/155—Locally discharging the dyes with reductants
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/92—Synthetic fiber dyeing
- Y10S8/921—Cellulose ester or ether
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/92—Synthetic fiber dyeing
- Y10S8/922—Polyester fiber
Definitions
- the present invention relates to a method for producing etching reserve prints on textile materials which consist of hydrophobic fibers or predominantly contain hydrophobic fibers, e.g. B. in connection with cellulose, in particular with cotton, or in connection with wool, one or more white-etchable disperse dyes and optionally one or more etch-resistant disperse dyes being applied in the form of a liquor or printing paste and then carefully dried or dried and then one Etching reserve printing paste is printed in the desired pattern, which optionally additionally contains one or more etching-resistant disperse dyes, the order of printing on the etching reserve printing paste and the printing paste being reversed and, if a printing paste is used, drying or intermediate drying can be omitted, and subsequent heat treatment at 100 to 230 ° C.
- hydrophobic fibers or predominantly contain hydrophobic fibers e.g. B. in connection with cellulose, in particular with cotton, or in connection with wool
- the textile material is colored at the printed areas by the indestructible dye.
- Colored prints on a dark background can also be obtained if the dark background is made with a mixture of an etchable and a different colored, non-etchable dye.
- the known etching printing process is therefore modified in such a way that the textile material is first padded with a dye liquor containing disperse dye and then carefully dried or dried so that the dye is not yet fixed , ie Solution of the dye in which hydrophobic fiber takes place.
- the desired pattern is then printed on the dried or dried-on padded fabric with the etching printing paste and the fabric treated in this way is then subjected to a heat treatment, the base dye immigrating into the polyester at the non-printed areas at the same time, i.e. is fixed, and the dye is destroyed at the areas printed with etching printing paste, i.e. no coloring takes place.
- This process is also known as etching reserve pressure.
- etching reserve printing which is simple in itself, involves a number of technical difficulties which often make its use more difficult. It is usually not easy to completely destroy the base dye with the etchant. If this does not succeed, a colored residue remains on the etched areas, the shade of which can vary between yellow-brown and dull violet or reddish gray tones and which soils the white background at the etched areas. This leads to white etch which appears to be unclean or, in the event that a colored etch is to be produced, to a falsification of the shade of the etchant-resistant dye.
- etching printing pastes which contain relatively strong reducing or oxidizing agents, such as e.g. B. alkali formaldehyde sulfoxylates, or even heavy metal salts, such as tin-2-chloride.
- relatively strong reducing or oxidizing agents such as e.g. B. alkali formaldehyde sulfoxylates, or even heavy metal salts, such as tin-2-chloride.
- strong etching agents it is usually possible to achieve a perfect white etching print, but damage to the fiber material often occurs. Furthermore, these etchants are usually not cheap.
- zinc-2-chloride is used, the hydrochloric acid that splits off causes severe corrosion in the dampers.
- JP-A-56-165079, 56-159378, 57-029683, 57-029684 and 57-029685 describe the use of reducing sugars in the presence of alkali as an etchant.
- DE-A-31 13 732 relates to an etching or etching reserve printing process for textile materials made of hydrophobic fibers, in which a combination of an organic reducing agent with alkoxylated amines is used as the etching agent, alkyl sulfinates, reducing mono- or disaccharides and / or thiourea dioxide as reducing agents is used.
- Dyes are known from DE-A-26 12 740, 26 12 741, 26 12 742, 26 12 790, 26 12 791, 26 12 792, 28 36 391, 30 21 269 and 30 35 912 which are etched by aqueous alkalis can either destroy their chromophore or convert their carbonic ester or sulfonamide groups into a salt-like structure, whereby the dyes lose their affinity for the fiber.
- Such dyes by the processes described leads to fiber damage by saponification, which is particularly intolerable in the case of very light, thin qualities.
- such dyes can generally only be prepared using special, complex processes and from preliminary products produced specifically for this type of dye. However, they also show defects in the application. After the etching, for example, they show a certain affinity for and contaminate hydrophilic accompanying tissues, or they tend to thermomigrate, or they have poor drawing properties and thus have only a low color yield on the fiber.
- Their special structure also usually has a negative impact on the fastness to use, such as. B. lightfastness and thermosetting fastness.
- Compounds that can form a thiolate structure are e.g. B. the corresponding acids to the above thiolates in combination with inorganic or organic bases, which produce a pH of at least 8 in water.
- thermolyzable compounds are e.g. B. aromatic or aliphatic disulfides, which are optionally used in combination with inorganic or organic bases.
- Suitable hydrolyzable compounds, especially in an alkaline medium are e.g. B. the alkyl or aryl esters of thiocarbonic acid, thiocarboxylic acid or thiophosphoric acid derivatives.
- Me ⁇ represents an equivalent of a cation or alkali or alkaline earth metal or an optionally substituted ammonium ion.
- Monovalent alkane radicals representing R are branched or preferably straight-chain alkyl radicals; m-valent alkane radicals are those which differ from branched or preferably straight-chain alkanes by substitution of m hydrogen atoms deduce. If the carbon chain of the alkane radical is interrupted by a phenylene radical, the 1,3- and 1,4-phenylene radicals are preferred.
- alkane radicals interrupted by -O-, -S- or -NR 2- those interrupted by -0- are preferred.
- alkane chains are interrupted by -S- or -NR 2- , then preferably only one -S- or one -NR 2- group is present. This also applies if, in addition to the interruption by -S- or -NR 2- , the alkane chain has further interruptions by -O-.
- m-valent radicals R which are derived from trialkylamines, are preferably trivalent. They correspond to the formula where R 4 in turn has the definition that applies to divalent radicals R.
- the R 4 radicals are preferably divalent alkane radicals, which are optionally substituted and, with a chain length> 3, can be interrupted once or more than once by a distance of at least 2 C atoms by -O-.
- M-valent radicals R which are derived from polyalkylalkylene polyamines, correspond to the formula wherein R 5 is a direct bond or a radical R 4 .
- etchants with a thiolate structure are also to be understood in the following as those compounds which are capable of forming a thiolate structure under suitable ambient conditions (for example corresponding acids, hydrolytically or thermolytically cleavable precursors).
- Suitable etching agents of formula 1 to be used according to the invention can come from the series of thiocarbamates.
- A is a C atom
- B is an O atom
- X is a group -NR 2- .
- etching agents of the formula I to be used according to the invention comes from the series of trithiocarbonic acid derivatives, where A is a C atom, B is an S atom and X is also an S atom.
- etching agents of formula 1 to be used according to the invention are the salts of thio- or di-thiocarbonic acids, in which A is a C atom, B is a 0 or S atom and X is a direct bond.
- Preferred etchants of the formula to be used according to the invention are compounds from the series of the di-thiocarbaminates, where A is a C atom, B is an S atom and X is a group -NR 2 - , and from the series of the di-thiophosphoric acid esters, where A stands for POR 2 , B for an S atom and X for an O atom.
- Particularly preferred etching agents of formula 1 to be used according to the invention are compounds of the xanthate series, where A is a C atom, B is an S atom and X is an O atom.
- the number of the above-mentioned substituents attached to the hydrocarbon radicals representing RR 2 and R 3 depends on their structure. Simple substituents, such as halogen atoms, hydroxy, lower alkoxy, 1 to 6, preferably 1 to 3 identical or different, can be bonded to one of the hydrocarbon radicals. More extensive substituents, such as those which contain a phenyl nucleus, but also substituents with stronger neighboring group effects, such as cyan, carboxyl or alkoxycarbonyl, are generally only present once. Overall, simple substitution is preferred.
- Optionally substituted aryl radicals which can represent R and R 2 are phenyl, naphthyl-1 and naphthyl-2 radicals which are mono- to triple-fluorine, chlorine, bromine, alkyl having 1 to 4 carbon atoms, alkoxy with 1 to 4 C atoms, nitro, cyan, carboxyl, alkoxycarbonyl with 1 to 4 C atoms, mono- or dialkylaminocarbonyl with 1 to 4 C atoms in each alkyl radical, hydroxysulfonyl, alkoxysulfonyl with 1 to 4 C atoms, alkylsulfonyl with 1 to 4 C atoms in the alkyl radical, phenylsulfonyl, mono- or dialkylaminosulfonyl with 1 to 4 C atoms in each alkyl radical can be substituted.
- M-valent aromatic radicals which stand for R are 1,2-, 1,3- and 1,4-phenylene or 1,2-, 1,4-, 1,6- or 1,8-naphthylene.
- the phenylene radicals, in particular the 1,3-phenylene radical and very particularly the 1,4-phenylene radical, are preferred.
- Preferred monovalent radicals R or preferred radicals R 1 and R 2 are. Alkyl radicals having 1 to 4 carbon atoms, which are substituted by hydroxy, alkoxy having 1 to 4 carbon atoms, phenoxy, phenyl, chlorine, bromine or cyano, in particular simple can be substituted. Another preferred meaning of R 1 is hydrogen.
- Preferred divalent radicals R are ethylene and polymethylene with 3 to 6 C atoms, which, if they have 2 or more C atoms, by phenylene or, if they have 4 or more C atoms, at a distance of at least 2 C atoms can be interrupted by 1 to 2 oxygen atoms, or the 1,4-phenylene radical.
- Alkali or alkaline earth metals, for whose cation Me 9 stands, are, for. B. lithium, sodium, potassium, magnesium, calcium, strontium and barium.
- Ammonium ions which stand for Me $ can carry up to 2 radicals of R 1 and one radical of R 2 or can be derived from a 5- or 6-ring nitrogen heteroxy, such as pyridine, lutidine or pyrrolidine.
- Preferred cations are the ammonium ion and ammonium ions, which carry up to 3 alkyl radicals with 1 to 4 carbon atoms, which are optionally substituted by hydroxy, alkoxy with 1 to 4 carbon atoms.
- Very particularly preferred cations Me 9 are the sodium or potassium ion.
- salts of optionally substituted aliphatic or aromatic thiols of the general formula III can also be used in which R has the meanings mentioned above with the exception of hydrogen, can be used according to the invention.
- Preferred salts of aliphatic thiols are the mono- and divalent salts of thioglycolic acid.
- the sodium and potassium salts are particularly preferred.
- Corresponding acids that can form compounds with thiolate structure with inorganic or organic bases are, for. B. thiols, such as the thioglycolic acid ester, and preferably thioglycolic acid.
- Inorganic bases in the sense of the above statements are, for. B. the hydroxides, oxides, or salts of weak acids, such as the carbonates, hydrogen carbonates, phosphates, hydrogen phosphates and acetates of the above metals, the cation of which can represent Me ⁇ ; organic bases are e.g. B. the amines corresponding to the above-mentioned ammonium ions.
- Preferred etchants to be used according to the invention are also the salts of the hydrogen sulfide HS ⁇ Me ⁇ and S 2 ⁇ Me ⁇ 2 and the polysulfanes Me ⁇ 2 S x with 2 to 4, preferably 2, S atoms.
- etchants to be used according to the invention are disulfides, which can decompose thermally in particular in the presence of bases into compounds having a thiolate structure, such as, for example, B. the thiurams of the general formula IV
- Compounds which release compounds with thiolate structure by alkaline hydrolysis are e.g. B. di (hydroxycarbonylmethyl) tri-thiocarbonic acid ester or the inner salt of S-hydroxycarbonylmethylthiourea.
- a prerequisite for the use of compounds which form a thiolate structure through neutralization, thermal decomposition or alkaline hydrolysis is that this formation has ended and the compound with the thiolate structure can still have a caustic effect on the dye by the process according to the invention before this is fixed on the fiber.
- Combinations of salts of thiocyanic acid with compounds which have or can form a thiolate structure are combinations of e.g. B. sodium, potassium or ammonium rhodanide with compounds of the formulas I to V, in particular with salts from the series of di-thiocarbaminates, di-thiophosphoric acid esters, xanthates or thioglycolic acid.
- etching agents to be used according to the invention can be used as a single substance. Because of their compatibility with one another, combinations of several etching agents according to the invention can also be used.
- etchants to be used according to the invention can also be used in combination with inorganic or organic bases which produce a pH of at least 8 in water to provide the etching reserve for dyes which would not be completely etched by these bases alone, or in which these bases are in such large quantities would have to be used that fiber damage would result.
- Suitable etching reserve printing pastes are all preparations which allow the abovementioned etching agents to be applied to the tissue and which, under the application conditions, ensure that the printing paste is dispensed as evenly as possible to the tissue and deliver a pressure which is as sharp as possible.
- the compounds which have a thiolate structure or can form one are added to the printing pastes which are usually used.
- the etching agents are expediently added from the starting components during the production of the printing pastes.
- concentrations of the etchant in the etching reserve printing pastes of 0.1 to 250 g / kg, preferably 1 to 130 g / kg, are required in order to ensure, in the case of the application quantities of the etching reserve printing paste that are usually used, that the substrates to be printed on have the necessary properties the amount of etchant required for the etching is present. This amount depends on the depth of color of the coloring, the etchability of the dyes used and the activity of the etchant.
- the etchant is used in the usual application quantities of the etching printing paste and at the specified concentrations in a molar ratio of etchant: caustic dyes of 1: (1 to 10,000).
- the etching reserve printing pastes contain, in addition to the etching agents, water, thickening agents and auxiliaries (e.g. swelling agents, dispersing agents, fixing accelerators) and, if appropriate, etching-resistant dyes.
- auxiliaries e.g. swelling agents, dispersing agents, fixing accelerators
- Suitable thickeners for etching reserve printing pastes to be used according to the invention are, for example: starch degradation products such as dextrin; nonionic starch derivatives such as British gum; Gums such as gum arabic; Johanis bread kernel flour, in particular kernel flour ether, tragacanth; Guar derivatives, especially guar ethers, cellulose ether carboxylic acids.
- the etching reserve printing pastes can also contain other conventional auxiliaries and additives, such as. B.
- etching reserve printing pastes such as e.g. B. glycerol and / or polyglycols, such as polyethylene glycol, with an average molecular weight of 300 to 500, and / or polypropylene glycols, as z. B. are described in DE-A-29 51 312, or products based on N, N-dialkyl-substituted lower carbonamides, such as. B. N, N-di-cyanoethyl formamide.
- etching-resistant disperse dyes can also be incorporated in the etching reserve printing pastes.
- the etching reserve printing pastes used according to the invention preferably contain no reducing agents or oxidizing agents apart from the etching agents to be used according to the invention.
- all disperse dyes can be etched, the chromophore of which is destroyed by the etching reserve printing pastes and / or which are converted by this etching reserve printing pastes into a form which does not absorb onto the hydrophobic fibers.
- Dyes that can be etched by the method according to the invention are, in particular, mono- and disazo dyes.
- Monoazo dyes which can be etched by the method according to the invention are e.g. B. those with carbocyclic or heterocyclic diazo and / or coupling components from the series of anilines, naphthylamines, phenols, naphthols, 5- or 6-ring heterocycles, which may optionally be gas-condensed.
- Suitable disazo dyes are e.g. B. those whose central component is derived from anilines, naphthylamines or 5- or 6-ring heterocyclic amines.
- Examples of etchable azo dyes are: C.I. Disperse Yellow 7, 23, 68, 103 and 180; C.I.
- the process according to the invention is suitable for textile materials which consist of hydrophobic fibers, for example polypropylene, polyacrylonitrile, polyamide, cellulose triacetate, but especially polyester fibers, but also for textile materials which mix these hydrophobic fibers with cellulose, in particular cotton, or in Mix with wool included.
- suitable polyester fibers are those based on polybutylene terephthalate, poly-1,4-cyclohexylene-dimethylene terephthalate, but in particular polyethylene terephthalate, these polyesters, e.g. B. with a view to easier dyeability, can also be modified, for example by cocondensation of other components, for. B. other dicarboxylic acids and / or other diols.
- the method according to the invention is also suitable for textile materials which predominantly contain hydrophobic fibers alongside other fibers, such as, for example, B. cell or cotton.
- those textile materials come into consideration that still provide a uniform appearance when dyeing or printing with disperse dyes.
- the textile material can e.g. B. in the form of random nonwovens, felts, carpets, woven, knitted or knitted sheets or pieces.
- the process according to the invention is carried out by applying the white-etchable disperse dyes to the textile material in the form of liquors or printing pastes.
- the textile material When using a dye liquor, the textile material is z. B. impregnated in a conventional manner, for. B. padded or splashed.
- the dye liquors or printing pastes can contain one or more of the white-etchable disperse dyes mentioned in addition to known customary dyeing or printing aids, such as, for example, dispersing agents, wetting agents, foam damping agents and block aids.
- the impregnated textile material is squeezed to a liquor absorption of 50 to 120%.
- the textile materials treated in this way are then dried so carefully that no dye fixation takes place in the fiber. This can e.g. B.
- the temperature is about 60 to 80 ° C, maximum about 100 ° C with a corresponding reduction in time.
- the textile materials prepared in this way are then printed in the desired pattern using one of the abovementioned etching reserve printing pastes.
- the impregnated and printed textile materials are then subjected to a heat treatment between 100 and 230 ° C.
- the heat is preferably supplied by compressed steam.
- superheated steam or hot air is preferably used as the heat transfer medium.
- the heat treatment is preferably carried out using superheated steam, in particular at 170 to 200 ° C.
- a special embodiment of the method according to the invention consists in that the dye liquor additionally contains, in addition to white-etchable dispersion dyes, one or more dispersion dyes which are resistant to the etching agents according to the invention and are therefore not destroyed. If one proceeds as above, then multicolored designs are obtained.
- the white-etchable disperse dyes can also be printed on the textile material in the form of printing pastes and then overprinted in the desired pattern with the etching reserve printing paste.
- a drying or intermediate drying between the two printing processes is not absolutely necessary, so that wet-wet work can also be carried out.
- the textile prints are then fixed and completed as described above.
- etching reserve printing pastes of the type mentioned which in turn contain one or more resistant dispersion dyes, are printed on the fund impregnated or printed with white-etchable dispersion dyes.
- etching reserve printing paste which contains one or more etching agents of the type mentioned, in the desired pattern on the textile material and to print the textile material thus printed after drying or intermediate drying or without drying or intermediate drying, ie "wet-on wet "with a printing paste that contains one or more white-etchable dyes.
- the textile material treated in this way is subjected to the heat treatment already mentioned above in order to fix the dye at the points not covered with etching reserve printing paste and to destroy the dye at the places covered with etching reserve printing paste and, as already stated above, is completed.
- the etching reserve printing paste additionally contains one or more etching-resistant disperse dyes and / or the printing paste.
- for one or more white-etchable disperse dyes also contains one or more etch-resistant disperse dyes.
- the dyes are present in the padding liquors, printing pastes or in the etching reserve printing pastes in finely dispersed form, as is customary and known for disperse dyes.
- the padding liquors or printing pastes which are to be used according to the invention are also prepared in a manner known per se by mixing the flatting or printing paste constituents with the necessary amount of water and liquid finely dispersed or solid redispersible settings of the dyes.
- Etching-resistant disperse dyes which can be combined with the etchable dyes for the production of multi-colored designs, are e.g. B. anthraquinone, naphthalimide, nitro, quinophthalone or methine dyes or suitable caustic-resistant dyes are such.
- parts by weight to parts by volume behave like kilograms to liters.
- a polyester fabric is woven with a fleet of 20 parts by weight of the liquid commercial form of C.I. Disperse Blue 165, 3 parts by weight of citric acid, 20 parts by weight of an anti-migration agent based on polyacrylamide and 877 parts by weight of water at 20 to 30 ° C with a squeezing effect of 70% and carefully dried at 60 to 80 ° C.
- a pattern is then overprinted with an etching reserve printing paste which contains 500 parts by weight of a 14% core meal ether thickener, 80 parts by weight of glycerin, 80 parts by weight of polyglycol 400 and 50 g of potassium xanthate to 1000 parts by weight.
- a white etch on a blue background with a sharp stand and very good color fastness is obtained.
- a polyester fabric is padded and dried as described in Example 1. Then, with an etching reserve printing paste which contains 375 parts by weight of a 14% core meal ether thickener, 125 parts by weight of a 5% starch ether thickener, 20 parts by weight of glycerol and 80 parts by weight of polyglycol 400, 1 part by weight of thioglycolic acid and 40 parts by weight of potash per 1000 parts by weight. After fixing under superheated steam for 7 minutes at 175 ° C. and finishing as in Example 1, a white etch is obtained on a blue background with a sharp stand and very good coloristic properties.
- a polyester fabric is, as described in Example 1, with a liquor, but instead of C.I. Disperse Blue 165 20 parts by weight of the liquid commercial form of C.I. Disperse Brown 1 contains, padded and dried. Then, as in Example 1, a padding liquor which, however, contains 2 parts by weight of sodium sulfide and 80 parts by weight of potash instead of potassium xanthate, is overprinted, fixed and aftertreated. This gives a white etching on a reddish-brown background with a sharp stand and very good coloristic properties.
- a polyester fabric is printed in film printing with an etching reserve printing paste, which consists of 500 parts by weight of a 5% core meal thickener, 80 parts by weight glycerin, 80 parts by weight polyglycol 400, 80 parts by weight potassium xanthate, 20 parts by weight of a block aid based on fatty acid polyglycol ester and 220 parts by weight water.
- the fabric is then "wet-on-wet" overprinted with an ink consisting of 20 parts by weight of C.I.
- Disperse Blue 165/1 300 parts by weight of a low-viscosity alginate thickener (10%) and 200 parts by weight of a starch ether (120%), 5 parts by weight of a decalcifying agent based on polyphosphate, 3 parts by weight of citric acid in 1000 parts by weight.
- steaming is carried out for 7 minutes at 175 ° C., then reductively aftertreated, rinsed, soaped and dried with 2 parts by weight of hydrosulfite and 3 parts by volume of a 50% sodium hydroxide solution at 80 ° C. for 15 minutes. You get a white pattern on a blue background.
- a cellulose triacetate fabric is, as described in Example 1, with a liquor containing 30 parts by weight of the liquid commercial form of C.I. Contains Disperse Yellow 180 per 1000 parts by volume, padded and carefully dried. It is then overprinted with an etching reserve printing paste as in Example 1 and dried. After fixing with superheated steam for 7 minutes at 175 ° C, the pressure is rinsed, neutralized, soaped and dried. The printed areas appear white on a yellow background.
- a polyester fabric is padded and dried as described in Example 1. Then, as in Example 1, with an etching paste which, however, instead of the potassium xanthate, 2 parts by weight of thioglycolic acid and 80 parts by weight of potash and an additional 40 parts by weight of the liquid commercial form of C.I. Disperse Red 303 contains, overprinted in a pattern. After fixing under superheated steam for 7 minutes at 175 ° C. and aftertreatment as in Example 1, a brilliant red etching on a blue background with a sharp stand and very good coloristic properties is obtained.
- Example 2 A polyester fabric is padded and dried as described in Example 1. Then, as in Example 2, an etching reserve paste, which, however, contains 80 parts by weight of bis (isopropoxythiocarbonyl) disulfide instead of the thioglycolic acid, is overprinted, fixed and aftertreated. In this way, one also obtains a white etching on a blue background with a sharp stand and very good coloristic fastness properties.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Coloring (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19833339158 DE3339158A1 (de) | 1983-10-28 | 1983-10-28 | Verfahren zur herstellung von aetzreservedrucken auf hydrophoben textilmaterialien |
DE3339158 | 1983-10-28 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0143969A1 EP0143969A1 (de) | 1985-06-12 |
EP0143969B1 true EP0143969B1 (de) | 1987-11-25 |
Family
ID=6212972
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP84112741A Expired EP0143969B1 (de) | 1983-10-28 | 1984-10-23 | Verfahren zur Herstellung von Ätzreservedrucken auf hydrophoben Textilmaterialien |
Country Status (5)
Country | Link |
---|---|
US (1) | US4571246A (ko) |
EP (1) | EP0143969B1 (ko) |
JP (1) | JPS60110988A (ko) |
KR (1) | KR850003451A (ko) |
DE (2) | DE3339158A1 (ko) |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE551775C (de) * | 1927-05-24 | 1932-06-04 | I G Farbenindustrie Akt Ges | Verfahren zur Erzeugung von Zwei- oder Mehrfarbeneffekten auf mit Nitroanthrachinonen oder Substitutionsprodukten derselben gefaerbten Celluloseaethern, -estern oder dere n Umwandlungsprodukten |
GB877028A (en) * | 1959-08-27 | 1961-09-13 | Ici Ltd | Improved colouring process |
NL8004160A (nl) * | 1980-07-18 | 1982-02-16 | Epec Dinon | Samenstelling voor het etsbedrukken van textielmaterialen. |
DE3128984A1 (de) * | 1980-07-25 | 1982-03-18 | CIBA-GEIGY AG, 4002 Basel | "aetzreservedruckverfahren zum bedrucken von polyester enthaltenden fasermaterialien unter einsatz eines reduzierenden kohlenhydrate enthaltenden aetzmittels" |
DE3113732A1 (de) * | 1981-04-04 | 1982-10-21 | Basf Ag, 6700 Ludwigshafen | Verfahren zum bedrucken von synthesefasern |
DE3132416A1 (de) * | 1981-08-17 | 1983-02-24 | Hoechst Ag, 6000 Frankfurt | Verwendung von thiokohlensaeure- und -phosphorsaeurederivaten als reservemittel |
DE3209327A1 (de) * | 1982-03-15 | 1983-09-15 | Cassella Ag, 6000 Frankfurt | Verfahren zur herstellung von aetzreservedrucken auf hydrophoben textilmaterialien |
-
1983
- 1983-10-28 DE DE19833339158 patent/DE3339158A1/de not_active Withdrawn
-
1984
- 1984-09-17 US US06/651,590 patent/US4571246A/en not_active Expired - Fee Related
- 1984-10-23 EP EP84112741A patent/EP0143969B1/de not_active Expired
- 1984-10-23 DE DE8484112741T patent/DE3467786D1/de not_active Expired
- 1984-10-25 JP JP59223118A patent/JPS60110988A/ja active Pending
- 1984-10-26 KR KR1019840006689A patent/KR850003451A/ko not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
JPS60110988A (ja) | 1985-06-17 |
EP0143969A1 (de) | 1985-06-12 |
DE3467786D1 (en) | 1988-01-07 |
DE3339158A1 (de) | 1985-05-09 |
KR850003451A (ko) | 1985-06-17 |
US4571246A (en) | 1986-02-18 |
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