EP2313550B1 - Method for gently aftertreating dyed textiles - Google Patents
Method for gently aftertreating dyed textiles Download PDFInfo
- Publication number
- EP2313550B1 EP2313550B1 EP09781304A EP09781304A EP2313550B1 EP 2313550 B1 EP2313550 B1 EP 2313550B1 EP 09781304 A EP09781304 A EP 09781304A EP 09781304 A EP09781304 A EP 09781304A EP 2313550 B1 EP2313550 B1 EP 2313550B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- process according
- mol
- units
- polypropylene
- carbon atoms
- 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.)
- Active
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- 239000004753 textile Substances 0.000 title claims description 70
- 238000000034 method Methods 0.000 title claims description 35
- -1 polypropylene Polymers 0.000 claims description 64
- 229920001155 polypropylene Polymers 0.000 claims description 53
- 239000004743 Polypropylene Substances 0.000 claims description 52
- 239000000463 material Substances 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 35
- 239000000835 fiber Substances 0.000 claims description 34
- 229920000728 polyester Polymers 0.000 claims description 32
- 229920000578 graft copolymer Polymers 0.000 claims description 26
- 238000009472 formulation Methods 0.000 claims description 25
- 239000004094 surface-active agent Substances 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 239000013011 aqueous formulation Substances 0.000 claims description 16
- 229920001400 block copolymer Polymers 0.000 claims description 16
- 239000002736 nonionic surfactant Substances 0.000 claims description 16
- 239000000654 additive Substances 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 12
- 125000002947 alkylene group Chemical group 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 9
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 7
- 239000006260 foam Substances 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 5
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical group C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims description 2
- 150000002334 glycols Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 238000004043 dyeing Methods 0.000 description 17
- 239000000975 dye Substances 0.000 description 16
- 239000004744 fabric Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- 239000002202 Polyethylene glycol Substances 0.000 description 8
- 229920001223 polyethylene glycol Polymers 0.000 description 8
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 7
- 239000000986 disperse dye Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 150000002009 diols Chemical class 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid group Chemical group C(CCCCC(=O)O)(=O)O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 5
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229920000428 triblock copolymer Polymers 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004435 Oxo alcohol Substances 0.000 description 3
- 229920002873 Polyethylenimine Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000004042 decolorization Methods 0.000 description 3
- 229920000359 diblock copolymer Polymers 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 238000010186 staining Methods 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- 210000002268 wool Anatomy 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 150000003014 phosphoric acid esters Chemical group 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 102100037681 Protein FEV Human genes 0.000 description 1
- 101710198166 Protein FEV Proteins 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical class OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- HQPMKSGTIOYHJT-UHFFFAOYSA-N ethane-1,2-diol;propane-1,2-diol Chemical compound OCCO.CC(O)CO HQPMKSGTIOYHJT-UHFFFAOYSA-N 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 150000002211 flavins Chemical class 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000000687 hydroquinonyl group Chemical class C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- SBGKURINHGJRFN-UHFFFAOYSA-N hydroxymethanesulfinic acid Chemical compound OCS(O)=O SBGKURINHGJRFN-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 229920006030 multiblock copolymer Polymers 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004045 reactive dyeing Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000002351 wastewater Substances 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
- D06P5/02—After-treatment
-
- 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
- D06P1/52—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 synthetic macromolecular substances
-
- 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
- D06P1/60—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 polyethers
-
- 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
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/34—Material containing ester groups
- D06P3/52—Polyesters
- D06P3/54—Polyesters using dispersed dyestuffs
-
- 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
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/79—Polyolefins
-
- 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
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/79—Polyolefins
- D06P3/794—Polyolefins using dispersed 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
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/02—After-treatment
- D06P5/04—After-treatment with organic compounds
- D06P5/08—After-treatment with organic compounds macromolecular
Definitions
- the invention relates to a process for the aftertreatment of dyed and / or printed textiles for removing excess amounts of colorants, in which an aqueous formulation is used which comprises at least one graft copolymer having a hydrophilic main chain and also surfactants.
- Polyester fibers are widely used raw materials for the production of textile materials. Textiles made of polyester fibers can be colored by means of various dyeing processes from aqueous baths and / or printed by means of suitable textile printing inks. For example, polyesters can be dyed in an exhaust process at 120 ° -130 ° C. with disperse dyestuffs.
- the remaining on the surface excess dye can be removed, for example, by a reductive Nachmaschinesche with hydrosulfite and NaOH at 60-70 ° C. Thereafter, the fabric is usually rinsed, depending on the color depth 1 to 3 times. In the last rinse, the pH of the textile material is preferably adjusted to 4-7 with acetic acid.
- a third known method is the use of surfactants for after-washing.
- Surfactants alone generally do not have a sufficient effect.
- Polypropylene is a highly suitable polymer for the production of textile materials, but textiles made from polypropylene fibers are difficult to dye from aqueous baths due to the nonpolar nature of polypropylene. It is therefore known to improve the subsequent dyeability of polypropylene from aqueous dyebaths by adding suitable auxiliaries.
- a disperse dye-dyeable fiber comprising a blend of a polyolefin and an amorphous, glycol-modified PET (PET-G).
- PET-G amorphous, glycol-modified PET
- maleic anhydride is preferably used.
- WO 2006/128796 discloses a process for coloring polyolefins using polyolefins blended with a block copolymer of at least one nonpolar block consisting essentially of isobutene units and at least one polar block consisting essentially of oxyalkylene units.
- polyesters and / or polyamides can also be incorporated as auxiliaries.
- the object of the invention was therefore to provide a gentle process for after-washing, which avoids discoloration of the textiles.
- the textile materials comprise polyester and / or polypropylene fibers and in which the said materials are treated with an aqueous formulation of at least one anionic and / or nonionic surfactant (A). at a temperature of 20 to 100 ° C, and wherein the aqueous solution further contains at least one graft copolymer (B) comprising a straight-chain or branched, hydrophilic backbone comprising N and / or O atoms and side chains grafted thereon
- A anionic and / or nonionic surfactant
- B graft copolymer
- “Textile materials” may in principle be all types of textile materials, such as fibers for textile use, for example filaments or staple fibers, as well as semi-finished products or intermediates such as yarns, fabrics, knits, knitted fabrics, nonwovens or nonwovens. It may also be finished products, such as clothing or home textiles.
- the textile materials include polyester and / or polypropylene fibers. They may consist solely of polyester fibers and / or polypropylene fibers, but of course may also be used in combination with other materials such as polyamide fibers or natural fibers. A combination can be made at different stages of production. For example, it is already possible to produce filaments of a plurality of polymers with a defined geometric arrangement at the melt-spinning stage. In yarn production, fibers of other polymers may be incorporated, or fiber blends may be made from staple fibers. Furthermore, various yarns may be processed together and, finally, fabrics, knits or the like comprising polyester and / or polypropylene fibers may be joined together with chemically dissimilar fabrics.
- Suitable polypropylene grades for the production of fibers are known in principle to the person skilled in the art. They are relatively high molecular weight, viscous products, which are characterized in the usual way by their melt flow index (determined according to ISO 1133). According to the invention, at least one polypropylene having a melt flow index MFR (230 ° C., 2.16 kg) of 0.1 to 60 g / 10 min is used.
- polypropylene homopolymers may also be polypropylene copolymers which comprise, in addition to the propylene, small amounts of other comonomers.
- Suitable comonomers may in particular be other olefins such as, for example, ethylene and 1-butene, 2-butene, isobutene, 1-pentene, 1-hexene, 1-heptene, 1-octene, styrene or ⁇ -methylstyrene, dienes and / or polyenes.
- the proportion of comonomers in the polypropylene is generally not more than 20% by weight, preferably not more than 10% by weight.
- polypropylene having a melt flow index MFR (230 ° C., 2.16 kg) of 1 to 50 g / 10 min, more preferably 10 to 45 g / 10 min and, for example, 30 to 40 g / 10 min.
- the amount of the polypropylene is 80 to 99 wt.%, Based on the sum of all components of the undyed fiber, preferably 85 to 99 wt.%, Particularly preferably 90 to 98 wt.% And for example 93 to 97 wt.%.
- the polypropylene fiber for improving the dyeability comprises 1 to 20% by weight of at least one polyester.
- This may be conventional PET with a melting point of 255 to 265 ° C. It is particularly advantageous to use modified PET which has additional soft segments and accordingly has a lower degree of crystallization or melting point.
- polyesters can be used which have a melting point of 50 to 200 ° C.
- Lower melting point polyesters can be obtained by substituting a portion of the terephthalic acid units in the PET for aliphatic dicarboxylic acid units, especially adipic acid units, to synthesize the polyesters.
- the ethylene glycol units can also be replaced by longer-chain diols, in particular C 3 to C 6 alkanediols, for example 1,4-butanediol or 1,6-hexanediol.
- Polyesters preferred for carrying out the invention have at least two different dicarboxylic acid units (X). They comprise at least 5 to 80 mol% of terephthalic acid units (X1) and 20 to 95 mol% of units of aliphatic 1, ⁇ -dicarboxylic acids (X2) having 4 to 10 carbon atoms. The total amount of (X1) and (X2) is at least 80 mol%, the% figures being based on the total amount of all dicarboxylic acid units in the polyester.
- the aliphatic 1, ⁇ -dicarboxylic acid units (X2) may, for example, be succinic acid, glutaric acid, adipic acid or sebacic acid. It is preferably adipic acid.
- dicarboxylic acid units (X1) and (X2) various dicarboxylic acid units may still be present therefrom.
- dicarboxylic acid units X1 and (X2)
- various dicarboxylic acid units may still be present therefrom.
- Dicarboxylic acid units and / or cycloaliphatic dicarboxylic acid units are other aromatic ones Dicarboxylic acid units and / or cycloaliphatic dicarboxylic acid units.
- mixtures of different dicarboxylic acid units can be used.
- the amount of terephthalic acid units (X1) is 20 to 70 mol% and the amount of (X2) is 30 to 80 mol%.
- the sum of (X1) and (X2) is at least 90 mol%, more preferably at least 98 mol%, and most preferably 100 mol%.
- the diol units (Y) are selected from the group of aliphatic, cycloliphatic and / or polyether diols, wherein 50 to 100 mol% of aliphatic 1, ⁇ -diols (Y1) are present, and the percentages are based on the total amount of all diols.
- the aliphatic diols having 4 to 10 carbon atoms (Y1) may be, for example, 1,4-butanediol, 1,5-butanediol or 1,6-hexanediol.
- (Y1) is 1,4-butanediol.
- polyether diols examples include diethylene glycol, triethylene glycol, polyethylene glycol or polypropylene glycol.
- cycloaliphatic diols examples include cyclopentane or cyclohexanediols. Of course, aliphatic diols which do not correspond to the definition (Y1) can also be used. Examples include in particular ethylene glycol or propylene glycol.
- the polyesters may of course also include other components for fine control of the properties.
- Examples include building blocks which have additional functional groups. Particular mention should be made here of amino groups. Also to be mentioned are building blocks for chain extension.
- Preferred polyesters of the type mentioned have a melting point of 50 to 200 ° C.
- the melting point is 60 to 180 ° C, more preferably 80 to 160 ° C, most preferably 100 to 150 ° C and for example 110-130 ° C.
- the glass transition temperature is preferably 20-35 ° C., preferably 25-30 ° C., without the invention being restricted thereto.
- the number average molecular weight M n should generally be 5000 to 50 000 g / mol, preferably 10000 to 30 000 g / mol. Have proven particularly useful 20,000 to 25,000 g / mol.
- the ratio M w / M n is preferably 3 to 6, for example 4 to 5. It is furthermore advantageous for the polyester to have a melt flow rate MFR of 2 to 6 g / 10 min (ISO 1133, 190 ° C., 2.16 kg).
- a preferred bulk density is from 1.2 to 1.35 g / cm 3, more preferably 1.22 -1.30 g / cm 3.
- the preferred Vicat softening temperature is 75 to 85 ° C, more preferably 78-82 ° C (VST A / 50, ISO 306).
- polyesters can be used as an additive.
- the amount of the polyesters is preferably from 1 to 15% by weight, more preferably from 2 to 10% by weight and, for example, from 3 to 7% by weight.
- the polypropylene preferably used as an additive in addition 0.1 to 10 wt.% Of at least one block copolymer having at least one nonpolar block having a number average molecular weight M n of at least 200 g / mol and a polar block with a number average molar Mass M n of at least 500 g / mol comprises included.
- the amount of block copolymer is preferably from 0.2 to 6% by weight, more preferably from 0.5 to 4% by weight, and for example from 0.75 to 3% by weight.
- non-polar block which is composed essentially of isobutene units
- a polar block which is composed essentially of oxyalkylene units, and whose average molar mass M n is at least 1000 g / mol.
- the oxyalkylene units are preferably ethylene oxide units.
- the block copolymers are preferably triblock copolymers having a middle block of oxyalkylene units and two terminal blocks of isobutene, the blocks being linked together via suitable linking units.
- the polar blocks each have an average molar mass M n of 1000 to 20,000 g / mol.
- M n is preferably from 1250 to 18000 g / mol, more preferably from 1500 to 15000 g / mol, and most preferably from 2500 to 8000 g / mol.
- the non-polar blocks generally each have an average molar mass M n of 200 to 10,000 g / mol.
- M n is preferably from 300 to 8000 g / mol, particularly preferably from 400 to 6000 g / mol and very particularly preferably from 500 to 5000 g / mol.
- the block copolymers may be diblock, triblock or multiblock copolymers. Preference is given to diblock and triblock copolymers, in particular triblock copolymers which have a central polar block and two terminal nonpolar blocks. It may also be mixtures of diblock and triblock copolymers.
- the abovementioned block copolymers interact synergistically with the polyester and bring about particularly good dyeability. Preference is therefore given to an additive system comprising at least one polyester and at least one block copolymer of the type mentioned. But it is also possible to use only a polyester or only said block copolymer as an additive.
- the dyeing and / or printing of the textile materials can be carried out by methods known in principle to those skilled in the art.
- disperse dyes may preferably be used.
- the term "disperse dye” is known to the person skilled in the art. Disperse dyes are dyes with a low water solubility, which are used in disperse, colloidal form for dyeing, in particular for dyeing fibers and textile materials. Details of the dyeing and / or printing of textile materials are, for example, in WO 2006/128796 Page 15 to page 20 describe.
- an aqueous formulation of at least one anionic and / or nonionic surfactant (A) and at least one graft copolymer (B) is used.
- formulations for treating textiles are often referred to as "liquor”.
- the aqueous formulation used essentially comprises water as solvent.
- optional water-miscible solvents may be present, for example, alcohols such as methanol, ethanol or propanol.
- the solvent comprises at least 80% by weight of water with respect to the sum of all solvents of the aqueous formulation, preferably at least 90% by weight, more preferably at least 95% by weight, and very particularly preferably only water is used as solvent.
- the formulation furthermore contains at least one anionic and / or nonionic surfactant (A). At least one nonionic surfactant is preferred used. Of course, mixtures of several different surfactants can be used.
- nonionic surfactants include surfactants (A1) of the general formula (I) R 1 -O- (CH 2 -CH (R 2 ) -O) n -H.
- n is a number from 3 to 25, preferably 4 to 15 and more preferably 5 to 10.
- R 1 is an aliphatic and / or aromatic, straight-chain or branched hydrocarbon radical having 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms and especially preferably 12 to 16 carbon atoms.
- R 1 is preferably a straight-chain or branched, aliphatic hydrocarbon radical.
- R 1 may be radicals derived from fatty alcohols or preferably oxoalcohols.
- radicals R 2 independently of one another represent hydrogen or an alkyl radical having 1 to 6 carbon atoms, preferably hydrogen or methyl and particularly preferably hydrogen. If several different radicals R 2 are present, it should be at least 60%, preferably at least 80% of the radicals R 2 is hydrogen, this statement being based on the total number of all radicals R 2 .
- Nonionic surfactants (A1) are commercially available.
- surfactants include low-foaming nonionic surfactants (A2). Such surfactants are known in principle to the person skilled in the art.
- (A2) may be nonionic surfactants of the general formula (II) R 1 -O- (CH 2 -CH (R 3 ) -O) m -R 4 , wherein R 1 is as defined above.
- m is a number from 3 to 30, preferably 5 to 25 and particularly preferably 10 to 20.
- R 3 may be hydrogen, or an alkyl radical having 1 to 6 carbon atoms, preferably hydrogen or methyl, wherein at least 60%, preferably at least 80% of the radicals R 3 , based on the total number of all radicals R 3 is hydrogen. Particularly preferably, R 3 is exclusively hydrogen.
- the group R 4 is a group which is more hydrophobic than the group - (CH 2 -CH (R 3 ) -O) m - in formula (II).
- R 4 may be a group - (CH 2 -CH (R 5 ) -O) z -H, where z is a number from 1 to 15, preferably from 2 to 10.
- R 5 is hydrogen or an alkyl radical having 1 to 6 carbon atoms, preferably hydrogen, methyl or ethyl, with the proviso that at least 60% of the groups R 5, based on the total number of all groups R 5, is an alkyl radical having 1 to 6 Carbon atoms is.
- R 5 is methyl.
- Such block copolymers can be obtained by first alkoxylating the starter alcohol with ethylene oxide or at least 60 mol% of ethylene oxide-containing alkylene oxide mixtures and the resulting alkoxy alcohol in a second stage with propylene oxide and / or higher alkylene oxides or at least 60 mol% propylene oxide and / or higher alkylene oxides further alkoxylated alkylene oxide mixtures.
- R 4 include straight-chain or branched alkyl radicals having 1 to 20 carbon atoms, preferably 6 to 14 carbon atoms, or groups of the formula --CO-R 4 , where R 4 has the meaning mentioned.
- Such structures can be obtained by etherification or esterification of corresponding nonionic surfactants.
- low-foam nonionic surfactants are, for example, in WO 92/14808 .
- Low-foaming nonionic surfactants are commercially available.
- graft copolymers is used in the usual sense for copolymers which have a straight-chain or branched polymer backbone (main chain) and branching off (grafted) side chains, which may already be termed oligomers or polymers by their length.
- the polymer backbone and the side chains are chemically different in nature.
- the straight-chain or branched main chain is hydrophilic. It has N and / or O atoms, which are preferably part of the main chain itself.
- the N and / or O atoms of the main chain are separated from each other by groups of hydrocarbons, preferably from 2 to 4 hydrocarbon groups. They may preferably be 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene or 1,4-butylene groups.
- the graft copolymer (B) is a graft copolymer (B1) having a main chain consisting essentially of alkylene oxide units, the main chain having a number average molecular weight M n of 300 to 60,000 g / mol, preferably 600 to 10,000 g / mol and more preferably 2000 to 8000 g / mol.
- the main chain generally comprises at least 90 mol% of alkylene oxide units. They are preferably ethylene oxide and / or propylene oxide units, which are generally at least 50 mol%, preferably at least 70 mol% and particularly preferably at least 90 mol% of the alkylene oxide units are ethylene oxide units. Particularly preferably, the main chain is polyethylene glycol.
- the side chains consist essentially of ethylenically unsaturated monomers. These are preferably ethylenically unsaturated monomers having functional groups. Suitable monomers include vinyl derivatives or acrylic derivatives such as vinyl acetate, vinylamine, vinylpyrrolidone, vinylimidazole, vinyl esters, acrylic acid or acrylic esters. According to the The invention relates to the ethylenically unsaturated monomers of the side chains at least 50 mol% vinyl acetate, preferably at least 80 mol% of vinyl acetate and particularly preferably exclusively vinyl acetate.
- the graft copolymers (B1) can be prepared in a manner known in principle by carrying out the polymerization of the ethylenically unsaturated monomers of the side chains in the presence of polyalkylene oxides, in particular polyethylene glycol.
- the quantitative ratio of polyalkylene oxides to ethylenically unsaturated monomers is preferably selected such that the graft copolymer comprises 30 to 80% by weight of polyalkylene oxide, preferably 30 to 50% by weight of polyalkylene oxide.
- (B1) is a graft copolymer of polyethylene glycol and vinyl acetate with 30 to 50 wt.% Polyethylene glycol, wherein the main chain has a number average molecular weight M n of 4000 to 8000 g / mol.
- the graft copolymer (B) is a graft copolymer (B2) having a main chain consisting essentially of alkyleneimine units, wherein the main chain has a number average molecular weight M n of 300 to 10,000 g / mol, preferably 300 up to 1000 g / mol.
- the backbone is preferably polyethyleneimine, more preferably hyperbranched polyethylenimine typically obtained in the polymerization of ethyleneimine.
- the side chains are polyether units.
- Such graft copolymers (B2) can be obtained in a manner known in principle by alkoxylation of polyethyleneimine, in particular with ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, preferably ethylene oxide and / or propylene oxide. If different alkylene oxides are used, they may be present statically or else as block copolymers.
- the number of grafted Alkylenoxidiseren is usually at 5 to 100 per side group preferably 5 to 50.
- the aqueous formulation may optionally comprise further components (C) as auxiliary agents.
- components include foam suppressants, wetting and deaerating agents or dispersants.
- the aqueous formulation additionally comprises at least one foam damper (C1).
- foam damper may, for example, be foam silencers based on polysiloxanes, such as, for example, polydimethylsiloxanes.
- silicon-free foam suppressants such as fatty alcohol derivatives, disperse silicic acid or polyethers such as polypropylene glycol, poly (propylene glycol-ethylene glycol) copolymers or polypropylene glycol derivatives.
- an aqueous formulation which additionally comprises at least one wetting agent (C2).
- wetting aids include primary, secondary or tertiary phosphoric acid esters of alcohols, such as phosphoric acid esters of 2-ethylhexyl alcohol. Sulfosuccinates or other small-molecule surfactants can also be used for this purpose.
- a formulation may comprise at least one sponge damper (C1) and at least one wetting aid (C2).
- concentrations of the components of the formulation are determined by those skilled in the art according to the desired properties of the formulation.
- the concentration of the surfactants (A) in the Formulltation is usually 0.01 g / l to 5 g / l. preferably 0.02 g / l to 2 g / l, more preferably 0.05 g / l to 1 g / l and most preferably 0.1 g / l to 0.5 g / l.
- the weight ratio of low-foaming surfactants (A2) to the total amount of all surfactants should as a rule be at least 1: 1.
- the concentration of the graft copolymers (B) in the formulation is generally 0.5 g / l to 10 g / l. preferably 0.1 g / l to 5 g / l, more preferably 0.2 g / l to 2 g / l and most preferably 0.3 g / l to 1 g / l.
- the weight ratio of graft copolymers (B) to surfactants (A) in the formulation is at least 1: 1.
- the weight ratio (B) / (A) is 1: 1 to 20: 1, more preferably 2: 1 to 10: 1 and for example 3: 1 to 8: 1.
- the concentration of auxiliaries (C), if present, is generally up to 5 g / l, preferably 0.01 g / l to 2 g / l, more preferably 0.02 g / l to 1 g / l and most preferably 0 , 05 g / l to 0.6 g / l.
- the process according to the invention for post-dying colored and / or printed textile materials is a partial step in the course of the production process of textile materials and is generally carried out immediately after the dyeing and / or printing of the textile materials, typically with the textile dye itself, without being ruled out should, the procedure also until a later Time to perform.
- the textile material is treated with the aqueous formulation ("liquor"), for example by simple immersion.
- the weight ratio of textile materials to the aqueous formulation (“liquor ratio") is generally 1: 3 to 1:40, preferably 1: 5 to 1:10.
- the treatment is usually carried out at 20 to 100 ° C, preferably 30 to 90 ° C and particularly preferably 40 to 70 ° C.
- the duration of the aftertreatment is generally 5 to 60 minutes, preferably 10 to 30 minutes and particularly preferably 15 to 25 minutes.
- the textile material is usually rinsed once or several times with water.
- the process according to the invention has several advantages over the reductive after-cleaning, in particular in the after-treatment of textile materials containing polypropylene:
- the excess color is removed from the surface of the fabric without significantly worsening the color depth of the dyeing. So it only works on the surface and does not penetrate into the interior of the fiber material.
- This is not only an advantage over the reductive process, but also over the post-cleaning with surfactants. Since these are low molecular weight surfactants can be incorporated into the interior of polymeric materials such as e.g. Polypropylene penetrate, and migrate together with dyes back out.
- hydrosulfite and NaOH there are also ecological advantages, since neither hydrosulfite nor NaOH can reach the wastewater.
- formulations with hydrosulfite / NaOH inevitably have an alkaline pH, so that must be neutralized again after the aftertreatment.
- the formulations used according to the invention are at most slightly alkaline, so that the neutralization can be dispensed with.
- the fabric of additized polypropylene was prepared according to the WO 2006/128796 It was a polypropylene with a melt flow rate of 33 g / 10 min (230 ° C, 2.16 kg) used.
- the polypropylene contains as an additive about 5 wt.% Of a polyester having a melting point of 94 ° C, prepared according to WO 2006/128796 , Page 33 and about 1 wt.% Of a polyisobutene-polyethylene oxide-polyisobutene block copolymer (molecular weight M n of blocks: about 1000 - about 6000 - about 1000), prepared according to WO 2006/128796 , Page 21 (example block copolymer 2).
- the polypropylene and the additives were used in a twin-screw extruder according to the WO 2006/128796 , Page 17 mixed together, spun into threads and processed into a textile fabric.
- the textile fabric of PET and polypropylene were washed before the dyeing tests with a commercial industrial detergent.
- the staining was carried out by methods known to the person skilled in the art in an A-HIBA® staining apparatus.
- the dye used was weighed in, water was added and the bomb was heated for about 20 minutes in a 60 ° C hot water bath until the dye was dissolved.
- the remaining additives for the dyebath were added (4.8 g of a 5% solution of a commercial wetting agent (Basojet ® XP) in water, 75 g of a 1% solution of a UV stabilizer in water (Cibafast® PEX)) and the pH of the dyeing liquor with a buffer solution (21 ml / l glacial acetic acid and 30 g / l Naacetat) to 4.5. Total amount of formulation 200 ml each.
- a commercial wetting agent Basojet ® XP
- a 1% solution of a UV stabilizer in water Cibafast® PEX
- a buffer solution 21 ml / l glacial acetic acid and 30 g / l Naacetat
- the textile was removed well rinsed with hot water and rinsed with cold water. Then it was spun and dried in a drying oven at 60 ° C circulating air.
- the polyester and polypropylene fabrics were each stained with commercially available dyes, namely a black disperse dye (Panacron® Black AM-B, 3 wt.% In dye liquor), a red disperse dye (Dianix ® Deep Red SF, 2 wt.% In dyeing liquor) and a yellow disperse dye (Dianix ® flavins, 1 wt.% in dye liquor).
- a black disperse dye Panacron® Black AM-B, 3 wt.% In dye liquor
- a red disperse dye Dianix ® Deep Red SF, 2 wt.% In dyeing liquor
- a yellow disperse dye Dianix ® flavins, 1 wt.% in dye liquor
- Water is first heated without additives to the desired temperature for after-treatment. After reaching the temperature, the additives are added as a concentrate in aqueous solution so that the desired concentration is established, and at the same time the textile sample is added. The textile sample is agitated for the desired treatment time in the formulation, after which the formulation is decanted, rinsed with warm and then cold water.
- the textile sample is then in a solution of 0.5 l of water with 2 ml conc. Briefly rinsed acetic acid, centrifuged and dried in the laboratory dryer for 2 min at 120 ° C and 700 rev / min.
- the particular formulation, temperature and duration of the treatment are summarized in Table 1 below.
- the color depth of the dye before and after the aftertreatment was assessed.
- the color change of the material is determined via the gray scale for assessing the change of color (ISO 105-A02: 1993 DIN-EN 20105-A02 1994).
- the change of color is indicated in notes 1-5 (5: lowest change, 1: highest change).
- the wash fastness of the aftertreated samples was carried out with a wash fastness test according to DIN ISO 105-C06-A1S without using steel balls.
- the aftertreated fabric is washed at 40 ° C.
- the dyed textile is used to wash white fabrics made of other textile materials (wool, cotton, polyamide). It is judged how strongly the white tissues discolour.
- the evaluation is carried out according to gray scale for the evaluation of the Anblutens ISO105-A03: 1993 DIN EN 20105-A03: 1994). The color intensity is given in grades 1-5 (5: lowest color pickup foreign tissue, 1: highest color pickup foreign tissue).
- Table 1 shows examples and comparative examples with three other dyes as well as textiles made of both polypropylene and PET fibers.
- the aftertreatment was carried out under the same conditions either with NaHSO 3 / NaOH or the formulation to be used according to the invention.
- the tests show that the decolorization of the polypropylene textiles in the case of after-treatment with the formulation according to the invention is lower in each case than in the after-treatment with NaHSO 3 / NaOH. Nevertheless, the inventively post-treated polypropylene textiles do not stain more strongly in the wash fastness test.
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Description
Die Erfindung betrifft ein Verfahren zum Nachbehandeln gefärbter und/oder bedruckter Textilien zum Entfernen überschüssiger Anteile von Farbmitteln, bei dem man eine wässrige Formulierung einsetzt, welche mindestens ein Pfropfcopolymer mit einer hydrophilen Hauptkette sowie Tenside umfasst.The invention relates to a process for the aftertreatment of dyed and / or printed textiles for removing excess amounts of colorants, in which an aqueous formulation is used which comprises at least one graft copolymer having a hydrophilic main chain and also surfactants.
Fasern aus Polyester sind weit verbreitete Rohstoffe zur Herstellung textiler Materialien. Textilien aus Polyesterfasern können mittels verschiedener Färbeprozesse aus wässrigen Bädern eingefärbt werden und/oder mittels geeigneter Textildruckfarben bedruckt werden. Polyester können beispielsweise mit Dispersionsfarbstoffen bei 120°-130°C in Ausziehverfahren eingefärbt werden.Polyester fibers are widely used raw materials for the production of textile materials. Textiles made of polyester fibers can be colored by means of various dyeing processes from aqueous baths and / or printed by means of suitable textile printing inks. For example, polyesters can be dyed in an exhaust process at 120 ° -130 ° C. with disperse dyestuffs.
Nach dem Einfärben von Textilien folgt üblicherweise ein Nachwaschschritt, bei dem ein eventueller Überschuss von Farbmitteln von der Oberfläche der textilen Materialien entfernt wird, da nicht fixierte Farbstoffe zu einem Abfärben der Textilien führen können. Außerdem können nicht fixierte Farbstoffe beim Waschen der Textilien mit andersfarbigen Textilien zusammen zum unerwünschten Verfärben dieser andersfarbigen Textilien führen.After the dyeing of textiles usually follows a Nachwaschschritt, in which a possible excess of colorants is removed from the surface of the textile materials, since unfixed dyes can lead to a discoloration of the textiles. In addition, non-fixed dyes when washing textiles with differently colored textiles together can lead to the undesired discoloration of these different colored textiles.
Der auf der Oberfläche zurückgebliebene überschüssige Farbstoff kann beispielsweise durch eine reduktive Nachwäsche mit Hydrosulfit und NaOH bei 60-70°C entfernt werden. Danach wird das Textilgut üblicherweise gespült, je nach Farbtiefe 1 bis 3-mal. Im letzten Spülbad wird vorzugsweise der pH-Wert des Textilgutes mit Essigsäure auf 4-7 gestellt.The remaining on the surface excess dye can be removed, for example, by a reductive Nachwäsche with hydrosulfite and NaOH at 60-70 ° C. Thereafter, the fabric is usually rinsed, depending on the color depth 1 to 3 times. In the last rinse, the pH of the textile material is preferably adjusted to 4-7 with acetic acid.
Es ist weiterhin bekannt, zur reduktiven Nachwäsche Hydroxymethansulfinsäure bzw. Derivate davon einzusetzen. Der Nachteil dieses Verfahrens ist, dass es nicht für alle Farbstoffe geeignet ist, insbesondere nicht für einige Hydrochinonderivate.It is furthermore known to use hydroxymethanesulfinic acid or derivatives thereof for the reductive after-wash. The disadvantage of this method is that it is not suitable for all dyes, especially not for some hydroquinone derivatives.
Eine dritte bekannte Methode ist der Einsatz von Tensiden zur Nachwäsche. Tenside alleine haben aber in der Regel keine ausreichende Wirkung.A third known method is the use of surfactants for after-washing. Surfactants alone, however, generally do not have a sufficient effect.
Weitere Einzelheiten zu derartigen Nachwaschprozessen sind beispielsweise
Polypropylen ist ein zur Herstellung textiler Materialien hervorragend geeignetes Polymer, aber Textilien aus Polypropylenfasern lassen sich aber aufgrund des unpolaren Charakters von Polypropylen nur sehr schlecht aus wässrigen Bädern färben. Es ist daher bekannt, die nachträgliche Anfärbbarkeit von Polypropylen aus wässrigen Färbebädern durch Zusatz von geeigneten Hilfsmitteln zu verbessern.Polypropylene is a highly suitable polymer for the production of textile materials, but textiles made from polypropylene fibers are difficult to dye from aqueous baths due to the nonpolar nature of polypropylene. It is therefore known to improve the subsequent dyeability of polypropylene from aqueous dyebaths by adding suitable auxiliaries.
So offenbart beispielsweise
Zum Einfärben derartiger Textilien aus dotiertem Polypropylen kann ähnlich vorgegangen werden wie bei der Einfärbung von Polyestern.For coloring such textiles from doped polypropylene can be proceeded similar to the coloring of polyesters.
Bei Textilien aus dotiertem Polypropylen besteht aber die Gefahr, dass das eingefärbte, dotierte Polypropylen durch eine starke reduktive Nachwäsche zumindest teilweise entfärbt werden kann. Selbst bei einer sehr schwachen reduktiven Nachwäsche (2g /l Hydrosulfit und 0.5 g/L NaOH) wird bereits ein Verlust an Farbtiefe des gefärbten Textils beobachtet.With textiles made of doped polypropylene, however, there is a risk that the dyed, doped polypropylene can be at least partially decolorized by a strong reductive after-wash. Even with a very weak reductive after-wash (2 g / l hydrosulfite and 0.5 g / l NaOH), a loss of color depth of the dyed textile is already observed.
Aufgabe der Erfindung war es daher, ein schonendes Verfahren zur Nachwäsche bereitzustellen, welches eine Entfärbung der Textilien vermeidet.The object of the invention was therefore to provide a gentle process for after-washing, which avoids discoloration of the textiles.
Dementsprechend wurde ein Verfahren zum Nachbehandeln von gefärbten und/oder bedruckten textilen Materialien gefunden, wobei die textilen Materialien Polyester - und/oder Polypropylenfasern umfassen, und bei dem man die besagten Materialien mit einer wässrigen Formulierung mindestens eines anionischen und/oder nichtionischen Tensids (A) bei einer Temperatur von 20 bis 100°C behandelt, und wobei die wässrige Lösung darüber hinaus mindestens ein Pfropfcopolymer (B) enthält, welches eine geradkettige oder verzweigte, hydrophile, N- und/oder O-Atome umfassende Hauptkette sowie darauf aufgepfropfte Seitenketten umfasstAccordingly, a process has been found for the aftertreatment of dyed and / or printed textile materials, wherein the textile materials comprise polyester and / or polypropylene fibers and in which the said materials are treated with an aqueous formulation of at least one anionic and / or nonionic surfactant (A). at a temperature of 20 to 100 ° C, and wherein the aqueous solution further contains at least one graft copolymer (B) comprising a straight-chain or branched, hydrophilic backbone comprising N and / or O atoms and side chains grafted thereon
Zu der Erfindung ist im Einzelnen das Folgende auszuführen:
- Zur Ausführung des erfindungsgemäßen Verfahrens werden gefärbte und/oder bedruckte textile, Polyester- und/oder Polypropylenfasern umfassende Materialien, mit einer wässrigen Formulierung nachbehandelt.
- To carry out the process according to the invention, dyed and / or printed textile, polyester and / or polypropylene fibers comprising materials are aftertreated with an aqueous formulation.
Bei "textilen Materialien" kann es sich prinzipiell um alle Arten textiler Materialien handeln, wie Fasern für den textilen Einsatz, beispielsweise Filamente oder Stapelfasern, sowie Halbfabrikate oder Zwischenprodukte wie beispielsweise Garne, Gewebe, Gestricke, Gewirke, Vliese oder Vliesstoffe. Es kann sich auch um Fertigprodukte handeln, wie beispielsweise Bekleidungsstücke oder Heimtextilien."Textile materials" may in principle be all types of textile materials, such as fibers for textile use, for example filaments or staple fibers, as well as semi-finished products or intermediates such as yarns, fabrics, knits, knitted fabrics, nonwovens or nonwovens. It may also be finished products, such as clothing or home textiles.
Die textilen Materialien umfassen Polyester- und/oder Polypropylenfasern. Sie können ausschließlich aus Polyesterfasern und/oder Polypropylenfasern bestehen, können aber selbstverständlich auch in Kombination mit anderen Materialien, wie beispielsweise Polyamid-Fasern oder natürlichen Fasern verwendet werden. Eine Kombination kann auf verschiedenen Fertigungsstufen vorgenommen werden. Beispielsweise kann man bereits auf der Stufe des Schmelzeverspinnens Filamente aus mehreren Polymeren mit definierter geometrischer Anordnung herstellen. Bei der Garnherstellung können Fasern aus anderen Polymeren mit eingearbeitet werden oder es können Fasermischnungen aus Stapelfasern hergestellt werden. Weiterhin können verschiedenartige Garne miteinander verarbeitet werden und schließlich können auch Gewebe, Gestricke oder dergleichen, welche Polyester- und/oder Polypropylenfaseen umfassen mit chemisch andersartigen Geweben miteinander verbunden werden.The textile materials include polyester and / or polypropylene fibers. They may consist solely of polyester fibers and / or polypropylene fibers, but of course may also be used in combination with other materials such as polyamide fibers or natural fibers. A combination can be made at different stages of production. For example, it is already possible to produce filaments of a plurality of polymers with a defined geometric arrangement at the melt-spinning stage. In yarn production, fibers of other polymers may be incorporated, or fiber blends may be made from staple fibers. Furthermore, various yarns may be processed together and, finally, fabrics, knits or the like comprising polyester and / or polypropylene fibers may be joined together with chemically dissimilar fabrics.
In einer bevorzugten Variante handelt es sich um textile Materialien, welche Polypropylenfasern umfassen, wobei die Polypropylenfasern geeignete Additive zur Verbesserung der Anfärbbarkeit enthalten.In a preferred variant, these are textile materials which comprise polypropylene fibers, the polypropylene fibers containing suitable additives for improving dyeability.
Geeignete Polypropylensorten zur Herstellung von Fasern sind dem Fachmann prinzipiell bekannt. Es handelt sich um relativ hochmolekulare, zähfließende Produkte, welche in üblicher Art und Weise durch Ihren Schmelzflussindex (bestimmt nach ISO 1133) charakterisiert werden. Erfindungsgemäß wird mindestens ein Polypropylen mit einem Schmelzflussindex MFR (230°C, 2,16 kg) von 0,1 bis 60 g / 10 min eingesetzt.Suitable polypropylene grades for the production of fibers are known in principle to the person skilled in the art. They are relatively high molecular weight, viscous products, which are characterized in the usual way by their melt flow index (determined according to ISO 1133). According to the invention, at least one polypropylene having a melt flow index MFR (230 ° C., 2.16 kg) of 0.1 to 60 g / 10 min is used.
Es kann sich hierbei um Polypropylen-Homopolymere handeln. Es kann sich aber auch um Polypropylen-Copolymere handeln, welche neben dem Propylen geringe Mengen anderer Comonomere umfassen. Bei geeigneten Comonomeren kann es sich insbesondere um andere Olefine wie beispielsweise Ethylen sowie 1-Buten, 2-Buten, Isobuten, 1-Penten, 1-Hexen, 1-Hepten, 1-Octen, Styrol oder α-Methylstyrol, Diene und/oder Polyene handeln. Der Anteil von Comonomere im Polypropylen beträgt im Allgemeinen maximal 20 Gew. %, bevorzugt maximal 10 Gew. %. Art und Menge der Comonomere werden vom Fachmann je nach den gewünschten Eigenschaften der Faser gewählt. Selbstverständlich kann auch eine Mischung mehrerer verschiedener Sorten von Polypropylen eingesetzt werden. Bevorzugt handelt es sich um Polypropylene mit einem Schmelzflussindex MFR (230°C, 2,16 kg) von 1 bis 50 g / 10 min, besonders bevorzugt 10 bis 45 g / 10 min und beispielsweise 30 bis 40 g / 10 min.These may be polypropylene homopolymers. However, it may also be polypropylene copolymers which comprise, in addition to the propylene, small amounts of other comonomers. Suitable comonomers may in particular be other olefins such as, for example, ethylene and 1-butene, 2-butene, isobutene, 1-pentene, 1-hexene, 1-heptene, 1-octene, styrene or α-methylstyrene, dienes and / or polyenes. The proportion of comonomers in the polypropylene is generally not more than 20% by weight, preferably not more than 10% by weight. The type and amount of the comonomers are chosen by the skilled person depending on the desired properties of the fiber. Of course, a mixture of several different types of polypropylene can be used. Preference is given to polypropylenes having a melt flow index MFR (230 ° C., 2.16 kg) of 1 to 50 g / 10 min, more preferably 10 to 45 g / 10 min and, for example, 30 to 40 g / 10 min.
Die Menge des Polypropylens beträgt 80 bis 99 Gew. %, bezogen auf die Summe aller Bestandteile der ungefärbten Faser, bevorzugt 85 bis 99 Gew. %, besonders bevorzugt 90 bis 98 Gew. % und beispielsweise 93 bis 97 Gew. %.The amount of the polypropylene is 80 to 99 wt.%, Based on the sum of all components of the undyed fiber, preferably 85 to 99 wt.%, Particularly preferably 90 to 98 wt.% And for example 93 to 97 wt.%.
In einer bevorzugten Ausführungsform der Erfindung umfasst die Polypropylenfaser zur Verbesserung der Anfärbbarkeit 1 bis 20 Gew. % mindestens eines Polyesters. Hierbei kann es sich um übliches PET mit einem Schmelzpunkt von 255 bis 265°C handeln. Besonders vorteilhaft kann modifiziertes PET eingesetzt werden, welches zusätzliche Weichsegmente aufweist und dementsprechend einen niedrigeren Kristallisationsgrad bzw. Schmelzpunkt aufweist. Besonders vorteilhaft können zur Ausführung der Erfindung Polyester eingesetzt werden, welche einen Schmelzpunkt von 50 bis 200°C aufweisen.In a preferred embodiment of the invention, the polypropylene fiber for improving the dyeability comprises 1 to 20% by weight of at least one polyester. This may be conventional PET with a melting point of 255 to 265 ° C. It is particularly advantageous to use modified PET which has additional soft segments and accordingly has a lower degree of crystallization or melting point. Particularly advantageous for carrying out the invention, polyesters can be used which have a melting point of 50 to 200 ° C.
Polyester mit einem niedrigeren Schmelzpunkt können erhalten werden, indem man zur Synthese der Polyester einen Teil der Terephthalsäureeinheiten im PET gegen aliphatische Dicarbonsäureeinheiten, insbesondere gegen Adipinsäureeinheiten ersetzt. Zusätzlich oder anstelle dieser Substitution können auch die Ethylengylkoleinheiten durch längerkettige Diole, insbesondere C3- bis C6-Alkandiole, wie beispielsweise 1,4-Butandiol oder 1,6-Hexandiol ersetzt werden.Lower melting point polyesters can be obtained by substituting a portion of the terephthalic acid units in the PET for aliphatic dicarboxylic acid units, especially adipic acid units, to synthesize the polyesters. In addition to or instead of this substitution, the ethylene glycol units can also be replaced by longer-chain diols, in particular C 3 to C 6 alkanediols, for example 1,4-butanediol or 1,6-hexanediol.
Zur Ausführung der Erfindung bevorzugte Polyester weisen mindestens zwei verschiedene Dicarbonsäureeinheiten (X) auf. Sie umfassen mindestens 5 bis 80 mol % Terephthalsäureeinheiten (X1) sowie 20 bis 95 mol % Einheiten aus aliphatischen 1, ω-Dicarbonsäuren (X2) mit 4 bis 10 Kohlenstoffatomen. Die Gesamtmenge von (X1) und (X2) beträgt hierbei mindestens 80 mol %, wobei die %-Angaben jeweils auf die Gesamtmenge aller Dicarbonsäureeinheiten im Polyester bezogen sind.Polyesters preferred for carrying out the invention have at least two different dicarboxylic acid units (X). They comprise at least 5 to 80 mol% of terephthalic acid units (X1) and 20 to 95 mol% of units of aliphatic 1, ω-dicarboxylic acids (X2) having 4 to 10 carbon atoms. The total amount of (X1) and (X2) is at least 80 mol%, the% figures being based on the total amount of all dicarboxylic acid units in the polyester.
Bei den aliphatischen 1,ω-Dicarbonsäureeinheiten (X2) kann es sich beispielsweise um Bernsteinsäure, Glutarsäure, Adipinsäure oder Sebacinsäure handeln. Bevorzugt handelt es sich um Adipinsäure.The aliphatic 1, ω-dicarboxylic acid units (X2) may, for example, be succinic acid, glutaric acid, adipic acid or sebacic acid. It is preferably adipic acid.
Neben den Dicarbonäureeinheiten (X1) und (X2) können noch davon verschiedene Dicarbonsäureinheiten anwesend sein. Zu nennen sind beispielsweise andere aromatische Dicarbonsäureeinheiten und/oder cycloaliphatische Dicarbonsäureeinheiten. Selbstverständlich können auch Gemische verschiedener Dicarbonäureeinheiten verwendet werden.In addition to the dicarboxylic acid units (X1) and (X2), various dicarboxylic acid units may still be present therefrom. To name a few, for example, are other aromatic ones Dicarboxylic acid units and / or cycloaliphatic dicarboxylic acid units. Of course, mixtures of different dicarboxylic acid units can be used.
Bevorzugt beträgt die Menge an Terephthalsäureeinheiten (X1) 20 bis 70 mol % und die Menge an (X2) 30 bis 80 mol %. Bevorzugt beträgt die Summe von (X1) und (X2) mindestens 90 mol %, besonders bevorzugt mindestens 98 mol % und ganz besonders bevorzugt 100 mol %.Preferably, the amount of terephthalic acid units (X1) is 20 to 70 mol% and the amount of (X2) is 30 to 80 mol%. Preferably, the sum of (X1) and (X2) is at least 90 mol%, more preferably at least 98 mol%, and most preferably 100 mol%.
Die Dioleinheiten (Y) werden ausgewählt aus der Gruppe der aliphatischen, cycloliphatischen und/oder Polyetherdiolen, wobei 50 bis 100 mol % aliphatischer 1,ω-Diole (Y1) vorhanden sind, und die %-Angaben auf die Gesamtmenge aller Diole bezogen sind.The diol units (Y) are selected from the group of aliphatic, cycloliphatic and / or polyether diols, wherein 50 to 100 mol% of aliphatic 1, ω-diols (Y1) are present, and the percentages are based on the total amount of all diols.
Bei den aliphatischen Diolen mit 4 bis 10 Kohlenstoffatomen (Y1) kann es sich beispielsweise um 1,4-Butandiol, 1,5-Butandiol oder 1,6-Hexandiol handeln. Bevorzugt handelt es sich bei (Y1) um 1,4-Butandiol.The aliphatic diols having 4 to 10 carbon atoms (Y1) may be, for example, 1,4-butanediol, 1,5-butanediol or 1,6-hexanediol. Preferably, (Y1) is 1,4-butanediol.
Beispiele für Polyetherdiole umfassen Diethylenglykol, Triethylenglykol, Polyethylenglykol oder Polypropylenglykol. Beispiele für cycloaliphatische Diole umfassen Cyclopentan- oder Cyclohexandiole. Selbstverständlich können auch aliphatische Diole, welche nicht der Definition (Y1) entsprechen eingesetzt werden. Beispiele umfassen insbesondere Ethylenglykol oder Propylenglykol.Examples of polyether diols include diethylene glycol, triethylene glycol, polyethylene glycol or polypropylene glycol. Examples of cycloaliphatic diols include cyclopentane or cyclohexanediols. Of course, aliphatic diols which do not correspond to the definition (Y1) can also be used. Examples include in particular ethylene glycol or propylene glycol.
Die Polyester können selbstverständlich auch noch weitere Komponenten zur Feinsteuerung der Eigenschaften umfassen. Beispiele umfassen Baueinheiten, welche noch zusätzliche funktionelle Gruppen aufweisen. Zu nennen sind hier insbesondere Aminogruppen. Weiterhin zu nennen sind Bausteine zur Kettenverlängerung.The polyesters may of course also include other components for fine control of the properties. Examples include building blocks which have additional functional groups. Particular mention should be made here of amino groups. Also to be mentioned are building blocks for chain extension.
Bevorzugte Polyester der genannten Art weisen einen Schmelzpunkt von 50 bis 200°C auf. Bevorzugt beträgt der Schmelzpunkt 60 bis 180 °C, besonders bevorzugt 80 bis 160°C, ganz besonders bevorzugt 100 bis 150°C und beispielsweise 110-130°C. Die Glasübergangstemperatur beträgt bevorzugt 20-35°C, bevorzugt 25-30°C, ohne dass die Erfindung damit darauf beschränkt sein soll.Preferred polyesters of the type mentioned have a melting point of 50 to 200 ° C. Preferably, the melting point is 60 to 180 ° C, more preferably 80 to 160 ° C, most preferably 100 to 150 ° C and for example 110-130 ° C. The glass transition temperature is preferably 20-35 ° C., preferably 25-30 ° C., without the invention being restricted thereto.
Das zahlenmittlere Molekulargewicht Mn sollte in der Regel 5000 bis 50000 g/mol, bevorzugt 10000 bis 30000 g/mol betragen. Besonders bewährt haben sich 20.000 bis 25.000 g/mol. Das Verhältnis Mw / Mn beträgt bevorzugt 3 bis 6, beispielsweise 4 bis 5. Weiterhin vorteilhaft kann der Polyester eine Schmelzflussrate MFR von 2 - 6 g /10 min (ISO 1133, 190°C, 2,16 kg) aufweisen. Eine bevorzugte Massendichte beträgt 1,2 - 1,35 g/cm3, besonders bevorzugt 1,22 -1,30 g/cm3. Die bevorzugte Vicat-Erweichungstemperatur beträgt 75 bis 85°C, besonders bevorzugt 78-82°C (VST A/50, ISO 306).The number average molecular weight M n should generally be 5000 to 50 000 g / mol, preferably 10000 to 30 000 g / mol. Have proven particularly useful 20,000 to 25,000 g / mol. The ratio M w / M n is preferably 3 to 6, for example 4 to 5. It is furthermore advantageous for the polyester to have a melt flow rate MFR of 2 to 6 g / 10 min (ISO 1133, 190 ° C., 2.16 kg). A preferred bulk density is from 1.2 to 1.35 g / cm 3, more preferably 1.22 -1.30 g / cm 3. The preferred Vicat softening temperature is 75 to 85 ° C, more preferably 78-82 ° C (VST A / 50, ISO 306).
Weitere Einzelheiten zur Herstellung derartiger Polyester sind in
Selbstverständlich können auch verschiedene Polyester als Additiv eingesetzt werden. Bevorzugt beträgt die Menge der Polyester 1 bis 15 Gew. %, besonders bevorzugt 2 bis 10 Gew. % und beispielsweise 3 bis 7 Gew. %.Of course, various polyesters can be used as an additive. The amount of the polyesters is preferably from 1 to 15% by weight, more preferably from 2 to 10% by weight and, for example, from 3 to 7% by weight.
Neben dem genannten Polyester kann das bevorzugt verwendete Polypropylen als Additiv zusätzlich 0,1 bis 10 Gew. % mindestens eines Blockcopolymers, welches mindestens einen unpolaren Block mit einer zahlenmittleren molaren Masse Mn von mindestens 200 g/mol und einen polaren Block mit einer zahlenmittleren molaren Masse Mn von mindestens 500 g/mol umfasst, enthalten. Bevorzugt beträgt die Menge des Blockcopolymers 0,2 bis 6 Gew. %, besonders bevorzugt 0,5 bis 4 Gew. % und beispielsweise 0,75 bis 3 Gew. %.In addition to the stated polyester, the polypropylene preferably used as an additive in addition 0.1 to 10 wt.% Of at least one block copolymer having at least one nonpolar block having a number average molecular weight M n of at least 200 g / mol and a polar block with a number average molar Mass M n of at least 500 g / mol comprises included. The amount of block copolymer is preferably from 0.2 to 6% by weight, more preferably from 0.5 to 4% by weight, and for example from 0.75 to 3% by weight.
In einer bevorzugten Ausführungsform der Erfindung handelt es sich um einen unpolaren Block, welcher im Wesentlichen aus Isobuteneinheiten aufgebaut ist, sowie um einen polaren Block, welcher im Wesentlichen aus Oxyalkyleneinheiten aufgebaut ist, und dessen mittlere molare Masse Mn mindestens 1000 g/mol beträgt. Bei den Oxyalkyleneinheiten handelt es sich bevorzugt um Ethylenoxideinheiten. Die Blockcopolymere sind bevorzugt Dreiblockcopolymere mit einem Mittelblock aus Oxyalkyleneinheiten und zwei terminalen Blöcken aus Isobuten, wobei die Blöcke über geeignete verknüpfende Einheiten miteinander verbunden sind.In a preferred embodiment of the invention is a non-polar block, which is composed essentially of isobutene units, and a polar block which is composed essentially of oxyalkylene units, and whose average molar mass M n is at least 1000 g / mol. The oxyalkylene units are preferably ethylene oxide units. The block copolymers are preferably triblock copolymers having a middle block of oxyalkylene units and two terminal blocks of isobutene, the blocks being linked together via suitable linking units.
In der Regel weisen die polaren Blöcke jeweils eine mittlere molare Masse Mn von 1000 bis 20000 g/mol auf. Bevorzugt beträgt Mn 1250 bis 18000 g/mol, besonders bevorzugt 1500 bis 15000 g/mol und ganz besonders bevorzugt 2500 bis 8000 g/mol.In general, the polar blocks each have an average molar mass M n of 1000 to 20,000 g / mol. M n is preferably from 1250 to 18000 g / mol, more preferably from 1500 to 15000 g / mol, and most preferably from 2500 to 8000 g / mol.
Die unpolaren Blöcke weisen in der Regel jeweils eine mittlere molare Masse Mn von 200 bis 10000 g/mol auf. Bevorzugt beträgt Mn 300 bis 8000 g/mol, besonders bevorzugt 400 bis 6000 g/mol und ganz besonders bevorzugt 500 bis 5000 g/mol.The non-polar blocks generally each have an average molar mass M n of 200 to 10,000 g / mol. M n is preferably from 300 to 8000 g / mol, particularly preferably from 400 to 6000 g / mol and very particularly preferably from 500 to 5000 g / mol.
Bei den Blockcopolymeren kann es sich um Zweiblock-, Dreiblock- oder Multiblockcopolymere handeln. Bevorzugt handelt es sich um Zweiblock- und Dreiblockcopolymere, insbesondere um Dreiblockcopolymere, welche einen mittelständigen polaren Block sowie zwei terminale unpolare Blöcke aufweisen. Es kann sich auch um Mischungen aus Zweiblock- und Dreiblockcopolymeren handeln.The block copolymers may be diblock, triblock or multiblock copolymers. Preference is given to diblock and triblock copolymers, in particular triblock copolymers which have a central polar block and two terminal nonpolar blocks. It may also be mixtures of diblock and triblock copolymers.
Weitere Einzelheiten zu derartigen Blockcopolymeren und deren Herstellung sind in
Die genannten Blockcopolymere wirken mit dem Polyester synergistisch zusammen und bewirken eine besonders gute Anfärbbarkeit. Bevorzugt ist daher ein Additivsystem, welches mindestens einen Polyester sowie mindestens ein Blockcopolymer der genannten Art umfasst. Es ist aber auch möglich, nur einen Polyester oder nur das besagte Blockcopolymer als Additiv einzusetzen.The abovementioned block copolymers interact synergistically with the polyester and bring about particularly good dyeability. Preference is therefore given to an additive system comprising at least one polyester and at least one block copolymer of the type mentioned. But it is also possible to use only a polyester or only said block copolymer as an additive.
Das Einarbeiten der Additive in das undotierte Polypropylen sowie die Verarbeitung zu Fasern kann nach dem Fachmann bekannten Methoden erfolgen, beispielsweise durch Schmelzextrusion. Einzelheiten hierzu sind beispielsweise in
Das Einfärben und/oder Bedrucken der textilen Materialien kann nach dem Fachmann prinzipiell bekannten Methoden erfolgen. Hierzu können bevorzugt Dispersionsfarbstoffe verwendet werden. Der Begriff "Dispersionsfarbstoff" ist dem Fachmann bekannt. Dispersionsfarbstoffe sind Farbstoffe mit einer niedrigen Wasserlöslichkeit, welche in disperser, kolloider Form zum Färben, insbesondere zum Färben von Fasern und textilen Materialien eingesetzt werden. Einzelheiten zum Färben und/oder Bedrucken von textilen Materialien sind beispielsweise in
Zur erfindungsgemäßen Nachbehandlung wird eine wässrige Formulierung mindestens eines anionischen und/oder nichtionischen Tensids (A) sowie mindestens eines Pfropfcopolymers (B) eingesetzt. Im Bereich der Textiltechnik werden Formulierungen zum Behandeln von Textilien häufig auch als "Flotte" bezeichnet.For the after-treatment according to the invention, an aqueous formulation of at least one anionic and / or nonionic surfactant (A) and at least one graft copolymer (B) is used. In the field of textile technology, formulations for treating textiles are often referred to as "liquor".
Die eingesetzte wässrige Formulierung umfasst als Lösemittel im Wesentlichen Wasser. Daneben können optional noch mit Wasser mischbare Lösemittel anwesend sein, beispielsweise Alkohole wie Methanol, Ethanol oder Propanol. Im Regelfalle umfasst das Lösemittel mindestens 80 Gew. % Wasser bezüglich der Summe aller Lösemittel der wässrigen Formulierung, bevorzugt mindestens 90 Gew. %, besonders bevorzugt mindestens 95 Gew. %, und ganz besonders bevorzugt wird nur Wasser als Lösemittel eingesetzt.The aqueous formulation used essentially comprises water as solvent. In addition, optional water-miscible solvents may be present, for example, alcohols such as methanol, ethanol or propanol. As a rule, the solvent comprises at least 80% by weight of water with respect to the sum of all solvents of the aqueous formulation, preferably at least 90% by weight, more preferably at least 95% by weight, and very particularly preferably only water is used as solvent.
Als Komponente (A) enthält die Formulierung weiterhin mindestens ein anionisches und/oder nichtionisches Tensid (A). Bevorzugt wird mindestens ein nichtionisches Tensid eingesetzt. Selbstverständlich können auch Gemische mehrerer verschiedener Tenside eingesetzt werden.As component (A), the formulation furthermore contains at least one anionic and / or nonionic surfactant (A). At least one nonionic surfactant is preferred used. Of course, mixtures of several different surfactants can be used.
Beispiele geeigneter nichtionischer Tenside umfassen Tenside (A1) der allgemeinen Formel (I) R1-O-(CH2-CH(R2)-O)n-H. Hierbei steht n für eine Zahl von 3 bis 25, bevorzugt 4 bis 15 und besonders bevorzugt 5 bis 10. R1 steht für einen aliphatischen und/oder aromatischen, geradkettigen oder verzweigten Kohlenwasserstoffrest mit 8 bis 20 Kohlenstoffatomen, bevorzugt 10 bis 18 Kohlenstoffatomen und besonders bevorzugt 12 bis 16 Kohlenstoffatomen. Bevorzugt handelt es sich bei R1 um einen geradkettigen oder verzweigten, aliphatischen Kohlenwasserstoffrest. Beispielsweise kann es sich bei R1 um von Fettalkoholen oder bevorzugt Oxoalkoholen abgeleitete Reste handeln. Die Reste R2 stehen unabhängig voneinander für Wasserstoff oder einen Alkylrest mit 1 bis 6 Kohlenstoffatomen, bevorzugt Wasserstoff oder Methyl und besonders bevorzugt Wasserstoff. Sofern mehrere verschiedene Reste R2 anwesend sind, sollte es sich bei mindestens 60 %, bevorzugt mindestens 80 % der Reste R2 um Wasserstoff handeln, wobei diese Angabe auf die Gesamtzahl aller Reste R2 bezogen ist. Nichtionische Tenside (A1) sind kommerziell erhältlich.Examples of suitable nonionic surfactants include surfactants (A1) of the general formula (I) R 1 -O- (CH 2 -CH (R 2 ) -O) n -H. Here, n is a number from 3 to 25, preferably 4 to 15 and more preferably 5 to 10. R 1 is an aliphatic and / or aromatic, straight-chain or branched hydrocarbon radical having 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms and especially preferably 12 to 16 carbon atoms. R 1 is preferably a straight-chain or branched, aliphatic hydrocarbon radical. For example, R 1 may be radicals derived from fatty alcohols or preferably oxoalcohols. The radicals R 2 independently of one another represent hydrogen or an alkyl radical having 1 to 6 carbon atoms, preferably hydrogen or methyl and particularly preferably hydrogen. If several different radicals R 2 are present, it should be at least 60%, preferably at least 80% of the radicals R 2 is hydrogen, this statement being based on the total number of all radicals R 2 . Nonionic surfactants (A1) are commercially available.
Weitere Beispiele für Tenside umfassen schaumarme, nichtionische Tenside (A2). Derartige Tenside sind dem Fachmann prinzipiell bekannt.Further examples of surfactants include low-foaming nonionic surfactants (A2). Such surfactants are known in principle to the person skilled in the art.
Bevorzugt kann es sich bei (A2) um nichtionische Tenside der allgemeinen Formel (II) R1-O-(CH2-CH(R3)-O)m-R4 handeln, wobei R1 wie oben definiert ist. m steht für eine Zahl von 3 bis 30, bevorzugt 5 bis 25 und besonders bevorzugt 10 bis 20. Bei R3 kann es sich um Wasserstoff, oder einen Alkylrest mit 1 bis 6 Kohlenstoffatomen, bevorzugt Wasserstoff oder Methyl handeln, wobei es sich bei mindestens 60 %, bevorzugt mindestens 80 % der Reste R3, bezogen auf die Gesamtzahl aller Reste R3 um Wasserstoff handelt. Besonders bevorzugt handelt es sich bei R3 ausschließlich um Wasserstoff. Bei der Gruppe R4 handelt es sich um eine Gruppe, welche stärker hydrophob ist als die Gruppe -(CH2-CH(R3)-O)m- in Formel (II). Bei R4 kann es sich beispielsweise um eine Gruppe -(CH2-CH(R5)-O)z-H handeln, wobei z für eine Zahl von 1 bis 15, bevorzugt 2 bis 10 steht. R5 steht für Wasserstoff oder einen Alkylrest mit 1 bis 6 Kohlenstoffatomen, bevorzugt Wasserstoff, Methyl oder Ethyl mit der Maßgabe, dass es sich bei mindestens 60 % der Gruppen R5 bezogen auf die Gesamtzahl aller Gruppen R5 um einen Alkylrest mit 1 bis 6 Kohlenstoffatomen handelt. Bevorzugt handelt es sich bei R5 um Methyl. Derartige Blockcopolymere lassen sich erhalten, indem man den Starter-Alkohol zunächst mit Ethylenoxid oder mindestens 60 mol % Ethylenoxid enthaltenden Alkylenoxidgemischen alkoxyliert und den erhaltenen Alkoxyalkohol in einer zweiten Stufe mit Propylenoxid und/oder höheren Alkylenoxiden oder mindestens 60 mol % Propylenoxid und/oder höheren Alkylenoxide enthaltenden Alkylenoxidgemischen weiter alkoxyliert.Preferably, (A2) may be nonionic surfactants of the general formula (II) R 1 -O- (CH 2 -CH (R 3 ) -O) m -R 4 , wherein R 1 is as defined above. m is a number from 3 to 30, preferably 5 to 25 and particularly preferably 10 to 20. R 3 may be hydrogen, or an alkyl radical having 1 to 6 carbon atoms, preferably hydrogen or methyl, wherein at least 60%, preferably at least 80% of the radicals R 3 , based on the total number of all radicals R 3 is hydrogen. Particularly preferably, R 3 is exclusively hydrogen. The group R 4 is a group which is more hydrophobic than the group - (CH 2 -CH (R 3 ) -O) m - in formula (II). For example, R 4 may be a group - (CH 2 -CH (R 5 ) -O) z -H, where z is a number from 1 to 15, preferably from 2 to 10. R 5 is hydrogen or an alkyl radical having 1 to 6 carbon atoms, preferably hydrogen, methyl or ethyl, with the proviso that at least 60% of the groups R 5, based on the total number of all groups R 5, is an alkyl radical having 1 to 6 Carbon atoms is. Preferably, R 5 is methyl. Such block copolymers can be obtained by first alkoxylating the starter alcohol with ethylene oxide or at least 60 mol% of ethylene oxide-containing alkylene oxide mixtures and the resulting alkoxy alcohol in a second stage with propylene oxide and / or higher alkylene oxides or at least 60 mol% propylene oxide and / or higher alkylene oxides further alkoxylated alkylene oxide mixtures.
Weitere Beispiele für R4 umfassen geradkettige oder verzweigte Alkylreste mit 1 bis 20 Kohlenstoffatomen, bevorzugt 6 bis 14 Kohlenstoffatomen oder Gruppen der Formel - CO-R4, wobei R4 die genannte Bedeutung hat. Derartige Strukturen lassen sich durch Veretherung oder Veresterung entsprechender nichtionischer Tenside erhalten.Further examples of R 4 include straight-chain or branched alkyl radicals having 1 to 20 carbon atoms, preferably 6 to 14 carbon atoms, or groups of the formula --CO-R 4 , where R 4 has the meaning mentioned. Such structures can be obtained by etherification or esterification of corresponding nonionic surfactants.
Weitere Beispiele schaumarmer nichtionischer Tenside sind beispielsweise in
Der Begriff "Pfropfcopolymere" wird im üblichen Sinne für Copolymere verwendet, welche über ein geradkettiges oder verzweigtes Polymergerüst (Hauptkette) verfügen sowie davon abzweigende (aufgepfropfte) Seitenketten, welche von ihrer Länge her bereits selbst als Oligomere oder Polymere bezeichnet werden können. Das Polymergerüst und die Seitenketten sind chemisch unterschiedlicher Natur.The term "graft copolymers" is used in the usual sense for copolymers which have a straight-chain or branched polymer backbone (main chain) and branching off (grafted) side chains, which may already be termed oligomers or polymers by their length. The polymer backbone and the side chains are chemically different in nature.
Die geradkettige oder verzweigte Hauptkette ist hydrophil. Sie weist N- und/oder O-Atome auf, welche bevorzugt Bestandteil der Hauptkette selbst sind. Die N- und/oder O-Atome der Hauptkette sind durch Kohlenwasserstoffgruppen, bevorzugt 2 bis 4 Kohlenwasserstoffgruppen umfassende Gruppen voneinander getrennt. Bevorzugt kann es sich um 1,2-Ethylen-, 1,2-Propylen-, 1,3-Proyplen, 1,2-Butylen- oder 1,4-Butylengruppen handeln.The straight-chain or branched main chain is hydrophilic. It has N and / or O atoms, which are preferably part of the main chain itself. The N and / or O atoms of the main chain are separated from each other by groups of hydrocarbons, preferably from 2 to 4 hydrocarbon groups. They may preferably be 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene or 1,4-butylene groups.
Gemäβ der Erfindung handelt es sich bei dem Pfropfcopolymer (B) um ein Pfropfcopolymer (B1) mit einer Hauptkette, welche im Wesentlichen aus Alkylenoxideinheiten besteht, wobei die Hauptkette ein zahlenmittleres Molekulargewicht Mn von 300 bis 60000 g/mol, bevorzugt 600 bis 10000 g/mol und besonders bevorzugt 2000 bis 8000 g/mol aufweist.According to the invention, the graft copolymer (B) is a graft copolymer (B1) having a main chain consisting essentially of alkylene oxide units, the main chain having a number average molecular weight M n of 300 to 60,000 g / mol, preferably 600 to 10,000 g / mol and more preferably 2000 to 8000 g / mol.
Der Begriff "im Wesentlichen" soll hierbei bedeuten, dass die Hauptkette im Regelfalle mindestens 90 mol % Alkylenoxideinheiten umfasst. Bevorzugt handelt es sich um Ethylenoxid- und/oder Propylenoxideinheiten, wobei es sich in der Regel bei mindestens 50 mol %, bevorzugt mindestens 70 mol % und besonders bevorzugt mindestens 90 mol % der Alkylenoxideinheiten um Ethylenoxideinheiten handelt. Besonders bevorzugt handelt es sich bei der Hauptkette um Polyethylenglykol.The term "essentially" is intended here to mean that the main chain generally comprises at least 90 mol% of alkylene oxide units. They are preferably ethylene oxide and / or propylene oxide units, which are generally at least 50 mol%, preferably at least 70 mol% and particularly preferably at least 90 mol% of the alkylene oxide units are ethylene oxide units. Particularly preferably, the main chain is polyethylene glycol.
Die Seitenketten bestehen im Wesentlichen aus ethylenisch ungesättigten Monomeren. Bevorzugt handelt es sich hierbei um funktionelle Gruppen aufweisende ethylenisch ungesättigte Monomere. Geeignete Monomere umfassen Vinylderivate oder Acrylderivate wie beispielsweise Vinylacetat, Vinylamin, Vinylpyrrolidon, Vinylimidaol, Vinylester, Acrylsäure oder Acrylsäureester. Gemäβ der Erfindung handelt es sich bei den ethylenisch ungesättigten Monomeren der Seitenketten um mindestens 50 mol % Vinylacetat, bevorzugt mindestens 80 mol % Vinylacetat und besonders bevorzugt ausschließlich um Vinylacetat.The side chains consist essentially of ethylenically unsaturated monomers. These are preferably ethylenically unsaturated monomers having functional groups. Suitable monomers include vinyl derivatives or acrylic derivatives such as vinyl acetate, vinylamine, vinylpyrrolidone, vinylimidazole, vinyl esters, acrylic acid or acrylic esters. According to the The invention relates to the ethylenically unsaturated monomers of the side chains at least 50 mol% vinyl acetate, preferably at least 80 mol% of vinyl acetate and particularly preferably exclusively vinyl acetate.
Die Propfcopolymere (B1) sind in prinzipiell bekannter Art und Weise herstellbar, indem man die Polymerisation der ethylenisch ungesättigten Monomere der Seitenketten in Gegenwart von Polyalkylenoxiden, insbesondere Polyethylenglykol durchführt. Das Mengenverhältnis von Polyalkylenoxiden zu ethylenisch ungesättigten Monomeren wird bevorzugt so gewählt, dass das Pfropfcopolymer 30 bis 80 Gew. % Polyalkylenoxid, bevorzugt 30 bis 50 Gew. % Polyalkylenoxid umfasst.The graft copolymers (B1) can be prepared in a manner known in principle by carrying out the polymerization of the ethylenically unsaturated monomers of the side chains in the presence of polyalkylene oxides, in particular polyethylene glycol. The quantitative ratio of polyalkylene oxides to ethylenically unsaturated monomers is preferably selected such that the graft copolymer comprises 30 to 80% by weight of polyalkylene oxide, preferably 30 to 50% by weight of polyalkylene oxide.
Besonders bevorzugt handelt es sich bei (B1) um ein Propfcopolymer aus Polyethylenglykol und Vinylacetat mit 30 bis 50 Gew. % Polyethylenglykol, wobei die Hauptkette ein zahlenmittleres Molekulargewicht Mn von 4000 bis 8000 g/mol aufweist.Particularly preferred is (B1) is a graft copolymer of polyethylene glycol and vinyl acetate with 30 to 50 wt.% Polyethylene glycol, wherein the main chain has a number average molecular weight M n of 4000 to 8000 g / mol.
In einer zweiten Ausführungsform der Erfindung handelt es sich bei dem Pfropfcopolymer (B) um ein Pfropfcopolymer (B2) mit einer Hauptkette, welche im Wesentlichen aus Alkylenimineinheiten besteht, wobei die Hauptkette ein zahlenmittleres Molekulargewicht Mn von 300 bis 10000 g/mol, bevorzugt 300 bis 1000 g/mol aufweist. Bei der Hauptkette handelt es sich bevorzugt um Polyethylenimin, besonders bevorzugt um hochverzweigtes Polyethylenimin, wie es typischerweise bei der Polymerisation von Ethylenimin erhalten wird. Bei den Seitenketten handelt es sich um Polyethereinheiten. Derartige Propfcopolymere (B2) können in prinzipiell bekannter Art und Weise durch Alkoxylierung von Polyethylenimin erhalten werden, insbesondere mit Ethylenoxid, Propylenoxid, Butylenoxid oder Mischungen davon, bevorzugt Ethylenoxid und/oder Propylenoxid. Sofern verschiedene Alkylenoxide eingesetzt werden, können diese statisch oder auch als Blockcopolymere vorliegen. Die Zahl der aufgepropften Alkylenoxideinheiten liegt im Regelfalle bei 5 bis 100 pro Seitengruppe bevorzugt 5 bis 50.In a second embodiment of the invention, the graft copolymer (B) is a graft copolymer (B2) having a main chain consisting essentially of alkyleneimine units, wherein the main chain has a number average molecular weight M n of 300 to 10,000 g / mol, preferably 300 up to 1000 g / mol. The backbone is preferably polyethyleneimine, more preferably hyperbranched polyethylenimine typically obtained in the polymerization of ethyleneimine. The side chains are polyether units. Such graft copolymers (B2) can be obtained in a manner known in principle by alkoxylation of polyethyleneimine, in particular with ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, preferably ethylene oxide and / or propylene oxide. If different alkylene oxides are used, they may be present statically or else as block copolymers. The number of grafted Alkylenoxideinheiten is usually at 5 to 100 per side group preferably 5 to 50.
Über die Komponenten (A) und (B) hinaus kann die wässrige Formulierung optional noch weitere Komponenten (C) als Hilfsmittel umfassen. Beispiele derartiger Komponenten umfassen Schaumdämpfer, Netz- und Entlüftungsmittel oder Dispergiermittel.In addition to the components (A) and (B), the aqueous formulation may optionally comprise further components (C) as auxiliary agents. Examples of such components include foam suppressants, wetting and deaerating agents or dispersants.
In einer bevorzugten Ausführungsform der Erfindung umfasst die wässrige Formulierung zusätzlich mindestens einen Schaumdämpfer (C1). Hierbei kann es sich beispielsweise um Schaumdämpfer auf Basis von Polysiloxanen handeln, wie beispielsweise Polydimethylsiloxane. Bevorzugt handelt es sich um siliciumfreie Schaumdämpfer wie Fettalkoholderivate, disperse Kieselsäure oder Polyether wie Polypropylenglykol, Poly-(Propylenglykol-Ethylenglykol)-Copolymere oder Polypropylenglykolderivate. Ferner beschrieben wird hier eine wässrige Formulierung, welche zusätzlich mindestens ein Benetzungshiffsmittel (C2) umfasst. Beispiele für Benetzungshilfsmittel umfassen primäre, sekundäre oder tertiäre Phosphorsäureester von Alkoholen, wie beispielsweise Phosphorsäureester von 2-Ethylhexylalkohol. Auch Sulfosuccinate oder weitere kleinmolekulare Tenside können dafür eingesetzt werden.In a preferred embodiment of the invention, the aqueous formulation additionally comprises at least one foam damper (C1). These may, for example, be foam silencers based on polysiloxanes, such as, for example, polydimethylsiloxanes. Preference is given to silicon-free foam suppressants such as fatty alcohol derivatives, disperse silicic acid or polyethers such as polypropylene glycol, poly (propylene glycol-ethylene glycol) copolymers or polypropylene glycol derivatives. Also described here is an aqueous formulation which additionally comprises at least one wetting agent (C2). Examples of wetting aids include primary, secondary or tertiary phosphoric acid esters of alcohols, such as phosphoric acid esters of 2-ethylhexyl alcohol. Sulfosuccinates or other small-molecule surfactants can also be used for this purpose.
Eine Formulierung kann mindestens einen Schaumdämpfer (C1) und mindestens ein Benetzungshilfsmittel (C2) umfassen.A formulation may comprise at least one sponge damper (C1) and at least one wetting aid (C2).
Die Konzentrationen der Komponenten der Formulierung werden vom Fachmann je nach den gewünschten Eigenschaften der Formulierung bestimmt.The concentrations of the components of the formulation are determined by those skilled in the art according to the desired properties of the formulation.
Die Konzentration der Tenside (A) in der Formullerung beträgt in der Regel 0,01 g/l bis 5 g/l. bevorzugt 0,02 g/l bis 2 g/l, besonders bevorzugt 0.05 g/l bis 1 g/l und ganz besonders bevorzugt 0,1 g/l bis 0.5 g/l.The concentration of the surfactants (A) in the Formullerung is usually 0.01 g / l to 5 g / l. preferably 0.02 g / l to 2 g / l, more preferably 0.05 g / l to 1 g / l and most preferably 0.1 g / l to 0.5 g / l.
Das Gewichtsverhältnis schaumarmer Tenside (A2) zur Gesamtmenge aller Tenside sollte in der Regel mindestens 1:1 betragen.The weight ratio of low-foaming surfactants (A2) to the total amount of all surfactants should as a rule be at least 1: 1.
Die Konzentration der Pfropfcopolymere (B) in der Formulierung beträgt in der Regel 0.5 g/l bis 10 g/l. bevorzugt 0,1 g/l bis 5 g/l, besonders bevorzugt 0,2 g/l bis 2 g/l und ganz besonders bevorzugt 0,3 g/l bis 1 g/l.The concentration of the graft copolymers (B) in the formulation is generally 0.5 g / l to 10 g / l. preferably 0.1 g / l to 5 g / l, more preferably 0.2 g / l to 2 g / l and most preferably 0.3 g / l to 1 g / l.
In einer bevorzugten Ausführungsform beträgt das Gewichtsverhältnis von Pfropfcopolymeren (B) zu den Tensiden (A) in der Formulierung mindestens 1 : 1. Bevorzugt beträgt das Gewichtsverhältnis (B) / (A) 1:1 bis 20:1, besonders bevorzugt 2:1 bis 10:1 und beispielsweise 3:1 bis 8:1.In a preferred embodiment, the weight ratio of graft copolymers (B) to surfactants (A) in the formulation is at least 1: 1. Preferably, the weight ratio (B) / (A) is 1: 1 to 20: 1, more preferably 2: 1 to 10: 1 and for example 3: 1 to 8: 1.
Die Konzentration an Hilfsmitteln (C) beträgt -sofern vorhanden- in der Regel bis 5 g/l, bevorzugt 0.01 g/l bis 2 g/l, besonders bevorzugt 0,02 g/l bis 1 g/l und ganz besonders bevorzugt 0,05 g/l bis 0,6 g/l.The concentration of auxiliaries (C), if present, is generally up to 5 g / l, preferably 0.01 g / l to 2 g / l, more preferably 0.02 g / l to 1 g / l and most preferably 0 , 05 g / l to 0.6 g / l.
Selbstverständlich kann auch zunächst ein Konzentrat hergestellt werden, welches zum Einsatz entsprechend verdünnt wird.Of course, first of all a concentrate can be prepared, which is diluted accordingly for use.
Das erfindungsgemäße Verfahren zum Nachbehendeln gefärbter und/oder bedruckter textiler Materialien ist ein Teilschritt im Zuge des Herstellungsverfahrens textiler Materialien und wird im Regelfalle unmittelbar im Anschluss an das Einfärben und/oder Bedrucken der textilen Materialien durchgeführt, typischerweise beim Textilfärber selbst, ohne dass damit ausgeschlossen werden soll, das Verfahren auch erst zu einem späteren Zeitpunkt durchzuführen. In der Regel werden die textilen Materialien nach dem Färben direkt, d.h. ohne Trocknen, nachgewaschen, um die überschüssige Farbe vom Textil zu entfernen. Es ist aber auch möglich, zuerst zu trocknen und anschließend nachzuwaschen.The process according to the invention for post-dying colored and / or printed textile materials is a partial step in the course of the production process of textile materials and is generally carried out immediately after the dyeing and / or printing of the textile materials, typically with the textile dye itself, without being ruled out should, the procedure also until a later Time to perform. In general, the textile materials after dyeing directly, ie without drying, washed to remove the excess color from the textile. But it is also possible to dry first and then wash.
Zur Ausführung des erfindungsgemäßen Verfahrens wird das textile Material mit der wässrigen Formulierung ("Flotte") behandelt, beispielsweise durch einfaches Eintauchen. Das Gewichtsverhältnis von textilen Materialien zur wässrigen Formulierung ("Flottenverhältnis") beträgt in der Regel 1:3 bis 1:40, bevorzugt 1:5 bis 1:10.To carry out the process according to the invention, the textile material is treated with the aqueous formulation ("liquor"), for example by simple immersion. The weight ratio of textile materials to the aqueous formulation ("liquor ratio") is generally 1: 3 to 1:40, preferably 1: 5 to 1:10.
Die Behandlung wird in der Regel bei 20 bis 100°C, bevorzugt 30 bis 90°C und besonders bevorzugt 40 bis 70°C durchgeführt. Die Dauer der Nachbehandlung beträgt in der Regel 5 bis 60 min, bevorzugt 10 bis 30 min und besonders bevorzugt 15 bis 25 min.The treatment is usually carried out at 20 to 100 ° C, preferably 30 to 90 ° C and particularly preferably 40 to 70 ° C. The duration of the aftertreatment is generally 5 to 60 minutes, preferably 10 to 30 minutes and particularly preferably 15 to 25 minutes.
Nach der Behandlung wird das textile Material in der Regel einmal oder mehrere Male mit Wasser nachgespült.After the treatment, the textile material is usually rinsed once or several times with water.
Das erfindungsgemäße Verfahren hat gegenüber der reduktiven Nachreinigung mehrere Vorteile, insbesondere bei der Nachbehandlung von textilen Materialien, welche Polypropylen enthalten: Die überschüssige Farbe wird von der Oberfläche des Gewebes entfernt ohne die Farbtiefe der Färbung signifikant zu verschlechtern. Es wirkt also nur an der Oberfläche und dringt nicht in das Innere des Fasermaterials ein. Dies ist nicht nur ein Vorteil gegenüber den reduktiven Verfahren, sondern auch gegenüber der Nachreinigung mit Tensiden. Da diese niedermolekular sind, können Tenside in das Innere von polymeren Materialien wie z.B. Polypropylen eindringen, und gemeinsam mit Farbstoffen wieder nach außen migrieren. Gegenüber der Nachbehandlung mit Hydrosulfit und NaOH bestehen auch ökologische Vorteile, da weder Hydrosulfit noch NaOH ins Abwasser gelangen können. Außerdem weisen Formulierungen mit Hydrosulfit / NaOH zwangsläufig einen alkalischen pH-Wert auf, so dass nach der Nachbehandlung wieder neutralisiert werden muss. Die erfindungsgemäß verwendeten Formulierungen sind allenfalls leicht alkalisch, so dass die Neutralisation entfallen kann.The process according to the invention has several advantages over the reductive after-cleaning, in particular in the after-treatment of textile materials containing polypropylene: The excess color is removed from the surface of the fabric without significantly worsening the color depth of the dyeing. So it only works on the surface and does not penetrate into the interior of the fiber material. This is not only an advantage over the reductive process, but also over the post-cleaning with surfactants. Since these are low molecular weight surfactants can be incorporated into the interior of polymeric materials such as e.g. Polypropylene penetrate, and migrate together with dyes back out. Compared to the aftertreatment with hydrosulfite and NaOH, there are also ecological advantages, since neither hydrosulfite nor NaOH can reach the wastewater. In addition, formulations with hydrosulfite / NaOH inevitably have an alkaline pH, so that must be neutralized again after the aftertreatment. The formulations used according to the invention are at most slightly alkaline, so that the neutralization can be dispensed with.
Die folgenden Beispiele sollen die Erfindung näher illustrieren:
- Eingesetzte textile Materialien:
- Für die Tests wurden Testgewebe aus handelsüblichem PET sowie additiviertem Polypropylen eingesetzt.
- Applied textile materials:
- For the tests, test fabrics made of commercially available PET and additized polypropylene were used.
Das Gewebe aus additiviertem Polypropylen wurde gemäß dem von
Das textilen Flächengebilde aus PET und Polypropylen wurden vor den Färbeversuchen zur mit einem handelsüblichen Industriewaschmittel gewaschen.The textile fabric of PET and polypropylene were washed before the dyeing tests with a commercial industrial detergent.
Die Färbung wurde nach dem Fachmann prinzipiell bekannten Methoden in einem A-HIBA®-Färbeapparat vorgenommen.The staining was carried out by methods known to the person skilled in the art in an A-HIBA® staining apparatus.
Der jeweils verwendete Farbstoff wurde eingewogen, Wasser zugegeben und die Bombe ca. 20 min im 60°C heißem Wasserbad erhitzt bis der Farbstoff gelöst war.The dye used was weighed in, water was added and the bomb was heated for about 20 minutes in a 60 ° C hot water bath until the dye was dissolved.
Nach Abkühlen auf ca. 40°C wurden die übrigen Zusätze für das Färbebad zugegeben (4,8 g einer 5%-igen Lösung eines handelsüblichen Netzmittels (Basojet® XP) in Wasser, 75 g einer 1 %-igen Lösung eines UV-Stabilisators in Wasser (Cibafast® PEX)) und der pH-Wert der Färbeflotte mit einer Pufferlösung (21ml/l Eisessig und 30g/l Naacetat) auf 4,5 eingestellt. Gesamtmenge der Formulierung jeweils 200 ml.After cooling to about 40 ° C, the remaining additives for the dyebath were added (4.8 g of a 5% solution of a commercial wetting agent (Basojet ® XP) in water, 75 g of a 1% solution of a UV stabilizer in water (Cibafast® PEX)) and the pH of the dyeing liquor with a buffer solution (21 ml / l glacial acetic acid and 30 g / l Naacetat) to 4.5. Total amount of formulation 200 ml each.
Zur der Färbeflotte wurde jeweils 10 g der Textilprobe gegeben, die Bombe verschlossen und im Farbeapparat befestigt. Es wurde das folgende Temperaturprofil verwendet:
- 1. Schnell auf 130°C
- 2. 30 Minuten bei 130°C halten.
- 3. Von 130°C auf 70°C in 24 Minuten = 2,5°C/min
- 1. Fast to 130 ° C
- 2. Hold for 30 minutes at 130 ° C.
- 3. From 130 ° C to 70 ° C in 24 minutes = 2.5 ° C / min
Nach der Färbung wurde das Textil entnommen mit heißem Wasser gut durchgespült und mit kaltem Wasser nachgespült. Danach wurde es geschleudert und im Trockenschrank bei 60°C Umluft getrocknet.After dyeing, the textile was removed well rinsed with hot water and rinsed with cold water. Then it was spun and dried in a drying oven at 60 ° C circulating air.
Die Polyester- und Polypropylen-Textilien wurden jeweils mit handelsüblichen Farbstoffen eingefärbt, und zwar einem schwarzen Dispersionsfarbstoff (Panacron® Black AM-B, 3 Gew. % in Färbeflotte), einem roten Dispersionsfarbstoff (Dianix® Deep Red SF, 2 Gew. % in Färbeflotte) und einem gelben Dispersionsfarbstoff (Dianix® Flavine, 1 Gew. % in Färbeflotte).The polyester and polypropylene fabrics were each stained with commercially available dyes, namely a black disperse dye (Panacron® Black AM-B, 3 wt.% In dye liquor), a red disperse dye (Dianix ® Deep Red SF, 2 wt.% In dyeing liquor) and a yellow disperse dye (Dianix ® flavins, 1 wt.% in dye liquor).
Wasser wird zunächst ohne Additive auf die gewünschte Temperatur zur Nachbehandlung aufgeheizt. Nach dem Erreichen der Temperatur werden die Additive als Konzentrat in wässriger Lösung zugegeben, so dass sich die gewünschte Konzentration einstellt, und gleichzeitig wird die Textilprobe zugegeben. Die Textilprobe wird für die gewünschte Behandlungszeit in der Formulierung bewegt, danach die Formulierung dekantiert, mit warmem und anschließend mit kaltem Wasser nachgespült.Water is first heated without additives to the desired temperature for after-treatment. After reaching the temperature, the additives are added as a concentrate in aqueous solution so that the desired concentration is established, and at the same time the textile sample is added. The textile sample is agitated for the desired treatment time in the formulation, after which the formulation is decanted, rinsed with warm and then cold water.
Die Textilprobe wird dann in einer Lösung aus 0,5 I Wasser mit 2 ml conc. Essigsäure kurz gespült, abgeschleudert und im Labortrockner 2 min bei 120°C und 700 U/min getrocknet.The textile sample is then in a solution of 0.5 l of water with 2 ml conc. Briefly rinsed acetic acid, centrifuged and dried in the laboratory dryer for 2 min at 120 ° C and 700 rev / min.
Tenside (A):
Propfcopolymer (B):
Additve (C):
Surfactants (A):
Graft copolymer (B):
Additve (C):
Lösung der folgenden Komponenten in Wasser:
Solution of the following components in water:
Lösung der folgenden Komponenten in Wasser:
Solution of the following components in water:
Die jeweils verwendete Formulierung, Temperatur und Dauer der Behandlung sind in der nachfolgenden Tabelle 1 zusammengefasst. Beurteilt wurde jeweils die Farbtiefe der Färbung vor und nach der Nachbehandlung. Die Farbänderung des Materials wird über den Graumaßstab zur Bewertung der Änderung von Farbe (ISO 105-A02: 1993 DIN-EN 20105-A02 1994) ermittelt. Die Änderung der Farbe wird jeweils in Noten 1-5 angegeben (5: geringste Änderung, 1: höchste Änderung).The particular formulation, temperature and duration of the treatment are summarized in Table 1 below. The color depth of the dye before and after the aftertreatment was assessed. The color change of the material is determined via the gray scale for assessing the change of color (ISO 105-A02: 1993 DIN-EN 20105-A02 1994). The change of color is indicated in notes 1-5 (5: lowest change, 1: highest change).
Die Waschechtheit der nachbehandelten Proben wurde mit einem Waschechtheitstest nach DIN ISO 105-C06-A1S ohne Verwendung von Stahlkugeln durchgeführt.The wash fastness of the aftertreated samples was carried out with a wash fastness test according to DIN ISO 105-C06-A1S without using steel balls.
Bei diesem Test wird das nachbehandelte Gewebe bei 40°C gewaschen. Mit dem gefärbten Textil werden weiße Gewebe aus anderen textilen Materialien (Wolle, Baumwolle, Polyamid) gewaschen. Es wird beurteilt, wie stark sich die weißen Gewebe verfärben. Die Bewertung erfolgt nach Graumaßstab zur Bewertung des Anblutens ISO105-A03:1993 DIN EN 20105-A03:1994). Die Farbstärke wird jeweils in Noten 1-5 angegeben (5: geringste Farbaufnahme Fremdgewebe, 1: höchste Farbaufnahme Fremdgewebe).In this test, the aftertreated fabric is washed at 40 ° C. The dyed textile is used to wash white fabrics made of other textile materials (wool, cotton, polyamide). It is judged how strongly the white tissues discolour. The evaluation is carried out according to gray scale for the evaluation of the Anblutens ISO105-A03: 1993 DIN EN 20105-A03: 1994). The color intensity is given in grades 1-5 (5: lowest color pickup foreign tissue, 1: highest color pickup foreign tissue).
Die Ergebnisse sind ebenfalls in Tabelle 1 dargestellt. In einer zweiten Serie von Versuchen wurden die oben beschriebenen Textilien auf Basis von dotierten Polypropylenfasern mit 2 Gew.% eines blauen Dispersionsfarbstoffes (Serilen® Dark Blue RT-LS 200) eingefärbt. Die erhaltenen gefärbten Textilien wurden mit NaHSO3 / NaOH unter verschiedenen Bedingungen sowie mit der erfindungsgemäßen Formulierung nachbehandelt. Die Ergebnisse sind in Tabelle 2 dargestellt
1Farbtiefe nach dem Nachwaschen: 5 beste Benotung (geringe Änderung der Farbtiefe); 1 schlechteste Benotung (starke Änderung der Farbtiefe)
2Farbtiefe nach den Waschechtheitstest: 5 beste Benotung (geringste Farbaufnahme); 1 schlechteste Benotung (starke Farbaufnahme)
1 color depth after washing: 5 best rating (slight change in color depth); 1 worst rating (strong change in color depth)
2 color depth after the wash fastness test: 5 best rating (lowest ink absorption); 1 worst rating (strong color pickup)
Die Bespiele und Vergleichsbeispiele in Tabelle 2 zeigen, dass eine konventionelle Nachbehandlung mit NaHSO3 und NaOH je nach den Bedinungen eine deutliche Entfärbung des eingefärbten Textils aus Polypropylenfasern zur Folge haben kann, und zwar ist die Entfärbung umso höher, je höher die Temperatur, je länger die Zeit und je konzentrierter die NaHSO3 / NaOH- Behandlungslösung. Die Entfärbung ist mit der erfindungsgemäßen Formulierung deutlich schwächer.The Examples and Comparative Examples in Table 2 show that conventional post-treatment with NaHSO 3 and NaOH may cause marked discoloration of the dyed polypropylene fabric, depending on the conditions, and the higher the temperature, the longer the decolorization the time and the more concentrated the NaHSO 3 / NaOH treatment solution. The decolorization is significantly weaker with the formulation according to the invention.
In Tabelle 1 sind Versuche Beispiele und Vergleichbeispiele mit drei anderen Farbstoffen sowie Textilien sowohl aus Polypropylen- wie aus PET-Fasern zusammengestellt. Die Nachbehandlung erfolgte jeweils unter gleichen Bedingungen entweder mit NaHSO3 / NaOH oder der erfindungsgemäß zu verwendenden Formulierung. Die Versuche zeigen, dass die Entfärbung der Polypropylentextilien bei Nachbehandlung mit der erfindungsgemäßen Formulierung jeweils geringer ist, als bei der Nachbehandlung mit NaHSO3 / NaOH. Dennoch färben die erfindungsgemäß nachbehandelten Polypropylentextilien beim Waschechtheitstest nicht stärker ab.Table 1 shows examples and comparative examples with three other dyes as well as textiles made of both polypropylene and PET fibers. The aftertreatment was carried out under the same conditions either with NaHSO 3 / NaOH or the formulation to be used according to the invention. The tests show that the decolorization of the polypropylene textiles in the case of after-treatment with the formulation according to the invention is lower in each case than in the after-treatment with NaHSO 3 / NaOH. Nevertheless, the inventively post-treated polypropylene textiles do not stain more strongly in the wash fastness test.
Claims (15)
- A process for aftertreatment of dyed and/or printed textile materials comprising polyester and/or polypropylene fibers comprising treating said materials with an aqueous formulation of at least one anionic and/or nonionic surfactant (A) at a temperature of 20 to 100°C, wherein the aqueous solution further comprises at least one graft copolymer (B), said graft copolymer (B) comprising a straight-chain or branched, hydrophilic main chain comprising nitrogen and/or oxygen atoms and also side chains grafted thereon, and said graft copolymer (B) comprising at least one selected from the group consisting of(B1) graft copolymers having a main chain consisting essentially of alkylene oxide units and also side chains consisting essentially of ethylenically unsaturated monomers, the main chain having a number average molecular weight Mn of 300 to 60 000 g/mol, and the main chain consisting of ethylene oxide units to an extent of at least 90 mol%, based on the amount of all alkylene oxide units, and the side chains comprising at least 50 mol% of vinyl acetate units, based on the amount of all monomers of the side chains, and(B2) graft copolymers having a main chain consisting essentially of alkyleneimine units and also side chains consisting essentially of polyether units, the main chain having a number average molecular weight Mn of 300 to 10 000 g/mol and the main chain consisting of ethyleneimine units to an extent of at least 90 mol%, based on the amount of all alkyleneimine units, and the side chains comprising polyalkylene oxide groups, the proportion of ethylene oxide and/or of propylene oxide units being at least 90 mol% with regard to the amount of all alkylene oxide units.
- The process according to claim 1 wherein the aqueous formulation comprises at least one nonionic surfactant (A1) of the general formula R1-O-(CH2-CH(R2)-O)n-H (I), where the radicals and indices in the formula (I) have the following meanings:n isa number from 3 to 25,R1 is an aliphatic and/or aromatic, straight-chain or branched hydrocarbyl radical having 8 to 20 carbon atoms,R2 in each occurrence is independently hydrogen or an alkyl radical having 1 to 6 carbon atoms, with the proviso that at least 60% of the R2 radicals, based on the total number of R2 radicals, comprise hydrogen.
- The process according to claim 1 or 2 wherein the aqueous formulation comprises at least one low-sudsing, nonionic surfactant (A2) of the general formula R1-O-(CH2-CH(R3)-O)m-R4 (II), where the radicals and indices in the formula (II) have the following meanings:m is a number from 3 to 30,R3 is hydrogen or an alkyl radical having 1 to 6 carbon atoms, with the proviso that at least 60% of the R3 radicals, based on the total number of R2 radicals, comprise hydrogen,R4 is a radical selected from the group consisting of• straight-chain or branched alkyl radicals having 1 to 20 carbon atoms,• groups of the formula -CO-R6, where R6 comprises a straight-chain or branched alkyl radical having 1 to 20 carbon atoms,• groups of the formula -(CH2-CH(R5)-O)z-H, where z is a number from 1 to 15 and R5 hydrogen or an alkyl radical having 1 to 6 carbon atoms, with the proviso that at least 60% of the R5 groups, based on the total number of all R5 groups, comprise an alkyl radical having 1 to 6 carbon atoms.
- The process according to any one of claims 1 to 3 wherein the aqueous formulation comprises at least one foam suppressant (C1).
- The process according to claim 4 wherein the foam suppressant (C1) comprises polypropylene glycol or a polypropylene glycol derivative.
- The process according to any one of claims 1 to 5 wherein the concentration of said surfactants (A) in the formulation is 0.01 g/l to 5 g/l.
- The process according to any one of claims 1 to 6 wherein the concentration of said graft copolymers (B) in the formulation is 0.5 g/l to 10 g/l.
- The process according to any one of claims 1 to 7 wherein the weight ratio of graft copolymers (B) to surfactants (A) is in the range from 1:1 to 20:1.
- The process according to any one of claims 2 to 8 wherein the formulation comprises at least one surfactant (A1) and at least one low-sudsing surfactant (A2) in a weight ratio of at least 1:1 for low-sudsing surfactants (A2) to total amount of all surfactants.
- The process according to any one of claims 1 to 9 wherein the textile materials comprise polypropylene fibers.
- The process according to any one of claims 1 to 10 wherein the textile materials consist of polypropylene fibers.
- The process according to claim 10 or 11 wherein the polypropylene fibers comprise 1% to 15% by weight of at least one polyester as an additive, the stated weight being based on the amount of all components of the polypropylene fiber.
- The process according to claim 12 wherein said additive comprises a polyester having a melting point of 50 to 200°C.
- The process according to claim 12 or 13 wherein the polypropylene fibers comprise 0.1% to 10% by weight of at least one block copolymer as a further additive, the block copolymer comprising at least one apolar block having a number average molar mass Mn of at least 200 g/mol constructed essentially of isobutene units, and at least one polar block having a number average molar mass Mn of at least 500 g/mol, constructed essentially of oxyalkylene units.
- The process according to any one of claims 1 to 14 wherein the aftertreatment is carried out at 30 to 90°C.
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EP09781304A EP2313550B1 (en) | 2008-08-11 | 2009-07-30 | Method for gently aftertreating dyed textiles |
PL09781304T PL2313550T3 (en) | 2008-08-11 | 2009-07-30 | Method for gently aftertreating dyed textiles |
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EP09781304A EP2313550B1 (en) | 2008-08-11 | 2009-07-30 | Method for gently aftertreating dyed textiles |
PCT/EP2009/059893 WO2010018073A1 (en) | 2008-08-11 | 2009-07-30 | Method for gently aftertreating dyed textiles |
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EP (1) | EP2313550B1 (en) |
CN (1) | CN102177291B (en) |
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ES (1) | ES2397071T3 (en) |
MX (1) | MX2011001326A (en) |
MY (1) | MY152745A (en) |
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MX2012000799A (en) | 2009-07-31 | 2012-02-28 | Basf Se | Method for producing spinnable and dyeable polyester fibers. |
DE102013113656A1 (en) * | 2013-12-06 | 2015-06-11 | Schill + Seilacher Gmbh | Use of a surfactant composition for the hydrophilic finishing of textile fibers and textile products made therefrom |
GB201600098D0 (en) * | 2016-01-04 | 2016-02-17 | Nikwax Ltd | Ascorbic acid dye clearing process patent |
CN107828533A (en) * | 2017-11-13 | 2018-03-23 | 东莞市古川纺织助剂有限公司 | A kind of fabric disperse dyes cleaning agent |
CN107815898A (en) * | 2017-11-13 | 2018-03-20 | 东莞市古川纺织助剂有限公司 | Reduction cleaner is exempted from a kind of bath of fabric polyester-cotton blend one |
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EP0287514A1 (en) | 1987-04-15 | 1988-10-19 | Ciba-Geigy Ag | Detergent for the after treatment of fiber reactive dyeings, process for its preparation and its use |
DE4105602A1 (en) | 1991-02-22 | 1992-08-27 | Basf Ag | USE OF A MIXTURE OF AT LEAST TWO ALCOXYLATED ALCOHOLS AS A FOAM-ABSORBING SURFACTANT ADDITIVE IN CLEANING AGENTS FOR MAINTENANCE CLEANING PROCESSES |
EP0918089A1 (en) * | 1997-11-24 | 1999-05-26 | The Procter & Gamble Company | Fabric care compositions |
US6447696B1 (en) | 1999-07-30 | 2002-09-10 | Nippon Shokubai Co., Ltd. | Grafted polymer and its production process and use |
DE10017197A1 (en) | 2000-04-07 | 2001-10-11 | Basf Ag | Alcohol alkoxylates as low-foaming or foam-suppressing surfactants |
DE10321396A1 (en) | 2003-05-12 | 2004-12-02 | Basf Ag | Processing aid for textile dyeing and printing comprises a copolymer of at least 2 monoethylenically unsaturated monomers containing at least one nitrogen containing heterocycle |
AU2003294749A1 (en) | 2002-12-03 | 2004-06-23 | Basf Aktiengesellschaft | Use of copolymers as auxiliaries for dyeing and printing textiles |
DE10256618A1 (en) * | 2002-12-03 | 2004-06-17 | Basf Ag | Method for after-cleaning dyed textiles, i.e. to remove unfixed dye, involves using copolymers of at least two mono-unsaturated monomers containing nitrogen heterocycles, e.g. N-vinylpyrrolidone and N-vinylimidazole |
EP1861430B1 (en) | 2005-03-11 | 2011-02-16 | Aquadye Fibers, Inc. | Dyed olefin yarn and textile fabrics using such yarns |
DE102005011608A1 (en) | 2005-03-14 | 2006-09-21 | Basf Ag | Esterified alkyl alkoxylates as low-foaming surfactants |
US20090039543A1 (en) | 2005-05-30 | 2009-02-12 | Basf Aktiengesellschaft | Polymer Composition Comprising Polyolefins And Amphiphilic Block Copolymers And Optionally Other Polymers And/Or Fillers And Method For Dying Compositions Of That Type Or Printing Thereon |
DE102006057221A1 (en) | 2006-12-01 | 2008-06-05 | Basf Se | Process for the preparation of dyed textile materials comprising polypropylene fibers |
CN101855273B (en) | 2007-11-09 | 2013-01-30 | 巴斯夫欧洲公司 | Alkoxylated polyalkanolamines |
JP5586471B2 (en) | 2007-11-09 | 2014-09-10 | ビーエーエスエフ ソシエタス・ヨーロピア | Amphiphilic water-soluble alkoxylated polyalkyleneimines having an inner polyethylene oxide block and an outer polypropylene oxide block |
JP5431349B2 (en) | 2007-11-23 | 2014-03-05 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for alkoxylation of amino group-containing polymer |
ES2569913T3 (en) | 2008-07-07 | 2016-05-13 | Basf Se | Enzyme composition comprising polymeric particles containing enzyme |
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US20110154582A1 (en) | 2011-06-30 |
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