EP0462806A2 - Process and composition for treating fabrics - Google Patents
Process and composition for treating fabrics Download PDFInfo
- Publication number
- EP0462806A2 EP0462806A2 EP19910305515 EP91305515A EP0462806A2 EP 0462806 A2 EP0462806 A2 EP 0462806A2 EP 19910305515 EP19910305515 EP 19910305515 EP 91305515 A EP91305515 A EP 91305515A EP 0462806 A2 EP0462806 A2 EP 0462806A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- fabric
- composition
- weight
- dye
- treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004744 fabric Substances 0.000 title claims abstract description 65
- 239000000203 mixture Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000011282 treatment Methods 0.000 claims abstract description 44
- 125000002091 cationic group Chemical group 0.000 claims abstract description 15
- 238000004900 laundering Methods 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 239000003599 detergent Substances 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 10
- 239000000975 dye Substances 0.000 description 44
- 239000000463 material Substances 0.000 description 17
- 239000004753 textile Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- -1 aliphatic alcohols Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 239000004902 Softening Agent Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- VHDFCBMXCOUFOE-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;2-[1-(4-chlorobenzoyl)-5-methoxy-2-methylindol-3-yl]acetic acid Chemical compound OCC(N)(CO)CO.CC1=C(CC(O)=O)C2=CC(OC)=CC=C2N1C(=O)C1=CC=C(Cl)C=C1 VHDFCBMXCOUFOE-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000007844 bleaching agent Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005008 domestic process Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- STOOUUMSJPLRNI-UHFFFAOYSA-N 5-amino-4-hydroxy-3-[[4-[4-[(4-hydroxyphenyl)diazenyl]phenyl]phenyl]diazenyl]-6-[(4-nitrophenyl)diazenyl]naphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC2=CC(S(O)(=O)=O)=C(N=NC=3C=CC(=CC=3)C=3C=CC(=CC=3)N=NC=3C=CC(O)=CC=3)C(O)=C2C(N)=C1N=NC1=CC=C([N+]([O-])=O)C=C1 STOOUUMSJPLRNI-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 102000013142 Amylases Human genes 0.000 description 1
- 108010065511 Amylases Proteins 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- YDCJAKNVIXFZCN-UHFFFAOYSA-N CCCCCCCCCCCCCCCCCCC=C.CN(C)C(N)N Chemical compound CCCCCCCCCCCCCCCCCCC=C.CN(C)C(N)N YDCJAKNVIXFZCN-UHFFFAOYSA-N 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 102000005575 Cellulases Human genes 0.000 description 1
- 108010084185 Cellulases Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical class OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 1
- 102000035195 Peptidases Human genes 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- YIQKLZYTHXTDDT-UHFFFAOYSA-H Sirius red F3B Chemical compound C1=CC(=CC=C1N=NC2=CC(=C(C=C2)N=NC3=C(C=C4C=C(C=CC4=C3[O-])NC(=O)NC5=CC6=CC(=C(C(=C6C=C5)[O-])N=NC7=C(C=C(C=C7)N=NC8=CC=C(C=C8)S(=O)(=O)[O-])S(=O)(=O)[O-])S(=O)(=O)O)S(=O)(=O)O)S(=O)(=O)[O-])S(=O)(=O)[O-].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+] YIQKLZYTHXTDDT-UHFFFAOYSA-H 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 235000019418 amylase Nutrition 0.000 description 1
- 229940025131 amylases Drugs 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 229940088598 enzyme Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002979 fabric softener Substances 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- HTPJPKXFBLUBPI-UHFFFAOYSA-I pentasodium 5-[[4-[[4-anilino-6-[[8-hydroxy-7-[[4-[(8-hydroxy-3,6-disulfonatonaphthalen-1-yl)diazenyl]-2-methoxy-5-methylphenyl]diazenyl]-3,6-disulfonatonaphthalen-1-yl]amino]-1,3,5-triazin-2-yl]amino]phenyl]diazenyl]-2-hydroxybenzoate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].COc1cc(N=Nc2cc(cc3cc(cc(O)c23)S([O-])(=O)=O)S([O-])(=O)=O)c(C)cc1N=Nc1c(O)c2c(Nc3nc(Nc4ccccc4)nc(Nc4ccc(cc4)N=Nc4ccc(O)c(c4)C([O-])=O)n3)cc(cc2cc1S([O-])(=O)=O)S([O-])(=O)=O HTPJPKXFBLUBPI-UHFFFAOYSA-I 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
Definitions
- This invention relates to a process and composition for treating fabrics to reduce the amount of dye released from coloured fabrics during wet treatments such as washing and rinsing processes.
- Dye fixing agents generally act in one of two ways either (i) as soaping aids to assist in the removal of loosely held dye from the fabric so that the remaining strongly held dye is relatively fast to subsequent wet treatments or (ii) as binding agents which assist in binding the loosely held dye to the fabric and thus improving the fastness of the dye to subsequent wet treatments.
- the present invention is concerned with the second (binding) type of dye fixing agent.
- the present invention seeks to provide a process and a composition which reduce the amount of dye released from coloured fabrics during wet treatments wherein the drawbacks of the art are mitigated to a substantial degree.
- Dye fixing agents when applied as an industrial treatment are generally either exhausted from a heated liquor comprising the fixing agent at specified level, salt to give an optimum ionic strength and pH adjusters to maintain the pH at low level or padded through the fabric using the heated liquor previously described. It is generally believed that liquor temperatures above 40°C are necessary to effect treatment. Thus in Sandoz technical literature on INDOSOL E-50 Liquid (27.02.84 Ref 6008.35.84), a cationic dye fixing agent, the treatment liquor is heated for 20-30 minutes at temperatures between 50 and 60°C to effect exhaustion.
- dye fixing agents may be exhausted onto fabrics as part of a domestic treatment process at temperatures below 40°C at generally lower levels than used industrially and that such a process may reduce the amount of dye released from coloured fabrics during wet treatments such as domestic laundering.
- the invention provides a process for the domestic treatment of a fabric to reduce the amount of dye released from the fabric during wet treatments comprising the steps of contacting the fabric with a solution of a composition comprising a cationic dye fixing agent wherein the temperature of the solution is below 40°C throughout the process.
- the process may be carried out as part of a domestic laundering process i.e. as part of the wash step or as part of the rinse step, or as a separate treatment.
- detergent active materials when added to the composition of the invention may enhance the effect of the dye fixing agent so that a substantial reduction in the amount of dye released from treated fabrics in subsequent wet treatments is seen. This is unexpected since the industrial literature teaches that a certain ionic strength in the treatment solution is needed to prevent excessive dye release. Thus it is particularly advantageous to incorporate the dye fixing agent in a nonionic based detergent powder or liquid which can then be used in the process of the invention.
- the present invention provides a composition comprising:
- the dye fixing agents suitable for use in the process of the invention are cationic species for example Indosol E-50, an aliphatic polyamine, ex Sandoz and Croscolor NOFF a dimethyldiallyl ammonium chloride polymer of molecular weight in the range 2,000 to 20,000 ex Crosfield.
- Other cationic dye fixing agents are described in "Aftertreatments for Improving the Fastness of Dyes on Textile Fibres" by Christopher C Cook (REV. PROG. COLORATION VOL 12 1982).
- Dye fixing agents suitable for use in the present invention are ammonium compounds such as fatty acid - diamine condensates e.g.
- the amount of dye fixing agent to be employed in the composition of the invention is preferably from 0.01% to 50% by weight of the composition, more preferably from 1% to 25% by weight, most preferably from 5% to 20% by weight.
- the process of the invention is particularly convenient when carried out as part of the rinse step of the laundering process, the temperature of the rinse water generally being between 5°C and 25°C, the dye fixing agent being part of a composition comprising ingredients normally associated with rinse conditioners.
- compositions according to the invention contain one or more detergent active materials, selected from soaps, non-soap anionic, nonionic, zwitterionic and amphoteric synthetic detergent active materials, cationic, nonionic, zwitterionic and amphoteric fabric softening materials and optionally one or more fabric softening materials.
- detergent active materials selected from soaps, non-soap anionic, nonionic, zwitterionic and amphoteric synthetic detergent active materials, cationic, nonionic, zwitterionic and amphoteric fabric softening materials and optionally one or more fabric softening materials.
- Nonionic materials are especially useful in the context of the present invention.
- Suitable nonionic compounds which may be used include in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.
- Specific nonionic detergent compounds are alkyl (C6-C22) phenols-ethylene oxide condensates, generally up to 25 EO, i.e. up to 25 units of ethylene oxide per molecule, the condensation products of aliphatic (C8-C18) primary or secondary linear or branched alcohols with ethylene oxide, generally up to 40 EO, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine.
- Other so-called nonionic detergent compounds include alkyl polyglycosides, long tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides.
- Amounts of amphoteric or zwitterionic detergent compounds can also be used in the compositions of the invention but this is not normally desired due to their relatively high cost. If any amphoteric or zwitterionic detergent compounds are used it is generally in small amounts.
- Suitable fabric softening compounds may for instance be selected from cationic fabric softening materials, nonionic fabric softening materials.
- Suitable materials include substantially water-insoluble quaternary ammonium compounds such as for instance disclosed in EP 89200545.5 and EP 239 910, amine materials, amphoteric fabric conditioning materials as disclosed in EP 89200545.5, clays, polysiloxanes as disclosed in EP 150 867 (Procter and Gamble Co.) and nonionic cellulose ethers as disclosed in EP 213 730 (Unilever).
- the effective amount of the detergent active or fabric softening compound or compounds used in the composition of the present invention is generally in the range of up to 50%, preferably up to 40% by weight, most preferably not more than 30% by weight of the composition.
- the level is between 1% and 50%, more preferably between 2% and 30%.
- Detergency compositions of the invention may include detergency builder to improve the efficiency of the detergent active, in particular to remove calcium hardness ions from the water and to provide alkalinity.
- the builder material may be selected from inorganic precipitating builders materials (such as alkali metal carbonates, bicarbonates, borates, orthophosphates and silicates), sequestering builder materials (such as alkali metal pyrophosphates, polyphosphates, amino polyacetates, phytates, polyphosphonates, aminopolymethylene phosphonates and polycarboxylates), ion-exchange builder materials (such as zeolites and amorphous alumino-silicates), organic precipitating builder materials (such as those having the formula (I): wherein: R1 is C10-C24 alkyl or alkenyl, or an arylalkyl or alkylaryl group of equivalent chain length; X is CH, CR2, N or CON; R2 is C1
- builder materials include sodium tripolyphosphate, mixtures thereof with sodium orthophosphate, sodium carbonate, mixtures thereof with calcite as a seed crystal, sodium citrate, zeolite and the sodium salt of nitrili- triacetic acid.
- the level of such builder material in the compositions of the invention may be up to 80% by weight, preferably from 20% to 70% by weight and most preferably from 30% to 60% by weight.
- Detergent compositions according to the invention preferably are alkaline, in that they yield a pH of more than 8.0 when added to water at a concentration of 1% by weight at 25°C.
- a detergent composition of the invention can contain any of the conventional additives in the amount in which such additives are normally employed in fabric washing detergent compositions.
- these additives include additional fabric softening agents.
- the fabric softening agent is a mixture of organic precipitating builder and either a cationic fabric softening agent or a fatty amine.
- lather boosters such as alkanolamides, particularly the monoethanolamides derivatives from palm kernel fatty acids and coconut fatty acids, lather depressants, oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate, peracid bleach precursors, chlorine-releasing bleaching agents such as tricloroisocyanuric acid, inorganic salts such as sodium sulphate, and, usually present in very minor amounts, fluorescent agents, perfumes including deodorant perfumes, enzymes such as cellulases, proteases and amylases, germicides and colourants.
- lather boosters such as alkanolamides, particularly the monoethanolamides derivatives from palm kernel fatty acids and coconut fatty acids
- lather depressants oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate, peracid bleach precursors, chlorine-releasing bleaching agents such as tricloroisocyanuric acid, inorganic salts such as sodium sulphate, and, usually present in very minor amounts, fluorescent
- compositions may be in any convenient form such as bars, powders, pastes or liquids which may be aqueous or non-aqueous and structured or unstructured.
- the detergent compositions may be prepared in any way appropriate to their physical form such as by dry-mixing the components, co-agglomerating them or dispersing them in a liquid carrier.
- the fabric softening agent may be incorporated as such or it may be incorporated in the form of particles.
- the dye fixing agent may be incorporated in liquid or solid form.
- compositions of the present invention which are specifically suitable for use in the rinse preferably comprise from 1 to 70% of a fabric softening compound.
- compositions of the present invention are preferably liquid and comprise an aqueous base, which may constitute from 5 to 97% by weight of the composition.
- the pH of fabric softening compositions for use in the rinse is preferably less than 8.0 when added to water at a concentration of 1% by weight of the composition.
- Dye fixing agents Indosol E-50 ex Sandox and Croscolor NOFF ex Crosfields Textile Chemicals were separately applied to cloths dyed (and unfixed) with a range of dyes. The application took place from a range of solutions at 20°C and 40°C and in each case both coloured and white cloths were present to assess the dye transfer taking place during the treatment process. Colour changes were measured as CIELAB ⁇ E values for DG5 illumination and 10° observer.
- the treated coloured cloths and treated white monitors were washed together in a detergent composition at 40°C for 15 minutes with clean white monitors.
- a control experiment was also carried out using untreated coloured cloths and clean monitors.
- the detergent composition in parts by weight was as follows:
- the results of ⁇ E measurements on the white monitors treated (Cloths 2, 4 and 6 from example 1) and untreated are as follows:
- Liquid fabric treatment compositions according to the invention suitable for use in the rinse cycle of a domestic washing machine are as follows:
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Coloring (AREA)
- Detergent Compositions (AREA)
Abstract
Description
- This invention relates to a process and composition for treating fabrics to reduce the amount of dye released from coloured fabrics during wet treatments such as washing and rinsing processes.
- In the field of industrial textile aftertreatment it is known to treat dyed or printed fabrics with dye "fixing" agents. Dye fixing agents generally act in one of two ways either (i) as soaping aids to assist in the removal of loosely held dye from the fabric so that the remaining strongly held dye is relatively fast to subsequent wet treatments or (ii) as binding agents which assist in binding the loosely held dye to the fabric and thus improving the fastness of the dye to subsequent wet treatments.
- The present invention is concerned with the second (binding) type of dye fixing agent.
- Under domestic conditions when mixed coloured fabrics and mixed loads of coloured and white fabrics are subjected to wet treatments such as the washing and rinsing steps of a laundering process there is a risk of dye transfer through the treatment liquor from one fabric to another, sometimes in spite of the fact that an industrial aftertreatment may have been applied. The dye transfer can result in the bleeding and fading of colours, discoloration and/or staining of the fabrics and is clearly undesirable. With fashion moving towards more coloured clothing and textile materials, especially multi-coloureds, the problem of dye transfer during wet treatments has become more acute.
- Various proposals have been made in the art to resolve this problem, but in the main these solutions rely on bleaching or rendering ineffective the dye once it has entered the wash or rinse solution. For example GB 1 368 400 (Procter & Gamble) EP 0 024 368 (Unilever) and EP 0 265 257 (Unilever).
- The present invention seeks to provide a process and a composition which reduce the amount of dye released from coloured fabrics during wet treatments wherein the drawbacks of the art are mitigated to a substantial degree.
- Dye fixing agents when applied as an industrial treatment are generally either exhausted from a heated liquor comprising the fixing agent at specified level, salt to give an optimum ionic strength and pH adjusters to maintain the pH at low level or padded through the fabric using the heated liquor previously described. It is generally believed that liquor temperatures above 40°C are necessary to effect treatment. Thus in Sandoz technical literature on INDOSOL E-50 Liquid (27.02.84 Ref 6008.35.84), a cationic dye fixing agent, the treatment liquor is heated for 20-30 minutes at temperatures between 50 and 60°C to effect exhaustion.
- Similarly in Crosfield Textile Chemicals literature on CROSCOLOR PMF (July 1981 Code No 7894) and CROSCOLOR NOFF (January 1988 Code No. 8544), both cationic dye fixing agents, exhaustion temperatures of 50°C for 20 minutes and 40°C for 20-25 minutes respectively are disclosed. It follows then that there is a prejudice in the industrial after-treatment field to process temperatures below 40°C.
- It is also generally believed that a high dye fixing agent concentration in the liquor is necessary to effect exhaustion. In Crosfield Textile Chemicals literature on CROSCOLOR PMF 10% on weight of goods is suggested.
- It has now surprisingly been found that dye fixing agents may be exhausted onto fabrics as part of a domestic treatment process at temperatures below 40°C at generally lower levels than used industrially and that such a process may reduce the amount of dye released from coloured fabrics during wet treatments such as domestic laundering.
- Accordingly, the invention provides a process for the domestic treatment of a fabric to reduce the amount of dye released from the fabric during wet treatments comprising the steps of contacting the fabric with a solution of a composition comprising a cationic dye fixing agent wherein the temperature of the solution is below 40°C throughout the process.
- The fact that a dye fixing effect is seen from a domestic process using dye fixing agents normally associated with industrial processes is truly surprising since in a domestic process pH, ionic strength and water hardness are not easily controlled.
- The process may be carried out as part of a domestic laundering process i.e. as part of the wash step or as part of the rinse step, or as a separate treatment.
- It has been found that detergent active materials when added to the composition of the invention may enhance the effect of the dye fixing agent so that a substantial reduction in the amount of dye released from treated fabrics in subsequent wet treatments is seen. This is unexpected since the industrial literature teaches that a certain ionic strength in the treatment solution is needed to prevent excessive dye release. Thus it is particularly advantageous to incorporate the dye fixing agent in a nonionic based detergent powder or liquid which can then be used in the process of the invention.
-
- i. a cationic dye fixing agent
- ii. a detergent active, preferably nonionic and optionally
- iii. a fabric softening compound.
- The dye fixing agents suitable for use in the process of the invention are cationic species for example Indosol E-50, an aliphatic polyamine, ex Sandoz and Croscolor NOFF a dimethyldiallyl ammonium chloride polymer of molecular weight in the range 2,000 to 20,000 ex Crosfield. Other cationic dye fixing agents are described in "Aftertreatments for Improving the Fastness of Dyes on Textile Fibres" by Christopher C Cook (REV. PROG. COLORATION VOL 12 1982). Dye fixing agents suitable for use in the present invention are ammonium compounds such as fatty acid - diamine condensates e.g. the hydrochloride, acetate, methosulphate and benzyl hydrochloride of oleyldiethyl aminoethylamide, oleylmethyl- diethylenediaminemethsulphate, monostearyl-ethylene diaminotrimethylammonium methosulphate and oxidised products of tertiary amines; derivatives of polymeric alkyldiamines, polyamine-cyanuric chloride condensates and aminated glycerol dichlorohydrins.
- The amount of dye fixing agent to be employed in the composition of the invention is preferably from 0.01% to 50% by weight of the composition, more preferably from 1% to 25% by weight, most preferably from 5% to 20% by weight.
- It has been found that the process of the invention is particularly convenient when carried out as part of the rinse step of the laundering process, the temperature of the rinse water generally being between 5°C and 25°C, the dye fixing agent being part of a composition comprising ingredients normally associated with rinse conditioners.
- The compositions according to the invention contain one or more detergent active materials, selected from soaps, non-soap anionic, nonionic, zwitterionic and amphoteric synthetic detergent active materials, cationic, nonionic, zwitterionic and amphoteric fabric softening materials and optionally one or more fabric softening materials. Nonionic materials are especially useful in the context of the present invention.
- Many suitable detergent compounds are commercially available and are fully described in the literature, for example in "Surface Active Agents and Detergents", Volumes I and II, by Shwartz, Perry and Berch.
- Suitable nonionic compounds which may be used include in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic detergent compounds are alkyl (C₆-C₂₂) phenols-ethylene oxide condensates, generally up to 25 EO, i.e. up to 25 units of ethylene oxide per molecule, the condensation products of aliphatic (C₈-C₁₈) primary or secondary linear or branched alcohols with ethylene oxide, generally up to 40 EO, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine. Other so-called nonionic detergent compounds include alkyl polyglycosides, long tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides.
- Amounts of amphoteric or zwitterionic detergent compounds can also be used in the compositions of the invention but this is not normally desired due to their relatively high cost. If any amphoteric or zwitterionic detergent compounds are used it is generally in small amounts.
- Suitable fabric softening compounds may for instance be selected from cationic fabric softening materials, nonionic fabric softening materials. Suitable materials include substantially water-insoluble quaternary ammonium compounds such as for instance disclosed in EP 89200545.5 and EP 239 910, amine materials, amphoteric fabric conditioning materials as disclosed in EP 89200545.5, clays, polysiloxanes as disclosed in EP 150 867 (Procter and Gamble Co.) and nonionic cellulose ethers as disclosed in EP 213 730 (Unilever).
- The effective amount of the detergent active or fabric softening compound or compounds used in the composition of the present invention is generally in the range of up to 50%, preferably up to 40% by weight, most preferably not more than 30% by weight of the composition. Preferably the level is between 1% and 50%, more preferably between 2% and 30%.
- Detergency compositions of the invention may include detergency builder to improve the efficiency of the detergent active, in particular to remove calcium hardness ions from the water and to provide alkalinity. The builder material may be selected from inorganic precipitating builders materials (such as alkali metal carbonates, bicarbonates, borates, orthophosphates and silicates), sequestering builder materials (such as alkali metal pyrophosphates, polyphosphates, amino polyacetates, phytates, polyphosphonates, aminopolymethylene phosphonates and polycarboxylates), ion-exchange builder materials (such as zeolites and amorphous alumino-silicates), organic precipitating builder materials (such as those having the formula (I):
wherein: R₁ is C₁₀-C₂₄ alkyl or alkenyl, or an arylalkyl or alkylaryl group of equivalent chain length; X is CH, CR₂, N or CON; R₂ is C₁-C₃ alkyl; Z is COOY or SO₃Y; Y is hydrogen or a solubilising cation, preferably alkali metal and especially sodium; and n and m, which may be the same or different, are O or integers from 1 to 4, or mixtures of any one or more of these materials. Preferred examples of builder materials include sodium tripolyphosphate, mixtures thereof with sodium orthophosphate, sodium carbonate, mixtures thereof with calcite as a seed crystal, sodium citrate, zeolite and the sodium salt of nitrili- triacetic acid. - The level of such builder material in the compositions of the invention may be up to 80% by weight, preferably from 20% to 70% by weight and most preferably from 30% to 60% by weight.
- Detergent compositions according to the invention preferably are alkaline, in that they yield a pH of more than 8.0 when added to water at a concentration of 1% by weight at 25°C.
- Apart from the components already mentioned, a detergent composition of the invention can contain any of the conventional additives in the amount in which such additives are normally employed in fabric washing detergent compositions. Examples of these additives include additional fabric softening agents. We have found particularly beneficial effects when the fabric softening agent is a mixture of organic precipitating builder and either a cationic fabric softening agent or a fatty amine. Other optional additives include the lather boosters such as alkanolamides, particularly the monoethanolamides derivatives from palm kernel fatty acids and coconut fatty acids, lather depressants, oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate, peracid bleach precursors, chlorine-releasing bleaching agents such as tricloroisocyanuric acid, inorganic salts such as sodium sulphate, and, usually present in very minor amounts, fluorescent agents, perfumes including deodorant perfumes, enzymes such as cellulases, proteases and amylases, germicides and colourants.
- The compositions may be in any convenient form such as bars, powders, pastes or liquids which may be aqueous or non-aqueous and structured or unstructured.
- The detergent compositions may be prepared in any way appropriate to their physical form such as by dry-mixing the components, co-agglomerating them or dispersing them in a liquid carrier. The fabric softening agent may be incorporated as such or it may be incorporated in the form of particles. The dye fixing agent may be incorporated in liquid or solid form.
- Compositions of the present invention which are specifically suitable for use in the rinse preferably comprise from 1 to 70% of a fabric softening compound.
- For use in the rinse cycle of the fabric laundry process, compositions of the present invention are preferably liquid and comprise an aqueous base, which may constitute from 5 to 97% by weight of the composition.
- The pH of fabric softening compositions for use in the rinse is preferably less than 8.0 when added to water at a concentration of 1% by weight of the composition.
- The invention will now be illustrated in the following non-limiting examples.
- Dye fixing agents Indosol E-50 ex Sandox and Croscolor NOFF ex Crosfields Textile Chemicals were separately applied to cloths dyed (and unfixed) with a range of dyes. The application took place from a range of solutions at 20°C and 40°C and in each case both coloured and white cloths were present to assess the dye transfer taking place during the treatment process. Colour changes were measured as CIELAB Δ E values for DG5 illumination and 10° observer.
- The treatments were as follows.
- A. The cloths were immersed in a solution of 0.05% by weight of fixing agent and a 0.25% by weight dispersion of Arquad 2HT a fabric softener at 20°C for 15 minutes.
- B. The cloths were immersed in the solution of A above at 40°C for 15 minutes.
- C. The cloths were immersed in a solution of 0.05% by weight of fixing agent and 0.05g/l of Synperonic A7 ex ICI, a nonionic detergent active at 20°C for 15 minutes.
- D. The cloths were immersed in the solution of C at 40°C for 15 minutes.
- The cloths used in Examples 1 and 2 were as follows:
- Cloth 1
- Cloth dyed with Direct Green 26
- Cloth 2
- White monitor treated along with Direct Green Cloth
- Cloth 3
- Cloth dyed with Direct Blue 25
- Cloth 4
- White Monitor treated along with Direct Blue cloth
- Cloth 5
- Cloth Dyed with Direct Red 80
- Cloth 6
- White Monitor treated along with Direct Red cloth
- The results are presented in Table 1.
- These results show that generally less dye transfer takes place during the process of the invention when the temperature of the solution is below 40°C. For example the Δ E values for treatment A are generally lower than those for treatment B (which is at the higher temperature) indicating that less dye transfer has taken place. This is also true for treatment C compared with treatment D at the higher temperature.
- The treated coloured cloths and treated white monitors were washed together in a detergent composition at 40°C for 15 minutes with clean white monitors. A control experiment was also carried out using untreated coloured cloths and clean monitors.
-
- These results show that the process of the invention reduces the amount of dye released from coloured fabrics during wet treatments such as washing. This can be seen in any of the Δ E values under treatment A or C where less dye transfer has occurred to cloths washed with dye fixed coloured fabrics than with the control fabrics.
-
-
Claims (10)
- A process for the domestic treatment of a fabric to reduce the amount of dye released from the fabric during wet treatments comprising the steps of contacting the fabric with a solution of a composition comprising a cationic dye fixing agent wherein the temperature of the solution is below 40°C throughout the process.
- A process as claimed in claim 1 wherein the temperature of the solution is between 5°C and 25°C throughout the process.
- A process as claimed in any preceding claim wherein the composition comprises from 0.01 to 50% by weight of the cationic dye fixing agent.
- A process as claimed in any preceding claim wherein the process is carried out as part of the rinse step of a laundering process.
- A composition for the domestic treatment of a fabric to reduce the amount of dye released from the fabric during wet treatments comprising:i. a cationic dye fixing agent andii. a detergent active.
- A composition as claimed in claim 5 wherein the detergent active is a nonionic detergent active.
- A composition as claimed in claim 5 or claim 6 wherein the composition additionally comprises a fabric softening compound.
- A detergent composition for the domestic treatment of a fabric to reduce the amount of dye released from the fabric during wet treatments comprising:i. from 0.01 to 50% by weight of a cationic dye fixing agent andii. from 1 to 50% by weight of a nonionic detergent active.
- A liquid fabric treatment composition for the domestic treatment of a fabric to reduce the amount of dye released from the fabric during wet treatments comprising:i. from 0.01 to 50% by weight of a cationic dye fixing agent;ii. from 1 to 50% by weight of a nonionic detergent active; andiii. from 1 to 50% by weight of a fabric softening compound.
- A liquid fabric treatment composition as claimed in claim 9 wherein the liquid composition comprises an aqueous base.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9013784 | 1990-06-20 | ||
GB909013784A GB9013784D0 (en) | 1990-06-20 | 1990-06-20 | Process and composition for treating fabrics |
Publications (3)
Publication Number | Publication Date |
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EP0462806A2 true EP0462806A2 (en) | 1991-12-27 |
EP0462806A3 EP0462806A3 (en) | 1992-05-27 |
EP0462806B1 EP0462806B1 (en) | 1997-01-29 |
Family
ID=10677937
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP91305515A Revoked EP0462806B1 (en) | 1990-06-20 | 1991-06-18 | Process and composition for treating fabrics |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP0462806B1 (en) |
JP (1) | JP2516490B2 (en) |
AT (1) | ATE148496T1 (en) |
AU (1) | AU637504B2 (en) |
BR (1) | BR9102567A (en) |
DE (1) | DE69124425T2 (en) |
ES (1) | ES2097186T3 (en) |
GB (1) | GB9013784D0 (en) |
ZA (1) | ZA914744B (en) |
Cited By (38)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5259994A (en) * | 1992-08-03 | 1993-11-09 | The Procter & Gamble Company | Particulate laundry detergent compositions with polyvinyl pyrollidone |
US5474690A (en) * | 1994-11-14 | 1995-12-12 | The Procter & Gamble Company | Concentrated biodegradable quaternary ammonium fabric softener compositions containing intermediate iodine value fatty acid chains |
US5545350A (en) * | 1992-05-12 | 1996-08-13 | The Procter & Gamble Company | Concentrated fabric softener compositions containing biodegradable fabric softeners |
EP0779358A2 (en) | 1995-12-16 | 1997-06-18 | Unilever Plc | Detergent composition |
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US5686376A (en) * | 1995-01-12 | 1997-11-11 | The Procter & Gamble Company | Chelating agents for improved color fidelity |
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US5707951A (en) * | 1995-03-03 | 1998-01-13 | The Procter & Gamble Company | Laundry composition containing dye fixatives and cellulase |
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Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0990695A1 (en) | 1998-09-30 | 2000-04-05 | Witco Surfactants GmbH | Fabric softener with dye transfer inhibiting properties |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2271284A2 (en) * | 1974-05-13 | 1975-12-12 | Croquevielle Alain | Washing powder for coloured - contg. amphoteric mixt. of polyglycolic esters and quaternary ammonium derivs. |
GB2059447A (en) * | 1979-09-17 | 1981-04-23 | Sandoz Products Ltd | Improving the Wash Fastness of Wool Dyeings |
JPS5696972A (en) * | 1979-12-28 | 1981-08-05 | Toray Industries | Enhancement of dyeing fastness |
FR2502143A1 (en) * | 1981-03-21 | 1982-09-24 | Kreussler Chem Fab | ACTIVE SUBSTANCE AND PROCESS FOR REDUCING THE TISSUE TERMINATION OF TEXTILE MATERIAL DURING WASHING OR CHEMICAL CLEANING |
GB2117013A (en) * | 1982-03-12 | 1983-10-05 | Sandoz Ltd | Aftertreatment of cationic dyed textiles |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2208970A1 (en) * | 1972-08-23 | 1974-06-28 | Croquevielle Al In | Washing powder for dyed linen - contg. sequestering agents, detergents, bleaches dye fixers and softening agents |
JPS57154481A (en) * | 1981-03-12 | 1982-09-24 | Sanyo Chemical Ind Ltd | Wet fastness increasing agent and method |
DE3413292A1 (en) * | 1984-04-09 | 1985-10-17 | Henkel KGaA, 4000 Düsseldorf | TEXTILE DETERGENT FOR COLORED TEXTILES |
JPS6220307A (en) * | 1985-07-19 | 1987-01-28 | Hitachi Ltd | Heat treatment apparatus |
US4822374A (en) * | 1986-06-17 | 1989-04-18 | Ciba-Geigy Corporation | Process for the aftertreatment of dyed cellulose fibers |
-
1990
- 1990-06-20 GB GB909013784A patent/GB9013784D0/en active Pending
-
1991
- 1991-06-18 AT AT91305515T patent/ATE148496T1/en active
- 1991-06-18 AU AU78461/91A patent/AU637504B2/en not_active Expired
- 1991-06-18 EP EP91305515A patent/EP0462806B1/en not_active Revoked
- 1991-06-18 DE DE69124425T patent/DE69124425T2/en not_active Revoked
- 1991-06-18 ES ES91305515T patent/ES2097186T3/en not_active Expired - Lifetime
- 1991-06-19 BR BR919102567A patent/BR9102567A/en not_active IP Right Cessation
- 1991-06-20 ZA ZA914744A patent/ZA914744B/en unknown
- 1991-06-20 JP JP3148797A patent/JP2516490B2/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2271284A2 (en) * | 1974-05-13 | 1975-12-12 | Croquevielle Alain | Washing powder for coloured - contg. amphoteric mixt. of polyglycolic esters and quaternary ammonium derivs. |
GB2059447A (en) * | 1979-09-17 | 1981-04-23 | Sandoz Products Ltd | Improving the Wash Fastness of Wool Dyeings |
JPS5696972A (en) * | 1979-12-28 | 1981-08-05 | Toray Industries | Enhancement of dyeing fastness |
FR2502143A1 (en) * | 1981-03-21 | 1982-09-24 | Kreussler Chem Fab | ACTIVE SUBSTANCE AND PROCESS FOR REDUCING THE TISSUE TERMINATION OF TEXTILE MATERIAL DURING WASHING OR CHEMICAL CLEANING |
GB2117013A (en) * | 1982-03-12 | 1983-10-05 | Sandoz Ltd | Aftertreatment of cationic dyed textiles |
Non-Patent Citations (1)
Title |
---|
WORLD PATENTS INDEX LATEST Week 8138, Derwent Publications Ltd., London, GB; AN 81-68853D & JP-A-56 096 972 (TORAY IND INC) 5 August 1981 * |
Cited By (59)
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US5767062A (en) * | 1992-11-16 | 1998-06-16 | The Procter & Gamble Company | Fabric softening compositions with dye transfer inhibitors for improved fabric appearance |
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US5789373A (en) * | 1996-01-31 | 1998-08-04 | Baker; Ellen Schmidt | Laundry additive compositions including dispersible polyolefin |
US6107270A (en) * | 1996-03-29 | 2000-08-22 | The Procter & Gamble Company | Dryer-added fabric softener composition to provide color and other fabric benefits in package in association with instructions for use |
WO1997041292A1 (en) * | 1996-05-02 | 1997-11-06 | The Procter & Gamble Company | Cleaning dyed fabrics |
EP0907701B1 (en) * | 1996-06-03 | 2002-12-18 | The Procter & Gamble Company | Fabric softening compositions |
WO1997046654A1 (en) * | 1996-06-03 | 1997-12-11 | The Procter & Gamble Company | Fabric softening compositions |
EP0811679A1 (en) * | 1996-06-03 | 1997-12-10 | The Procter & Gamble Company | Fabric softening compositions |
EP0811680A1 (en) * | 1996-06-03 | 1997-12-10 | The Procter & Gamble Company | Fabric softening compositions |
WO1997046652A1 (en) * | 1996-06-03 | 1997-12-11 | The Procter & Gamble Company | Fabric softening compositions |
US6352968B1 (en) | 1996-07-05 | 2002-03-05 | Lever Brothers Company, Division Of Conopco, Inc. | Detergent compositions |
WO1998012295A1 (en) * | 1996-09-19 | 1998-03-26 | The Procter & Gamble Company | Color care compositions |
WO1998012296A1 (en) * | 1996-09-19 | 1998-03-26 | The Procter & Gamble Company | Color care compositions |
WO1998017758A1 (en) * | 1996-10-18 | 1998-04-30 | The Procter & Gamble Company | Detergent compositions |
US6103685A (en) * | 1996-10-18 | 2000-08-15 | The Procter & Gamble Company | Detergent compositions |
US6465415B2 (en) | 1996-10-21 | 2002-10-15 | Basf Aktiengesellschaft | Use of polycationic condensates as color transfer inhibiting and color release reducing additive to detergents and fabric conditioners |
WO1998020098A1 (en) * | 1996-11-01 | 1998-05-14 | The Procter & Gamble Company | Color care compositions |
WO1998020099A1 (en) * | 1996-11-01 | 1998-05-14 | The Procter & Gamble Company | Color care compositions |
WO1998021301A1 (en) * | 1996-11-11 | 1998-05-22 | Basf Aktiengesellschaft | Use of quaternized polymerizates containing units of vinyl imidazol as a colour fixing and colour transfer inhibiting additive to detergent post-treatment agents and detergents |
US6156722A (en) * | 1996-12-31 | 2000-12-05 | The Procter & Gamble Company | Laundry detergent compositions comprising dye fixatives |
WO1998029529A1 (en) * | 1996-12-31 | 1998-07-09 | The Procter & Gamble Company | Laundry detergent compositions comprising dye fixatives |
GB2323385A (en) * | 1997-03-20 | 1998-09-23 | Procter & Gamble | Detergent compositions |
US6020302A (en) * | 1997-09-18 | 2000-02-01 | The Procter & Gamble Company | Color care compositions |
US6500796B1 (en) | 1997-11-24 | 2002-12-31 | The Procter & Gamble Company | Stabilized fabric softening compositions |
EP0924293A1 (en) * | 1997-11-24 | 1999-06-23 | The Procter & Gamble Company | Use of a crystal growth inhibitor to reduce fabric abrasion |
WO1999027056A1 (en) * | 1997-11-24 | 1999-06-03 | The Procter & Gamble Company | Stabilised fabric softening compositions |
EP0979861A1 (en) * | 1998-08-03 | 2000-02-16 | The Procter & Gamble Company | Fabric care compositions |
WO2000008128A1 (en) * | 1998-08-03 | 2000-02-17 | The Procter & Gamble Company | Fabric care compositions |
US6830593B1 (en) | 1998-08-03 | 2004-12-14 | The Procter & Gamble Company | Fabric care compositions |
WO2001044423A1 (en) * | 1999-12-17 | 2001-06-21 | Unilever Plc | Dye fixing composition |
US6627591B2 (en) | 1999-12-17 | 2003-09-30 | Unilever Home & Personal Care Usa Division Of Conopco, Inc. | Dye fixing composition |
US6573229B2 (en) | 2000-04-12 | 2003-06-03 | Unilever Home & Personal Care Usa Division Of Conopco Inc. | Laundry wash compositions |
US6596684B2 (en) | 2000-04-20 | 2003-07-22 | Unilever Home & Personal Care Usa Divison Of Conopco, Inc. | Granular detergent component and process for its preparation |
US6858570B2 (en) | 2001-03-03 | 2005-02-22 | Clariant Gmbh | Laundry detergents and laundry treatment compositions comprising one or more dye-transfer-inhibiting dye fixatives |
US7091167B2 (en) | 2001-03-03 | 2006-08-15 | Clariant Gmbh | Laundry detergents and laundry treatment compositions comprising dye-transfer-inhibiting dye fixatives |
EP2650353A3 (en) * | 2002-12-23 | 2014-01-15 | Basf Se | Laundry care products containing hydrophobically modified polymers as additives |
EP1645619A1 (en) | 2004-10-05 | 2006-04-12 | Cognis IP Management GmbH | Liquid Detergent Compositions |
EP2762556A4 (en) * | 2011-09-28 | 2016-01-06 | Jilin Hengtai Garment Washing And Dyeing Science And Technology Inst | Color enhancing detergent for colored textile and preparation method therefor |
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US10266981B2 (en) | 2013-03-15 | 2019-04-23 | Whirlpool Corporation | Methods and compositions for treating laundry items |
EP3903771A4 (en) * | 2018-12-27 | 2022-10-05 | Universidad de Santiago de Chile | Material that incorporates vitamin d for the subsequent release thereof and method for obtaining the material |
Also Published As
Publication number | Publication date |
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DE69124425D1 (en) | 1997-03-13 |
ES2097186T3 (en) | 1997-04-01 |
EP0462806A3 (en) | 1992-05-27 |
AU7846191A (en) | 1992-01-02 |
JP2516490B2 (en) | 1996-07-24 |
EP0462806B1 (en) | 1997-01-29 |
ZA914744B (en) | 1993-02-24 |
BR9102567A (en) | 1992-01-21 |
AU637504B2 (en) | 1993-05-27 |
DE69124425T2 (en) | 1997-05-15 |
ATE148496T1 (en) | 1997-02-15 |
JPH04257380A (en) | 1992-09-11 |
GB9013784D0 (en) | 1990-08-08 |
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